WO2011108667A1 - 感放射線性樹脂組成物、レジストパターン形成方法及びスルホニウム化合物 - Google Patents
感放射線性樹脂組成物、レジストパターン形成方法及びスルホニウム化合物 Download PDFInfo
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- WO2011108667A1 WO2011108667A1 PCT/JP2011/054969 JP2011054969W WO2011108667A1 WO 2011108667 A1 WO2011108667 A1 WO 2011108667A1 JP 2011054969 W JP2011054969 W JP 2011054969W WO 2011108667 A1 WO2011108667 A1 WO 2011108667A1
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- 0 *S([N-]S(*)(=O)=O)(=O)=O Chemical compound *S([N-]S(*)(=O)=O)(=O)=O 0.000 description 2
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/039—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
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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
- G03F7/20—Exposure; Apparatus therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
Definitions
- the present invention relates to a radiation-sensitive resin composition, a resist pattern forming method using the same, and a sulfonium compound used therefor.
- a lithography technique capable of microfabrication at a level of 0.10 ⁇ m or less is desired in order to obtain a higher degree of integration.
- near ultraviolet rays such as i-rays are used as radiation, and microfabrication at a level of 0.10 ⁇ m or less (subquarter micron level) is extremely difficult with this near ultraviolet rays. Therefore, in order to enable microfabrication at a level of 0.10 ⁇ m or less, development of a lithography technique using radiation having a shorter wavelength is being performed.
- Examples of radiation having a shorter wavelength include an emission line spectrum of a mercury lamp, far ultraviolet rays such as an excimer laser, an X-ray, and an electron beam.
- far ultraviolet rays such as an excimer laser, an X-ray, and an electron beam.
- KrF excimer laser wavelength 248 nm
- ArF excimer laser wavelength 193 nm
- photoresist films for excimer lasers have been proposed.
- the photoresist material for excimer laser include, for example, a component having an acid-dissociable functional group and a component that generates acid upon irradiation with radiation (hereinafter also referred to as “exposure”) (hereinafter also referred to as “acid generator”).
- exposure a component having an acid-dissociable functional group and a component that generates acid upon irradiation with radiation
- exposure hereinafter also referred to as “acid generator”.
- a composition using these chemical amplification effects hereinafter also referred to as “chemically amplified resist”
- t-butyl ester of carboxylic acid is specifically used.
- a composition containing a resin having a t-butyl carbonate group of a phenol group or a phenol and an acid generator has been reported.
- the t-butyl ester group or t-butyl carbonate group present in the resin is dissociated by the action of an acid generated by exposure so that the resin has an acidic group composed of a carboxyl group or a phenolic hydroxyl group. become.
- the exposed region of the photoresist film becomes readily soluble in an alkali developer, so that a desired resist pattern can be formed.
- a finer resist pattern for example, a fine resist pattern having a line width of about 45 nm.
- NA numerical aperture
- a new exposure apparatus is required for shortening the light source wavelength, but such an apparatus is expensive.
- the numerical aperture of the lens is increased, there is a problem that the depth of focus decreases even if the resolution can be improved because the resolution and the depth of focus are in a trade-off relationship.
- a liquid immersion lithography (liquid immersion lithography) method has been reported as a lithography technique for solving such problems.
- an immersion exposure liquid for example, pure water, a fluorine-based inert liquid, or the like
- the exposure optical path space that has been conventionally filled with an inert gas such as air or nitrogen is filled with an immersion exposure liquid having a refractive index (n) larger than that of air or the like.
- n refractive index
- Patent Document 4 When the sulfonium salt disclosed in Patent Document 4 is used for the radiation-sensitive resin composition, there are disadvantages that the pattern cross-sectional shape after development does not become rectangular or scum is generated. In addition, when the compositions disclosed in Patent Documents 1 to 3 are used for immersion exposure, there is a disadvantage in that defects resulting from undissolved residue during development occur. This defect is a defect that is considered to be caused by aggregation of components in the photoresist film in the developing solution and re-adhesion on the pattern.
- the present invention has been made in view of such disadvantages of the prior art, and the problem is that the resist pattern cross-sectional shape after development is excellent in rectangularity and hardly causes scum, particularly immersion exposure.
- An object of the present invention is to provide a radiation-sensitive resin composition that is less likely to cause development defects even when used in the above.
- the following radiation sensitive resin composition, resist pattern forming method and sulfonium compound are provided.
- a sulfonium compound represented by the following general formula (1) (hereinafter also referred to as “(A) compound”) and (B) a polymer serving as a base resin (hereinafter referred to as “(B) polymer”) A radiation-sensitive resin composition.
- R 1 is an (n 1 +1) valent aromatic hydrocarbon group having 6 to 30 carbon atoms and an (n 1 +1) valent aliphatic chain hydrocarbon having 1 to 10 carbon atoms.
- R 2 is an (n 2 +1) -valent aromatic hydrocarbon group having 6 to 30 carbon atoms
- 1 carbon atom Represents an (n 2 +1) -valent aliphatic chain hydrocarbon group having from 20 to 20, or an (n 2 +1) -valent alicyclic hydrocarbon group having from 3 to 20 carbon atoms, wherein R 3 has 6 to 30 carbon atoms.
- R 1 ⁇ R 3 may form a cyclic structure containing a sulfur cations bonded to each other.
- the hydrogen having the R 1 ⁇ R 3 is a group represented by the following general formula (2). However, if R there is a plurality of mutually independent .n 1 ⁇ n 3 each independently represents an integer of 0 to 5, provided that n 1 + n 2 + n 3 ⁇ 1 and X ⁇ represents an anion.
- R 4 represents an alkali-dissociable group.
- A represents an oxygen atom, —NR 5 — group, —CO—O— * group or —SO 2 —O— * group.
- R 5 represents a hydrogen atom or an alkali dissociable group, and “*” represents a bonding site with R 4.
- R 2 , R 3 , R, n 1 to n 3 and X ⁇ are as defined in the general formula (1), provided that R 2 and R 3 are bonded to each other.
- N 4 represents 0 or 1.
- R 41 represents a hydrocarbon group having 1 to 7 carbon atoms, in which part or all of the hydrogen atoms are substituted with fluorine atoms, provided that it is represented by the general formula (2a). When there are a plurality of Rs, the plurality of R 41 are independent of each other.
- [7] A step of forming a photoresist film on a substrate using the radiation sensitive resin composition according to any one of [1] to [6], and (2) exposing the photoresist film. And a step (3) of developing the exposed photoresist film to form a resist pattern.
- step (2) is a step of performing immersion exposure on the photoresist film.
- R 1 is an (n 1 +1) valent aromatic hydrocarbon group having 6 to 30 carbon atoms, an (n 1 +1) valent aliphatic chain carbonization having 1 to 10 carbon atoms.
- (N 3 +1) -valent aromatic hydrocarbon group, (n 3 +1) -valent aliphatic chain hydrocarbon group having 1 to 30 carbon atoms, or (n 3 +1) -valent fat having 3 to 30 carbon atoms refers to a cyclic hydrocarbon group.
- any two of R 1 ⁇ R 3 may form a cyclic structure containing a sulfur cations bonded to each other.
- R 1 ⁇ R 3 Some or all of the atom, optionally substituted .R is a group represented by the following general formula (2).
- n 1 ⁇ n 3 represents an integer of 0 to 5 independently of each other, provided that n 1 + n 2 + n 3 ⁇ 1 and X ⁇ represents an anion.
- R 4 represents an alkali-dissociable group.
- A represents an oxygen atom, —NR 5 — group, —CO—O— * group or —SO 2 —O— * group.
- R 5 represents a hydrogen atom or an alkali dissociable group, and “*” represents a bonding site with R 4.
- R 2 , R 3 , R, n 1 to n 3 and X ⁇ are as defined in the general formula (1), provided that R 2 and R 3 are bonded to each other.
- N 4 represents 0 or 1.
- R 41 represents a hydrocarbon group having 1 to 7 carbon atoms, in which part or all of the hydrogen atoms are substituted with fluorine atoms, provided that it is represented by the general formula (2a). When there are a plurality of Rs, the plurality of R 41 are independent of each other.
- the radiation-sensitive resin composition of the present invention is excellent in the rectangularity of the resist pattern cross-sectional shape after development, hardly produces scum, and exhibits an effect that development defects are hardly caused even when used for immersion exposure. .
- the resist pattern forming method of the present invention there is an effect that development defects hardly occur and a pattern having a good shape can be efficiently formed.
- the sulfonium compound of the present invention produces a radiation-sensitive resin composition that is excellent in the rectangularity of the cross-sectional shape of the resist pattern after development, hardly generates scum, and in particular, does not easily generate development defects even when used for immersion exposure. There is an effect that it is possible.
- the sulfonium compound of the present invention is a component that acts as an acid generator in the radiation-sensitive resin composition of the present invention described later, that is, a photoresist film formed by the radiation-sensitive resin composition is passed through an immersion exposure liquid.
- This is a component that generates an acid in the exposed area when exposed to light.
- This sulfonium compound is greatly different in that it has an alkali dissociable group as compared with a compound used in a conventional acid generator.
- the alkali dissociable group reacts with an alkali developer to generate a polar group.
- the occurrence of this polar group is considered to suppress aggregation of the sulfonium compound due to the developer and the rinsing liquid, and to make it difficult for defects derived from undissolved components to occur.
- Group represented by the general formula (2) is a group in which a hydroxyl group, an amino group, a carboxyl group, or a sulfoxyl group is modified with an alkali dissociable group.
- the group represented by the general formula (2) reacts with an alkaline aqueous solution as shown in the following reaction formula (3) to generate a polar group -AH.
- R 4 represents an alkali dissociable group.
- alkali dissociable group refers to a group that replaces a hydrogen atom in a polar functional group, and has a basic condition (for example, 2.38 mass% under a temperature condition of 23 ° C. A group that is dissociated by the action of an aqueous tetramethylammonium hydroxide solution.
- Such an alkali dissociable group is not particularly limited as long as it exhibits the above properties.
- a preferred example of the alkali-dissociable group when A is an oxygen atom or a —NR 5 — group includes a group represented by the following general formula (R 4 -1).
- R 41 represents a hydrocarbon group having 1 to 7 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.
- R 41 In the general formula (R 4 -1), preferred examples of R 41 include linear or branched alkyl groups having 1 to 7 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and all of the hydrogen atoms. Alternatively, there are alicyclic hydrocarbon groups having 3 to 7 carbon atoms partially substituted with fluorine atoms, and the like.
- linear or branched alkyl group having 1 to 7 carbon atoms include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2- ( 2-methylpropyl) group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group, 2 -(3-methylbutyl) group, neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4 -Methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- (3 -Methylpentyl) group, 3-
- alicyclic hydrocarbon group having 3 to 7 carbon atoms include a cyclopentyl group, a cyclopentylmethyl group, a 1- (1-cyclopentylethyl) group, a 1- (2-cyclopentylethyl) group, a cyclohexyl group, Examples thereof include a cyclohexylmethyl group, a cycloheptyl group, and a 2-norbornyl group.
- the group represented by R 41 is a linear or branched alkyl group having 1 to 7 carbon atoms, and one of the hydrogen atoms of the carbon atom linked to the carbonyl group is substituted with a fluorine atom, Or, a hydrogen atom of a carbon atom linked to a carbonyl group is not substituted, and a group in which all hydrogen atoms of other carbon atoms are substituted with fluorine atoms is more preferred, and a 2,2,2-trifluoroethyl group is more preferred. Particularly preferred.
- alkali dissociable group when A is a —CO—O— * group are represented by the following general formulas (R 4 -2) to (R 4 -4). There is a group to be.
- m 1 represents an integer of 0 to 5.
- R 6 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or a carbon number.
- m 2 represents an integer of 0 to 4.
- R 7 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a carbon number Represents an acyl group having 2 to 10 carbon atoms, or an acyloxy group having 2 to 10 carbon atoms, provided that when m 2 is 2 or more, a plurality of R 7 are independent of each other.
- R 8 and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, provided that R 8 and R 9 are bonded to each other to form a carbon atom. (An alicyclic structure of several 4 to 20 may be formed.)
- examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Etc. Of these, fluorine atoms are preferred.
- alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, 2- (2-methylpropyl) group, 1 -Pentyl group, 2-pentyl group, 3-pentyl group, 1- (2-methylbutyl) group, 1- (3-methylbutyl) group, 2- (2-methylbutyl) group, 2- (3-methylbutyl) group, Neopentyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1- (2-methylpentyl) group, 1- (3-methylpentyl) group, 1- (4-methylpentyl) group, 2- (2-methylpentyl) group, 2- (3-methylpentyl) group, 2- (4-methylpentyl) group, 3- (2-methylpentyl) group, 3- (3-methylpentyl) group, etc. .
- alkoxyl group having 2 to 10 carbon atoms examples include methoxy group, ethoxy group, n-butoxy group, t-butoxy group, propoxy group, isopropoxy group and the like.
- acyl group having 2 to 10 carbon atoms include acetyl group, ethylcarbonyl group, propylcarbonyl group and the like.
- examples of the acyloxy group having 2 to 10 carbon atoms include an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexane carbonyloxy group, an n-octane carbonyloxy group, etc. There is.
- the alkyl group having 1 to 10 carbon atoms is an alkyl group having 1 to 10 carbon atoms exemplified for R 6 and R 7. The same thing as a group can be illustrated.
- Examples of the alicyclic structure having 4 to 20 carbon atoms formed together with the carbon atoms to which R 8 and R 9 are bonded to each other include cyclopentyl group, cyclopentylmethyl group, 1- (1-cyclopentylethyl) Group, 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, 1- (1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) group, 2-norbornyl group and the like.
- R 4 -4 Specific examples of the group represented by the general formula (R 4 -4) include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, and a 1-pentyl group.
- methyl, ethyl, 1-propyl, 2-propyl, 1-butyl and 2-butyl are preferred.
- the group represented by the general formula (2) can be formed by fluoroacylating a functional group such as a hydroxyl group, an amino group, or a carboxyl group by a conventionally known method. More specifically, (1) esterification is performed by condensing an alcohol and a fluorocarboxylic acid in the presence of an acid, and (2) esterification is performed by condensing the alcohol and a fluorocarboxylic acid halide in the presence of a base. Can be mentioned.
- examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include groups derived from benzene and naphthalene.
- the aliphatic chain hydrocarbon group is derived from a linear or branched alkyl group such as methane, ethane, n-butane, 2-methylpropane, 1-methylpropane, tert-butane, and n-pentane. There are groups to do.
- examples of the alicyclic hydrocarbon group include groups derived from alicyclic hydrocarbons such as cyclobutane, cyclopentane, cyclohexane, cyclooctane, norbornyl group, tricyclodecane, tetracyclododecane, and adamantane.
- the cyclic structure is preferably a 5-membered ring or a 6-membered ring, and a 5-membered ring (that is, a tetrahydrothiophene ring) is Further preferred.
- examples of the substituent that may be substituted for some or all of the hydrogen atoms of R 1 to R 3 include a halogen atom, a linear or branched group having 1 to 10 carbon atoms, and the like.
- Examples of the linear or branched alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a tert-butyl group, and an n-pentyl group. Etc. Among these, a methyl group, an ethyl group, an n-butyl group, and a tert-butyl group are preferable.
- Examples of the linear or branched alkoxyl group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, Examples include tert-butoxy group. Among these, a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group are preferable.
- Examples of the linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and a 2-methylpropoxycarbonyl group. 1-methylpropoxycarbonyl group, tert-butoxycarbonyl group and the like. Among these, a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group are preferable.
- Examples of the linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a tert-butanesulfonyl group, and a cyclopentanesulfonyl group. Group, cyclohexanesulfonyl group and the like.
- a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group are preferable.
- alkoxyalkyl group examples include straight chain or branched chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, etc. And cyclic alkoxyalkyl groups.
- alkoxycarbonyloxy group examples include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n-butoxycarbonyloxy group, tert-butoxycarbonyloxy group, cyclopentyloxycarbonyloxy group, Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as cyclohexyloxycarbonyloxy.
- the sulfonium compound is preferably a compound represented by the general formula (1-1) in which R 1 is a phenyl group or a naphthyl group, and R 1 to R 3 are phenyl groups. More preferred is a compound represented by formula (1-1a).
- a sulfonium compound may be contained individually by 1 type, and may be contained in combination of 2 or more types.
- X ⁇ is an anion.
- the anion include anions represented by the following general formulas (4), (5), (6-1), (6-2) and the like.
- R 10 C p F 2p SO 3 — (4) (In the general formula (4), R 10 represents a hydrogen atom, a fluorine atom or a hydrocarbon group having 1 to 12 carbon atoms. P represents an integer of 1 to 10.)
- R 11 SO 3 - ⁇ (5 ) In the general formula (5), R 11 represents a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 12 carbon atoms.)
- R 12 independently represents a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, provided that two R 12 May combine with each other to form a cyclic structure having 5 to 10 ring members having a fluorine atom
- R 13 is independently of each other a carbon number having a fluorine atom.
- 1 to 10 represents a linear or branched aliphatic hydrocarbon group, provided that any two R 13 may be bonded to each other to form a cyclic structure having 5 to 10 ring members having a fluorine atom. .
- —C p F 2p — is a perfluoroalkylene group having p carbon atoms. This group may be linear or branched. In addition, it is preferable that p is 1, 2, 4 or 8.
- R 10 in the general formula (4) and R 11 in the general formula (5) are hydrocarbon groups having 1 to 12 carbon atoms
- the hydrocarbon group is an unsubstituted hydrocarbon group (that is, an alkyl group).
- the hydrogen atom of the hydrocarbon group is a hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, It may be a hydrocarbon group substituted with at least one of an alkoxycarbonyl group, an alkoxycarbonyloxy group and the like.
- this hydrocarbon group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, norbornyl group, norbornylmethyl. Group, hydroxynorbornyl group, adamantyl group.
- R 12 in the general formula (6-1) and R 13 in the general formula (6-2) are a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom
- Specific examples of the aliphatic hydrocarbon group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a dodecafluoropentyl group, and a perfluorooctyl group.
- two R 12 in the general formula (6-1) and any two R 13 in the general formula (6-2) are bonded to each other to form a divalent group having 5 to 10 ring members having a fluorine atom.
- the divalent group include tetrafluoroethylene group, hexafluoropropylene group, octafluorobutylene group, decafluoropentylene group, undecafluorohexylene group and the like. it can.
- This divalent group may have a substituent.
- X ⁇ include trifluoromethanesulfonate anion, perfluoro-n-butanesulfonate anion, perfluoro-n-octanesulfonate anion, 2-bicyclo [2.2.1] hept-2-yl-1,1 , 2,2-tetrafluoroethanesulfonate anion, 2-bicyclo [2.2.1] hept-2-yl-1,1-difluoroethanesulfonate anion, 1,1-difluoro-2- (1-adamantyl) ethane- 1-sulfonate anion, 6- (1-adamantanecarbonyloxy) -1,1,2,2-tetrafluorohexane-1-sulfonate anion, anions represented by the following formulas (7-1) to (7-7) There is.
- the sulfonium compound represented by the general formula (1) is obtained by, for example, reacting a compound represented by the following formula (1a) with a compound represented by the following formula (1b) or a derivative derived from the compound, A step (A) for obtaining a compound represented by the following formula (1c), a compound represented by the following formula (1c) and a compound represented by the following formula (1d) are reacted to form the above general formula ( It can synthesize
- the derivative of the compound represented by the following formula (1b) include a carboxylic acid ester compound and a carboxylic acid anhydride when the compound represented by the following formula (1b) is a carboxylic acid. be able to.
- R 1 , R 2 , R 3 , and n 1 to n 3 have the same meaning as the general formula (1), and R ′ is represented by the following general formula (2a ′). (However, when a plurality of R ′ are present, each R ′ is mutually independent. Z ⁇ represents a halogen atom.)
- R 4 has the same meaning as in general formula (2).
- M represents an alkali metal
- X has the same meaning as in general formula (1).
- reaction temperature is usually ⁇ 30 to 100 ° C., preferably ⁇ 20 to 90 ° C., particularly preferably ⁇ 10 to 80 ° C .; It is 1 to 48 hours, preferably 0.5 to 24 hours, particularly preferably 1 to 10 hours.
- an organic solvent such as methylene chloride, chloroform, carbon tetrachloride and / or 1,2-dichloroethane, water, or the like may be used as a solvent.
- the amount of the solvent to be used is generally 0.1-50 g, preferably 1-30 g, particularly preferably 2-20 g, per 1 g of compound (3).
- the molar ratio of the compound represented by the formula (1a) and the compound represented by the formula (1b) or a derivative derived from the compound (the compound represented by the formula (1b) or the compound) is usually 0.5 to 20, preferably 1 to 10.
- the conditions for Step B are not particularly limited, but the reaction temperature is usually ⁇ 30 to 100 ° C., preferably ⁇ 20 to 90 ° C., particularly preferably ⁇ 10 to 80 ° C .; It is 1 to 48 hours, preferably 0.5 to 24 hours, particularly preferably 1 to 10 hours.
- the molar ratio of the compound represented by the formula (1c) and the compound represented by the formula (1d) (the compound represented by the formula (1d) or the derivative derived from the compound / the above
- the compound represented by the formula (1c) is usually 0.1 to 20, preferably 0.5 to 5.
- the radiation-sensitive resin composition of the present invention contains (A) a compound as an acid generator and (B) a polymer.
- the radiation-sensitive resin composition of the present invention is excellent in the rectangularity of the cross-sectional shape of the resist pattern after development and hardly causes scum.
- the compound (A) has an alkali dissociable group, aggregation due to the developer and the rinsing liquid is suppressed, and it is considered that the compound is not likely to become a defect nucleus. Even when it is used for immersion exposure, an excellent effect is obtained that development defects are hardly caused.
- the acid generator generates an acid at an exposed portion by irradiation with radiation.
- the radiation sensitive resin composition of the present invention contains the compound (A) as an acid generator.
- the radiation sensitive resin composition of this invention may contain only (A) compound as an acid generator, (A) a compound and another acid generator (henceforth "other acid generator”). May also be included in combination.
- Examples of other acid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.
- onium salt compounds sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, diazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.
- at least one selected from the group consisting of an onium salt compound, a sulfonimide compound, and a diazomethane compound is preferable.
- Examples of other acid generators include compounds described in paragraphs 0086 to 0113 of International Publication No. 2009/051088.
- Particularly preferred specific examples of other acid generators include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenyl Sulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium 2,4-difluorobenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2- (norbornane- 2-yl) ethanesulfonate, triphenylsulfonium 2- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptane-2 Yl) -1,
- Triphenylsulfonium 2- (5-methanesulfonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-methanesulfonyloxy) Bicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (5-i-propanesulfonyloxybicyclo [2.2.1] heptane -2-yl) -1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (6-i-propanesulfonyloxybicyclo [2.2.1] heptan-2-yl) -1,1 , 2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (5
- the use ratio of the other acid generator can be appropriately selected according to the type, but is usually 95 parts by mass or less with respect to 100 parts by mass in total of the compound (A) and the other acid generator. , Preferably it is 90 mass parts or less, More preferably, it is 80 mass parts or less. If the use ratio of the other acid generator is excessive, the desired effect of the present invention may be impaired.
- the compounding amount of the acid generator can be variously selected according to the characteristics of the resist.
- the radiation-sensitive resin composition is a positive radiation-sensitive resin composition
- it is preferably 0.001 to 70 parts by weight, more preferably 0.01 to 70 parts by weight with respect to 100 parts by weight of the polymer (B). 50 parts by mass, particularly preferably 0.1 to 20 parts by mass.
- the amount of the acid generator is preferably 0.01 to 70 parts by mass with respect to 100 parts by mass of the polymer (B). More preferably, it is 0.1 to 50 parts by mass, and particularly preferably 0.5 to 20 parts by mass. There exists a tendency for a sensitivity and a resolution to fall that the compounding quantity of an acid generator is less than 0.01 mass part. On the other hand, if it exceeds 70 parts by mass, the coating property of the resist and the pattern shape tend to deteriorate.
- (B) Polymer for example, an alkali-insoluble or hardly alkali-soluble polymer having an acid-dissociable group, which is readily soluble in alkali when the acid-dissociable group is dissociated (hereinafter referred to as “( B1) polymer ”) and a polymer soluble in an alkali developer having at least one functional group having an affinity for an alkali developer (hereinafter also referred to as“ (B2) polymer ”).
- the functional group having affinity with the alkali developer include oxygen atom-containing functional groups such as phenolic hydroxyl groups, alcoholic hydroxyl groups, and carboxyl groups.
- the (B1) polymer can be suitably used as a base resin of a positive radiation sensitive resin composition.
- the said (B2) polymer can be used suitably as base resin of a negative type radiation sensitive resin composition.
- alkali insoluble or hardly soluble in alkali is employed when a resist pattern is formed from a photoresist film formed using a radiation sensitive resin composition containing (B1) a polymer.
- a film formed using only the polymer (B1) instead of the photoresist film is developed under alkaline development conditions, 50% or more of the initial film thickness of the film remains after development.
- the fluorine atom content ratio of the polymer (B) is preferably smaller than the fluorine atom content ratio of the polymer (C).
- the water repellency of the surface of the photoresist film formed by the radiation-sensitive resin composition containing the polymer (B) and the polymer (C) described later can be increased, and the upper layer film during the immersion exposure. Need not be formed separately.
- the fluorine atom content of the (B) polymer is usually less than 10% by mass, preferably 0 to 9% by mass, more preferably 0 when the total amount of the (B) polymer is 100% by mass. ⁇ 6% by mass.
- the fluorine atom content ratio of the polymer (B) can be measured by 13 C-NMR.
- the acid dissociable group in the polymer refers to, for example, a group in which a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group is substituted, and a group that dissociates in the presence of an acid.
- an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group
- Examples of such acid dissociable groups include substituted methyl group, 1-substituted ethyl group, 1-substituted-n-propyl group, 1-branched alkyl group, alkoxycarbonyl group, acyl group, cyclic acid dissociable group Etc.
- Examples of substituted methyl groups include the groups described in paragraph 0117 of WO2009 / 051088.
- Examples of the 1-substituted ethyl group include those described in paragraph 0118 of WO2009 / 051088.
- examples of the 1-substituted-n-propyl group include the group described in paragraph 0119 of WO2009 / 051088.
- Examples of the acyl group include the group described in paragraph 0120 of WO2009 / 051088.
- examples of the cyclic acid dissociable group include a group described in paragraph 0121 of WO2009 / 051088.
- benzyl group, t-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 1-ethoxy-n-propyl group, t-butyl Group, 1,1-dimethylpropyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group and the like are preferable.
- two or more acid dissociable groups may be present.
- the rate of introduction of acid-dissociable groups in the polymer ((B1) ratio of the number of acid-dissociable groups to the total number of acidic functional groups and acid-dissociable groups in the polymer) is the acid-dissociable group (B1) It can be appropriately selected depending on the type of polymer, but it is preferably 5 to 100 mol%, more preferably 10 to 100 mol%.
- the polymer is not particularly limited as long as it has the properties described above.
- (B1) As a preferred example of the polymer, a polymer in which at least one hydrogen atom of the phenolic hydroxyl group in poly (4-hydroxystyrene) is substituted with an acid dissociable group, 4-hydroxystyrene and / or 4- There are polymers in which at least one hydrogen atom of a phenolic hydroxyl group and / or a hydrogen atom of a carboxyl group in a copolymer of hydroxy- ⁇ -methylstyrene and (meth) acrylic acid is substituted with an acid dissociable group .
- (B1) polymer can be used individually by 1 type or in mixture of 2 or more types.
- the (B1) polymer can be variously selected depending on the type of radiation source used.
- the (B1) polymer when a KrF excimer laser is used as the radiation source, the (B1) polymer includes a repeating unit represented by the following general formula (8) (hereinafter also referred to as “repeating unit (8)”) and a repeating unit ( An alkali-insoluble or hardly alkali-soluble polymer (hereinafter also referred to as “polymer (KrF)”) having a repeating unit in which the phenolic hydroxyl group in 8) is protected with an acid-dissociable group is preferable.
- polymer (KrF) can also be used when using an ArF excimer laser, F 2 excimer laser, other radiation sources such as electron beams.
- R 14 represents a hydrogen atom or a monovalent organic group, provided that R 14 represents If there are multiple, they are independent of each other.
- repeating unit (8) a repeating unit in which a non-aromatic double bond of 4-hydroxystyrene is cleaved is particularly preferable.
- a polymer (KrF) may have other repeating units other than a repeating unit (8).
- repeating units examples include vinyl aromatic compounds such as styrene and ⁇ -methylstyrene; t-butyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyladamantyl (meth) acrylate ( Examples thereof include a repeating unit in which a polymerizable unsaturated bond of a (meth) acrylate ester is cleaved.
- the polymer (B1) is a repeating unit represented by the following general formula (9) (hereinafter also referred to as “repeating unit (9)”) and / or the following general A repeating unit represented by the formula (10) (hereinafter also referred to as “repeating unit (10)”) and a repeating unit represented by the following general formula (11) (hereinafter also referred to as “repeating unit (11)”) And insoluble or hardly alkali-soluble polymer (hereinafter also referred to as “polymer (ArF)”).
- the polymer (ArF) can also be used when other radiation sources such as a KrF excimer laser, an F 2 excimer laser, and an electron beam are used.
- R 15 represents a hydrogen atom, a methyl group or a trifluoromethyl group.
- a plurality of R 16 independently represent a hydrogen atom, a hydroxyl group, a cyano group, or a —COOR 19 group.
- R 19 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms.
- R 17 represents a single bond, an ether group, an ester group, a carbonyl group, a divalent aliphatic chain hydrocarbon group having 1 to 30 carbon atoms, or a divalent fat having 3 to 30 carbon atoms. It represents a cyclic hydrocarbon group, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, or a divalent group obtained by combining these.
- R Lc represents a monovalent organic group having a lactone structure.
- a plurality of R 18 are independently of each other a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched group having 1 to 4 carbon atoms.
- R 18 Represents an alkyl group. However, at least one of R 18 is an alicyclic hydrocarbon group or a derivative thereof. Further, any two R 18 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atoms to which they are bonded. )
- Preferred examples of the repeating unit (9) include 3-hydroxyadamantan-1-yl (meth) acrylate, 3,5-dihydroxyadamantan-1-yl (meth) acrylate, and 3-cyanoadamantane (meth) acrylate.
- R Lc monovalent organic group having a lactone structure represented by R Lc
- R Lc -6 monovalent organic group having a lactone structure represented by R Lc
- R 24 in represents an oxygen atom or a methylene group.
- R 27 represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms, or a linear chain having 1 to 4 carbon atoms. Jo or shows a branched alkoxy group.
- Preferred examples of the repeating unit (11) include 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, and 1-ethylcyclohexyl (meth) acrylate.
- the polymer (ArF) can also have other repeating units other than the repeating units (9) to (11).
- monomers that give other repeating units include (meth) acrylic acid 7-oxo-6-oxabicyclo [3.2.1] octane-4-yl, (meth) acrylic acid 2-oxotetrahydropyran -4-yl, 4-methyl-2-oxotetrahydropyran-4-yl (meth) acrylate, 5-oxotetrahydrofuran-3-yl (meth) acrylate, 2-oxotetrahydrofuran-3- (meth) acrylate (Meth) acrylic acid (5-oxotetrahydrofuran-2-yl) methyl, (meth) acrylic acid (3,3-dimethyl-5-oxotetrahydrofuran-2-yl) methyl, (meth) acrylic acid 2-hydroxy (Meth) acrylic acid esters such as ethyl; (meth) acrylamide, N
- monofunctional monomers such as dodeca-3-ene or derivatives thereof, methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2,5-dimethyl-2,5-hexane Diol di (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodecane dimethylol di ( There are polyfunctional monomers such as (meth) acrylate.
- the method for preparing the polymer is not particularly limited. For example, a method of introducing one or more acid-dissociable groups into an acidic functional group in an alkali-soluble polymer prepared in advance; one or more polymerizable unsaturated monomers having an acid-dissociable group are required A method of polymerizing together with one or more other polymerizable unsaturated monomers as required; one or more polycondensable components having an acid dissociable group, and polycondensation with other polycondensable components as necessary There are ways to do this.
- Polymerization of the polymerizable unsaturated monomer and the polymerization of the polymerizable unsaturated monomer having an acid dissociable group in preparing the alkali-soluble polymer are carried out according to the polymerizable unsaturated monomer used and the reaction medium.
- radical polymerization initiator, anion polymerization catalyst, coordination anion polymerization catalyst, cationic polymerization catalyst, etc. are appropriately selected, and bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, bulk-suspension It can implement by appropriate polymerization forms, such as superposition
- the polycondensation of the polycondensable component having an acid dissociable group can be preferably carried out in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acid catalyst.
- (B1) When the polymer is produced by polymerization of a polymerizable unsaturated monomer or through previous polymerization, (B1) the polymer is a polyfunctional monomer having two or more polymerizable unsaturated bonds
- a branched structure can be introduced by a repeating unit derived from the above and / or an acetal cross-linking group. By introducing such a branched structure, the heat resistance of the polymer (B1) can be improved.
- the introduction rate of the branched structure in the polymer (B1) can be appropriately selected depending on the branched structure and the type of polymer to be introduced, but it should be 10 mol% or less with respect to all repeating units. preferable.
- the molecular weight of the polymer is not particularly limited and may be appropriately selected.
- the weight molecular weight in terms of polystyrene (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC) is usually 1,000 to 500,000, preferably 2,000 to 400,000, and more preferably 3,000 to 300,000.
- the Mw of the polymer having no branched structure (B1) is preferably 1,000 to 150,000, and more preferably 3,000 to 100,000.
- the Mw of the (B1) polymer having a branched structure is preferably 5,000 to 500,000, more preferably 8,000 to 300,000.
- the ratio (Mw / Mn) of the number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC and Mw of the polymer (B1) is not particularly limited, and is usually 1 to 10, preferably 1 to 8, and more preferably 1 to 5. (B1) When the Mw / Mn of the polymer is in such a range, the photoresist film has excellent resolution performance.
- the radiation-sensitive resin composition of the present invention preferably contains (C) a polymer as a polymer additive.
- C due to the oil repellency of the polymer, (C)
- the distribution of the polymer tends to be high. That is, (C) the polymer is unevenly distributed on the surface of the photoresist film. Therefore, it is not necessary to separately form an upper layer film for the purpose of blocking the photoresist film from the immersion medium, and can be suitably used for the immersion exposure method.
- the polymer is not particularly limited as long as it has a fluorine atom in the polymer, but it is a polymer having a repeating unit having a fluorine atom (hereinafter also referred to as “repeating unit (C1)”). Is preferred. Specific examples of such a repeating unit (C1) include repeating units represented by the following general formulas (C1-1) to (C1-3) (hereinafter referred to as “repeating units (C1-1) to (C1-3)”. ) ”). (C) When the polymer has repeating units (C1-1) to (C1-3), it is possible to suppress elution of the acid generator and the acid diffusion controller in the photoresist film from the immersion exposure solution. it can.
- R 28 represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- Rf 1 represents at least one A hydrocarbon group having 1 to 30 carbon atoms in which a hydrogen atom is substituted with a fluorine atom, in formula (C1-2),
- R 29 represents a (g + 1) -valent linking group, and
- g represents 1 to 3
- R 30 represents a divalent linking group
- R 31 represents a hydrogen atom, a carbon number 1 to 30 represents a monovalent hydrocarbon group, an acid dissociable group, or an alkali dissociable group
- Rf 2 is independently a hydrogen atom, a fluorine atom, or at least one hydrogen atom is replaced by a fluorine atom
- Rf 1 in the general formula (C1-1) examples include a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or at least 1 There is an alicyclic hydrocarbon group having 4 to 20 carbon atoms in which one hydrogen atom is substituted with a fluorine atom, or a group derived therefrom.
- Examples of the linear or branched alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom include a group represented by R 41 in the general formula (R 4 -1). Among them, there are groups listed as specific examples of linear or branched alkyl groups having 1 to 7 carbon atoms.
- Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a group derived therefrom include a cyclopentyl group, a cyclopentylmethyl group, and 1- (1-cyclopentyl).
- Ethyl) group 1- (2-cyclopentylethyl) group, cyclohexyl group, cyclohexylmethyl group, 1- (1-cyclohexylethyl) group, 1- (2-cyclohexylethyl group), cycloheptyl group, cycloheptylmethyl group, Examples thereof include partially fluorinated or perfluoroalkylated groups of alicyclic hydrocarbon groups such as 1- (1-cycloheptylethyl) group, 1- (2-cycloheptylethyl) group, and 2-norbornyl group.
- Preferable examples of the monomer that gives the repeating unit (C1-1) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, and perfluoroethyl (meth).
- Acrylic acid ester perfluoro n-propyl (meth) acrylic acid ester, perfluoro i-propyl (meth) acrylic acid ester, perfluoro n-butyl (meth) acrylic acid ester, perfluoro i-butyl (meth) acrylic acid Ester, perfluoro t-butyl (meth) acrylate, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylate, 1- (2,2,3,3 , 4,4,5,5-octafluoropentyl) (meth) acrylic acid ester, perfluorocyclohexylmethyl (Meth) acrylic acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylic acid ester, 1- (3,3,4,4,5,5,6,6,7 , 7,8,8,9,9,10,10,10-heptadecafluorodecyl) (meth) acrylic acid ester, 1-
- R 31 represents a hydrogen atom or a monovalent organic group.
- the monovalent organic group include a monovalent hydrocarbon group having 1 to 30 carbon atoms, an acid dissociable group, and an alkali dissociable group.
- Examples of monovalent hydrocarbon groups having 1 to 30 carbon atoms include linear or branched aliphatic chain hydrocarbon groups having 1 to 10 carbon atoms and alicyclic hydrocarbon groups having 3 to 30 carbon atoms. There is. These hydrocarbon groups are the same as the linear or branched alkyl group having 1 to 7 carbon atoms and the alicyclic hydrocarbon group having 3 to 7 carbon atoms described in R 41 . Moreover, this hydrocarbon group may have a substituent. As such a substituent, the description of the substituent which R 1 to R 3 in the general formula (1) may have can be applied as it is.
- the acid dissociable group substitutes, for example, a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group A group that dissociates in the presence of an acid.
- a polar functional group such as a hydroxyl group or a carboxyl group A group that dissociates in the presence of an acid.
- t-butoxycarbonyl group tetrahydropyranyl group, tetrahydrofuranyl group, (thiotetrahydropyranylsulfanyl) methyl group, (thiotetrahydrofuranylsulfanyl) methyl group, alkoxy-substituted methyl group, alkylsulfanyl-substituted methyl group Etc.
- the alkoxyl group (substituent) in the alkoxy-substituted methyl group and the alkyl group (substituent) in the alkylsulfanyl-substituted methyl group include, for example, an alkoxyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. .
- the acid dissociable group also include a group represented by the following general formula (12). -C (R 32 ) 3 (12) (In the general formula (12), three R 32 are the same as R 18 in the general formula (11).)
- a group represented by the general formula (12) a group represented by the general formula (12), a t-butoxycarbonyl group, an alkoxy-substituted methyl group, and the like are preferable.
- a t-butoxycarbonyl group and an alkoxy-substituted methyl group are more preferable.
- an alkoxy-substituted methyl group and a group represented by the general formula (12) are more preferable.
- the solubility of the (C) polymer in the exposed portion of the photoresist film is increased. Since it can improve, it is preferable. This is considered to be because a polar group is generated by reacting with an acid generated at an exposed portion of the photoresist film in an exposure step in the resist pattern forming method described later.
- the alkali dissociable group substitutes a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group.
- the alkali-dissociable group is not particularly limited as long as it exhibits the above properties, but in the general formula (C1-2), a group represented by the general formula (R 4 -1) is preferable.
- groups represented by general formulas (R 4 -2) to (R 4 -4) are preferred.
- (C) When the polymer is a polymer having a repeating unit (C1-2) or (C1-3) having an alkali-dissociable group, (C) improving the affinity of the polymer for an alkali developer. Is preferable. This is considered to be because (C) the polymer reacts with the developer to generate a polar group in the development step of the resist pattern forming method described later.
- the repeating units (C1-2) and (C1-3) are a hydroxyl group that is a polar group. And have a carboxyl group.
- the affinity of the polymer (C) for the alkaline developer can be improved in the development step of the resist pattern forming method described later.
- R 29 represents a (g + 1) -valent linking group.
- a linking group include a single bond or a (g + 1) -valent hydrocarbon group having 1 to 30 carbon atoms. Further, there are combinations of these hydrocarbon groups with an oxygen atom, a sulfur atom, an imino group, a carbonyl group, a —CO—O— group, or a —CO—NH— group.
- G represents an integer of 1 to 3. However, when g is 2 or 3, the structures represented by the following general formula (C1-2-a) in the general formula (C1-2) are independent of each other.
- R 31 and Rf 2 are the same as R 31 and Rf 2 in the general formula (C1-2).
- chain structure R 29 examples include methane, ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, heptane, octane, nonane, decane, etc.
- Examples of the cyclic structure R 29 include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2, 6 ]
- R 29 an oxygen atom, a sulfur atom, an imino group, a carbonyl group, examples of the structure having a -CO-O- group, or a -CO-NH- group, the following general formula (R 29 -1) There is a structure represented by (R 29 -8).
- R 33 each independently represents a single bond, an aliphatic chain hydrocarbon group having 1 to 10 carbon atoms, or a group having 4 to 20 carbon atoms. An alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 30 carbon atoms is shown.
- R 29 in the general formulas (R 29 -1) to (R 29 -8) an aliphatic chain hydrocarbon group having 1 to 10 carbon atoms and an alicyclic group having 4 to 20 carbon atoms
- the description of R 29 in the general formula (C1-2-a) can be applied as it is.
- R 29 may have a substituent.
- the description of the substituent which R 1 to R 3 in the general formula (1) may have can be applied.
- the hydrocarbon group having 1 to 30 carbon atoms in which at least one hydrogen atom represented by Rf 2 is substituted with a fluorine atom may be represented by the general formula ( The same can be said for Rf 1 in C1-1).
- Examples of the partial structure represented by the following general formula (C1-2-b) in the general formulas (C1-2) and (C1-3) include the following formulas (C1-2-b1) to (C1-2): There is a partial structure represented by -b5). Among these, in the general formula (C1-2), a partial structure represented by the following formula (C1-2-b5) is preferable, and in the general formula (C1-3), the following formula (C1-2-b3) is preferable. ) Is preferable.
- repeating unit (C1-2) include repeating units represented by the following general formulas (C1-2-1) and (C1-2-2).
- R 28, R 29, R 31, and g is, R 28, R 29, R 31 in the general formula (C1-2), And the same as g.
- Examples of the compound giving such a repeating unit include compounds represented by the following general formulas (C1-2-m1) to (C1-2-m5).
- R 28 and R 31 have the same meaning as in the general formula (C2-1).
- R 31 is an acid-dissociable group or an alkali-dissociable group
- R 31 is a compound in which R 31 is a hydrogen atom is synthesized as a raw material can do.
- R 31 is when shown the general formula (R 4 -1) is a group represented by compounds can be formed by R 31 is fluoro acylated by known methods a compound having a hydrogen atom as an example .
- esterification is performed by condensing an alcohol and a fluorocarboxylic acid in the presence of an acid
- esterification is performed by condensing the alcohol and a fluorocarboxylic acid halide in the presence of a base.
- repeating unit (C1-3) examples include a repeating unit represented by the following general formula (C1-3-1).
- R 28, R 30 and R 31 of the general formula (C1-3) in, R 28, R same can be said with 30 and R 31.
- Examples of the compound giving such a repeating unit include compounds represented by the following general formulas (C1-3-m1) to (C1-3-m4).
- R 28 and R 31 can be said general formula (C1-3) in the same manner as R 28 and R 31 Description.
- R 31 is an acid dissociable group or an alkali dissociable group
- a compound or a derivative thereof in which R 31 is a hydrogen atom It can be synthesized as a raw material.
- a compound in which R 31 is represented by the general formula (R 4 -4) is represented by, for example, a compound represented by the following general formula (m-1) and a compound represented by the following general formula (m-2 It can synthesize
- R 28 , R 30 and Rf 2 are the same is true with the general formula (C1-3) in the R 28, R 30 and Rf 2.
- R 34 represents a hydroxyl group or a halogen atom.
- R 8 and R 9 same can be said that R 8 and R 9 in the general formula (R 4 -4).
- the polymer (C) may have only one type of repeating units (C1-1) to (C1-3) or two or more types, but the repeating unit (C1-1) It is preferable to have two or more of (C1-3), and it is particularly preferable to have a combination of the repeating unit (C1-2) and the repeating unit (C1-3).
- the polymer has, in addition to the repeating unit (C1), a repeating unit having an acid dissociable group other than the repeating unit (C1) (hereinafter also referred to as “repeating unit (C2)”), an alkali-soluble group.
- repeating unit excluding those corresponding to the repeating unit (C1)) (hereinafter also referred to as “repeating unit (C3)”) or repeating unit having a lactone skeleton (hereinafter referred to as “repeating unit (C4)”) It is preferable to further include
- repeating unit (C2) among the repeating units (11), the repeating unit represented by the general formula (C2-1) is particularly preferable.
- R 15 represents a hydrogen atom, a methyl group, or a trifluoromethyl group
- R 35 represents a linear or branched alkyl group having 1 to 4 carbon atoms.
- k represents an integer of 1 to 4.
- examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R 35 include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. N-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like.
- the polymer may have the repeating unit (C2) singly or in combination of two or more. Moreover, when it has a repeating unit (C3) or a repeating unit (C4) as (C) polymer, the solubility with respect to an alkali developing solution can be improved.
- the alkali-soluble group in the repeating unit (C3) is preferably a functional group having a hydrogen atom having a pKa of 4 to 11 from the viewpoint of improving solubility in an alkali developer.
- Specific examples of such functional groups include functional groups represented by general formula (C-3a) and formula (C-3b).
- R 36 represents a hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.
- the hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom represented by R 36 is substituted with a fluorine atom is not particularly limited, but is trifluoro A methyl group and the like are preferable.
- the main chain skeleton of the repeating unit (C3) is not particularly limited, but is preferably a skeleton such as methacrylic acid ester, acrylic acid ester, or ⁇ -trifluoroacrylic acid ester.
- repeating unit (C3) examples include repeating units derived from the compounds represented by the general formulas (C3-a-1) and (C3-b-1).
- R 38 represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- R 39 represents a single bond or a carbon number of 1-20.
- R 37 represents a hydrocarbon having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom Represents a group, and n represents 0 or 1.
- the polymer may have a single repeating unit (C3) or a combination of two or more.
- repeating unit (C4) there is a repeating unit (10).
- the content of the repeating unit (C1) is preferably 20 to 90 mol%, particularly preferably 20 to 80 mol%.
- the content of the repeating unit (C2) is usually 80 mol% or less, preferably 20 to 80 mol%, more preferably 30 to 70 mol%.
- the content ratio of the repeating unit (C2) is within this range, it is particularly effective from the viewpoint of reducing the difference between the advancing contact angle and the receding contact angle.
- the content of the repeating unit (C3) is usually 50 mol% or less, preferably 5 to 30 mol%, and more preferably 5 to 20 mol%.
- the content of the repeating unit (C4) is usually 50 mol% or less, preferably 5 to 30 mol%, more preferably 5 to 20 mol%.
- the polymer is, for example, a polymerizable unsaturated monomer corresponding to each predetermined repeating unit, a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. And can be prepared by polymerization in an appropriate solvent in the presence of a chain transfer agent, if necessary.
- a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds.
- Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, norbornane.
- Cycloalkanes such as benzene, toluene, xylene, ethylbenzene, cumene and other aromatic hydrocarbons; chlorobutanes, bromohexanes, dichloroethanes, halogenated hydrocarbons such as hexamethylene dibromide, chlorobenzene; ethyl acetate, Saturated carboxylic acid esters such as n-butyl acetate, i-butyl acetate and methyl propionate; ketones such as acetone, 2-butanone, 4-methyl-2-pentanone and 2-heptanone; tetrahydrofuran, dimethoxyethanes, di Ethers such as ethoxyethanes; Nord, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanol alcohols such like. These solvent can be used individually by 1 type or in mixture of 2 or more types.
- the Mw of the polymer is preferably 1,000 to 50,000, more preferably 1,000 to 40,000, and still more preferably 1,000 to 30,000. If Mw is less than 1,000, a photoresist film having a sufficient receding contact angle may not be formed. On the other hand, if it exceeds 50,000, the developability of the photoresist film may be lowered.
- the ratio (Mw / Mn) of Mw and Mn of the polymer (C) is preferably 1 to 5, and more preferably 1 to 4.
- the polymer is more preferable as the content of impurities such as halogen and metal is smaller.
- the content of impurities is small, the sensitivity, resolution, process stability, pattern shape and the like of the photoresist film can be further improved.
- the blending amount of the polymer (C) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer (B). Particularly preferred is 5 parts by mass. If it is less than 0.1 part by mass, the effect of containing the polymer (C) may not be sufficient. On the other hand, if it exceeds 20 parts by mass, the water repellency of the resist surface becomes too high and development failure may occur.
- the fluorine atom content rate in a polymer is larger than the fluorine atom content rate in (B) polymer.
- the total amount of the polymer (C) is 100% by mass, usually 5% by mass or more, preferably 5 to 50% by mass, and more preferably 5 to 45% by mass.
- the fluorine atom content can be measured by 13 C-NMR.
- the water repellency on the surface of the photoresist film can be increased, and there is no need to separately form an upper layer film during immersion exposure.
- the difference of the content rate of the fluorine atom in (B) polymer and the content rate of the fluorine atom in (C) polymer is 1 mass% or more. Preferably, it is 5 mass% or more.
- a conventionally well-known additive may be mix
- an acid diffusion control agent that controls the diffusion phenomenon of acid generated from the acid generator upon exposure in the photoresist film and suppresses an undesirable chemical reaction in the non-exposed region is preferable.
- blending such an acid diffusion control agent while being able to improve the storage stability of a radiation sensitive resin composition, the resolution can further be improved.
- Such an acid diffusion controller include nitrogen-containing organic compounds described in paragraphs 0176 to 0187 of International Publication No. 2009/051088.
- trialkylamines such as tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine; Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine N-containing organic compounds having an acid-dissociable group such as Nt-butoxycarbonyl-N ′, N ′′ -dicyclohexylamine; polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide; 2-phenylbenzimidazole, N -Nitrogen-containing heterocyclic compounds such as -t-butoxycarbonyl-2-phenylbenzimidazole, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, and the like.
- the organic compound is one kind alone, or two or more kinds. Combined and can be used.
- a compound represented by the general formula (D1-0) can also be used.
- X + Z - ⁇ (D1-0) (In the general formula (D1-0), X + represents a cation represented by the general formula (D1-1) or a cation represented by the general formula (D1-2).
- Z ⁇ represents OH ⁇ , R D1 -COO - anion represented by, R D1 -SO 3 - anion represented by, or R D1 -N -.
- R D1 is substituted Represents an optionally substituted alkyl group, a monovalent alicyclic hydrocarbon group, or an aryl group
- R D21 represents an optionally substituted fluorinated aliphatic chain hydrocarbon group, or a monovalent fluorinated group; Indicates an alicyclic hydrocarbon group.
- R D2 to R D4 each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom.
- R D5 And R D6 each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom.
- the compound represented by the general formula (D1-0) is used as an acid diffusion control agent that is decomposed by exposure and loses acid diffusion controllability (hereinafter also referred to as “photodegradable acid diffusion control agent”). .
- photodegradable acid diffusion control agent By containing this compound, the acid diffuses in the exposed area, and the acid diffusion is controlled in the unexposed area, so that the contrast between the exposed area and the unexposed area is excellent (that is, the boundary between the exposed area and the unexposed area). Therefore, it is particularly effective for improving LWR and MEEF of the radiation-sensitive resin composition of the present invention.
- R D2 to R D4 in formula (D1-1) each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom.
- a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom is preferable from the viewpoint of reducing solubility in a developer.
- R D5 and R D6 each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom.
- a hydrogen atom, an alkyl group, or a halogen atom is preferable.
- Z ⁇ in the general formula (D1-0) is represented by an anion represented by OH ⁇ , R D1 —COO — , R D1 —SO 3 ⁇ , or R D1 —N ⁇ —SO 2 —R D21.
- R D1 represents an optionally substituted alkyl group, a monovalent alicyclic hydrocarbon group, or an aryl group.
- R D21 represents an optionally substituted fluorinated aliphatic chain hydrocarbon group or a monovalent fluorinated alicyclic hydrocarbon group.
- Z ⁇ in the general formula (D1-0) is an anion represented by the following formula (D1-3) (that is, an anion in which R D1 is a phenol group), or represented by the following formula (D1-4). It is preferable that R D1 is a group derived from 1,7,7-trimethylbicyclo [2.2.1] heptan-2-one.
- the photodegradable acid diffusion controller is represented by the general formula (D1-0), and specifically, is a sulfonium salt compound or an iodonium salt compound that satisfies the above conditions.
- the sulfonium salt compound examples include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium acetate, diphenyl-4- Examples thereof include hydroxyphenylsulfonium salicylate, triphenylsulfonium 10-camphor sulfonate, 4-tert-butoxyphenyl diphenylsulfonium 10-camphor sulfonate, and the like.
- these sulfonium salt compounds can be used individually by 1 type or in combination of 2 or more types.
- the iodonium salt compound examples include bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxy Phenyliodonium acetate, 4-tert-butylphenyl-4-hydroxyphenyliodonium salicylate, bis (4-tert-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium 10-camphors And the like can be given Honeto.
- these iodonium salt compounds can be used individually by 1 type
- the compounding amount of the acid diffusion controller is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, and particularly preferably 0.005 to 100 parts by mass with respect to 100 parts by mass of the polymer (B). 5 parts by mass.
- a dissolution control agent having the property of increasing the solubility in an alkaline developer by the action of an acid.
- a dissolution control agent for example, a compound having an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, or a compound in which the hydrogen atom of the acidic functional group in the compound is substituted with an acid dissociable group Etc.
- the dissolution controller may be a low molecular compound or a high molecular compound.
- the radiation sensitive resin composition is a negative radiation sensitive resin composition
- the polymer dissolution control agent for example, (B1) polymer can be used.
- dissolution control agent can be used individually by 1 type or in mixture of 2 or more types.
- the compounding quantity of a dissolution control agent is 50 mass parts or less normally with respect to 100 mass parts of (B) polymers, Preferably it is 20 mass parts or less.
- a surfactant exhibiting an effect of improving coating properties, striations, developability and the like can be blended.
- a surfactant any of anionic, cationic, nonionic or amphoteric surfactants can be used, but nonionic surfactants are preferred.
- surfactant can be used individually by 1 type or in mixture of 2 or more types.
- the compounding quantity of surfactant is 2 mass parts or less normally as an active ingredient of surfactant with respect to 100 mass parts of (B) polymers, Preferably it is 1.5 mass parts or less.
- Nonionic surfactants include, for example, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, and “KP” (Shin-Etsu Chemical Co., Ltd.) under the following trade names: ), "Polyflow” (manufactured by Kyoeisha Chemical Co., Ltd.), “F Top” (manufactured by Gemco), “Megafuck” (manufactured by Dainippon Ink & Chemicals), “Florard” (manufactured by Sumitomo 3M), “Asahi Guard” ”And“ Surflon ”(manufactured by Asahi Glass Co., Ltd.).
- KP Shin-Etsu Chemical Co., Ltd.
- a sensitizer that absorbs the energy of radiation and transmits the energy to the acid generator, thereby increasing the amount of acid generated, and can improve the apparent sensitivity is formulated.
- Examples of such sensitizers include acetophenones, benzophenones, naphthalene, biacetyl, eosin, rose bengal, pyrenes, anthracene, phenothiazines and the like. These sensitizers can be used individually by 1 type or in mixture of 2 or more types.
- the compounding quantity of a sensitizer is 50 mass parts or less normally with respect to 100 mass parts of (B) polymers, Preferably it is 30 mass parts or less.
- a lactone compound (G) having an effect of efficiently segregating the polymer (C), which exhibits an effect of developing water repellency on the resist film surface in immersion exposure, to the resist film surface can be blended.
- the amount of the (C) polymer added can be reduced when the (C) polymer is contained. Therefore, without damaging the basic characteristics of the resist, the elution of the components from the photoresist film to the immersion exposure liquid is suppressed, and even if immersion exposure is performed by high-speed scanning, no droplets are left as a result. It is possible to maintain the water repellency of the resist film surface that suppresses immersion-derived defects such as watermark defects.
- lactone compound (G) examples include ⁇ -butyrolactone, valerolactone, mevalonic lactone, norbornane lactone, and the like.
- the lactone compound (G) may be used alone or in combination of two or more.
- the blending amount of the lactone compound (G) is usually 30 to 200 parts by mass, more preferably 50 to 150 parts by mass with respect to 100 parts by mass of the polymer (B).
- the blending amount of the lactone compound (G) is too small, sufficient water repellency on the resist film surface cannot be obtained even when a small amount of the (C) polymer is added.
- the compounding amount is excessive, the basic performance of the resist and the pattern shape after development may be remarkably deteriorated.
- additives other than those described above for example, dyes, pigments, adhesion aids, antihalation agents, storage stabilizers, antifoaming agents, shape improvers, etc.
- 4-hydroxy-4′-methylchalcone or the like can be blended.
- a dye or pigment by blending a dye or pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be mitigated, and the adhesion to the substrate can be improved by blending an adhesion assistant. be able to.
- the radiation-sensitive resin composition of the present invention is usually prepared by dissolving each component in a solvent (E) during use to form a uniform solution, and then, if necessary, for example, filtering with a filter having a pore diameter of about 0.2 ⁇ m. To prepare a composition solution.
- Examples of the solvent (E) include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, and (halogenated) hydrocarbons. More specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, acyclic Or cyclic ketones, acetate esters, hydroxyacetate esters, alkoxyacetate esters, acetoacetate esters, propionate esters, lactate esters, other substituted propionate esters, (substituted) butyrate esters, Pyruvate esters, N, N-dialkylformamides, N, N-dialkylacetamides, N-alkylpyrrolidones, (halogenated
- solvent (E) examples include the solvents described in Paragraph 0202 of International Publication No. 2009/051088.
- a solvent (E) can be used individually by 1 type or in mixture of 2 or more types.
- solvents such as benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1
- High-boiling solvents such as octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can be used.
- solvents can be used alone or in combination of two or more.
- the proportion of other solvents used is usually 50% by mass or less, preferably 30% by mass or less, based on the total solvent.
- the amount of the solvent (E) used is such that the total solid concentration of the composition solution is usually 5 to 50% by mass, preferably 10 to 50% by mass, more preferably 10 to The amount is 40% by mass, more preferably 10-30% by mass, and particularly preferably 10-25% by mass. By setting the total solid content concentration of the composition solution within this range, it is possible to ensure good in-plane uniformity during coating.
- Resist pattern formation method In the resist pattern forming method of the present invention, first, the composition solution prepared as described above was coated with, for example, a silicon wafer or aluminum by an appropriate application means such as spin coating, cast coating, or roll coating. A photoresist film is formed by coating on a substrate such as a wafer. Thereafter, in some cases, a heat treatment (hereinafter also referred to as “PB”) is performed in advance, and then the photoresist film is exposed through a predetermined mask pattern.
- PB heat treatment
- the radiation that can be used for exposure includes the emission line spectrum of a mercury lamp (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F 2 excimer, depending on the type of acid generator.
- Examples include deep ultraviolet rays such as laser (wavelength 157 nm) and EUV (wavelength 13 nm, etc.), X-rays such as synchrotron radiation, and charged particle beams such as electron beams.
- KrF excimer laser wavelength 248 nm
- ArF excimer laser wavelength 193 nm
- F 2 excimer laser wavelength 157 nm
- electron beam is particularly preferable.
- an immersion exposure liquid is disposed on the photoresist film, and the photoresist film is subjected to immersion exposure via the immersion exposure liquid.
- the exposure conditions such as the radiation dose are appropriately selected according to the blending composition of the radiation-sensitive resin composition, the type of additive, and the like.
- a heat treatment hereinafter also referred to as “PEB”
- the heating conditions for PEB vary depending on the composition of the radiation-sensitive resin composition, the type of additive, etc., but are usually 30 to 200 ° C., preferably 50 to 150 ° C.
- the exposed photoresist film is developed with an alkaline developer to form a predetermined positive or negative resist pattern.
- alkali developer examples include alkali metal hydroxide, ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4.0].
- An alkaline aqueous solution in which one or more alkaline compounds such as -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene are dissolved is used.
- a particularly preferred alkaline developer is an aqueous solution of tetraalkylammonium hydroxides.
- the concentration of the alkaline aqueous solution is preferably 10% by mass or less, more preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass. By setting the concentration of the alkaline aqueous solution to 10% by mass or less, dissolution of the non-exposed portion (in the case of positive type) or the exposed portion (in the case of negative type) into the alkaline developer can be suppressed.
- a surfactant or the like to the developer composed of an alkaline aqueous solution, whereby the wettability of the alkali developer with respect to the photoresist film can be enhanced.
- the developing solution which consists of alkaline aqueous solution After developing with the developing solution which consists of alkaline aqueous solution, generally it wash
- the obtained diphenyl (4- (3,3,3-trifluoropropanoyloxy) phenyl) sulfonium chloride was analyzed by NMR (trade name: JNM-EX270, manufactured by JEOL Ltd.). As a result, the chemical shifts obtained were as follows: 1 H-NMR ( ⁇ ppm (CD 3 OD): 3.45 (2H), 6.98-7.10 (2H), 7.47-7.89 (12H) ), 19 F-NMR ( ⁇ ppm (DMSO): 0.53), which was confirmed to be the target compound (note that 1 H-NMR is sodium 3-trimethylsilylpropionate 2-2,2,3 , 3-d 4 , 19 F-NMR, the peak of benzotrifluoride was 0 ppm (internal standard)). The purity was 99% (measured by 1 H-NMR).
- Example 1 Synthesis of (A-1) sulfonium compound The compound represented by the following formula (A-1) diphenyl (4- (3,3,3-trifluoropropanoyloxy) phenyl) sulfonium-1,1,2,2,3,3,4,4,4-nona Fluorobutane-1-sulfonate was synthesized by the following method.
- Example 2 (A-2) Synthesis of sulfonium compound) 2- (bicyclo [2.2.1] 2-heptanyl) -1 instead of sodium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate as a starting material Diphenyl (4- (3,3,3-trifluoropropanoyloxy) represented by the following formula (A-2) in the same manner as in Example 1 using sodium 1,2,2,2-tetrafluoroethanesulfonate ) Phenyl) sulfonium-2- (bicyclo [2.2.1] 2-heptanyl) -1,1,2,2-tetrafluoroethanesulfonate was synthesized.
- Example 4 (A-4) Synthesis of sulfonium compound
- Example 5 (A-5) Synthesis of sulfonium compound) Diphenyl (4- (3,3,3-trifluoropropanoyloxy) phenyl) sulfonium chloride and 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfone as starting materials 4- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononanoyloxy instead of sodium acid 4-) (2,2,3,3,4,4,5) represented by the following formula (A-5) in the same manner as in Example 1 using phenyl) dimethylsulfonium chloride and sodium trifluoromethanesulfonate. , 5,6,6,7,7,8,8,9,9,9-heptadecafluorononanoyloxy) phenyl) dimethylsulfonium-trifluoromethanesulfonate.
- a polymer (B) was prepared using the compounds (M-1) to (M-4) represented by the following formula.
- the polymerization solution was cooled with water to 30 ° C. or less, and poured into 1000 g of methanol, and the precipitated white powder was filtered off.
- the filtered white powder was dispersed in 200 g of methanol, washed in the form of a slurry, and then filtered off twice. It was dried at 50 ° C. for 17 hours to obtain a white powder copolymer (yield 39 g, yield 78%).
- This copolymer had Mw of 6100 and Mw / Mn of 1.4, and as a result of 13 C-NMR analysis, compound (M-1), compound (M-2), compound (M-3) And the content (mol%) of the repeating unit derived from the compound (M-4) was 42.2: 8.1: 8.4: 41.3, respectively.
- This copolymer is referred to as (B-1) polymer.
- a polymer (C) was prepared using the compounds (S-1) to (S-9) shown below.
- the polymerization solution was cooled with water to 30 ° C. or less, and the polymerization solution was transferred to a 2 L separatory funnel.
- the polymerization solution was diluted with 150 g of methanol, mixed with 600 g of hexane, then stirred with 21 g of distilled water, and allowed to stand for 30 minutes. Thereafter, the lower layer was collected to obtain a propylene glycol monomethyl ether acetate solution.
- the solid content (polymer) of the propylene glycol monomethyl ether acetate solution was 71%, Mw was 7100, and Mw / Mn was 1.3.
- the monomer solution (i) prepared in advance was added dropwise over 20 minutes and aged for 20 minutes, and then the monomer solution (ii) was added dropwise over 20 minutes. . Thereafter, the reaction was further performed for 1 hour, and the mixture was cooled to 30 ° C. or less to obtain a copolymer liquid.
- the obtained copolymer solution was concentrated to 150 g and then transferred to a separatory funnel. To this separatory funnel, 50 g of methanol and 400 g of n-hexane were added for separation and purification. After separation, the lower layer solution was recovered. The recovered lower layer solution was replaced with 4-methyl-2-pentanol to obtain a resin solution.
- the recovered upper layer liquid was replaced with 4-methyl-2-pentanol to obtain a resin solution.
- Mw of the copolymer contained in the obtained resin solution was 9,760, Mw / Mn was 1.51, and the yield was 65%.
- the content (mol%) of the repeating units derived from the compound (S-8) and the compound (S-9) was 95: 5, respectively, and the fluorine atom content ratio was 36.8%.
- This copolymer is referred to as “upper layer polymer (2)”.
- an upper layer film-forming composition (H) 7 parts of the polymer for the upper film (1) prepared in Synthesis Example 6, 93 parts of the polymer for the upper film (2) prepared in Synthesis Example 7, 10 parts of diethylene glycol monoethyl ether acetate, 4-methyl-2-hexanol (
- an upper layer film-forming composition (H) was prepared by mixing 10 parts of “MIBC”) and 90 parts of diisoamyl ether (hereinafter also referred to as “DIAE”).
- Example 6 Preparation of radiation-sensitive resin composition (T-1)) 100 parts of the (B-1) polymer prepared in Synthesis Example 2, 12.1 parts of the (A-1) sulfonyl compound synthesized in Example 1, (D-1) 1.5 parts of an acid diffusion controller, (E -1) 1800 parts of solvent, (E-2) 770 parts of solvent, and 30 parts of (G-1) additive were mixed to prepare a composition solution (T-1) of a radiation sensitive resin composition.
- Example 7 to 23 Preparation of radiation-sensitive resin compositions (T-2) to (T-18)
- Composition solutions (T-2) to (T-18) of each radiation-sensitive resin composition were prepared in the same manner as in Example 5 except that the formulation shown in Table 2 or Table 3 was used.
- Pattern formation method (P-1) A lower antireflection film having a film thickness of 77 nm was formed on the surface of an 8-inch silicon wafer using a lower antireflection film forming agent (trade name “ARC29A”, manufactured by Nissan Chemical Industries, Ltd.). A radiation sensitive resin composition was applied onto the surface of this substrate by spin coating, and SB (Soft Bake) was performed on a hot plate at 100 ° C. for 60 seconds to form a 120 nm-thick photoresist film.
- ARC29A trade name “ARC29A”
- This photoresist film was exposed through a mask pattern using a full-field reduction projection exposure apparatus full-field reduction projection exposure apparatus (trade name “NSRS306C”, manufactured by NIKON). Thereafter, PEB was performed at 100 ° C. for 60 seconds, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution (hereinafter also referred to as “TMAH aqueous solution”) at 25 ° C. for 60 seconds, washed with water, and dried. A positive resist pattern was formed.
- the positive resist pattern is a one-to-one line and space with a line width of 90 nm formed through a mask for forming a one-to-one line and space with a target dimension of 90 nm.
- a scanning electron microscope (trade name “S9380”, manufactured by Hitachi High-Technologies Corporation) was used to measure the resist pattern formed by this method. This pattern forming method is defined as (P-1).
- Pattern formation method (P-2) A 75 nm-thick photoresist film is formed from a radiation-sensitive resin composition on a 12-inch silicon wafer on which a lower antireflection film is formed in the same manner as in the pattern formation method (P-1), and softened at 120 ° C. for 60 seconds. Bake (SB) was performed. Next, the upper layer film-forming composition (H) was spin-coated on the formed photoresist film, and PB (90 ° C., 60 seconds) was performed to form an upper layer film having a thickness of 90 nm.
- PEB post-baking
- This positive resist pattern is a 1: 1 line and space with a line width of 50 nm formed through a mask for forming a 50 nm line and 100 nm pitch with a target dimension.
- This pattern forming method is defined as (P-3).
- Example 24 Formation of resist pattern
- P-1 the pattern formation method
- T-1 the radiation-sensitive resin composition prepared in Example 6.
- the pattern shape and scum of the formed resist pattern were evaluated by the following method. The results are also shown in Table 4.
- Examples 25 to 46 Formation of resist pattern
- a resist pattern was formed in the same manner as in Example 24 except that the radiation-sensitive resin composition and the pattern forming method are shown in Table 4.
- the method shown in [Development Defect 2] is used.
- the method shown in [Development Defect 1] is used. Development defects when used for immersion exposure were evaluated. These evaluation results are shown in Table 4 together with the pattern shape and scum evaluation results.
- a film having a film thickness of 110 nm is formed from a radiation-sensitive resin composition on a 12-inch silicon wafer on which the lower antireflection film is formed, and soft baking (SB) is performed at 110 ° C. for 60 seconds. Went.
- post-baking (PEB) was performed at 95 ° C. for 60 seconds. Thereafter, development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution, washed with water, and dried to form a positive resist pattern.
- the exposure amount for forming a line and space pattern having a width of 45 nm was determined as the optimum exposure amount.
- a line-and-space pattern having a line width of 45 nm was formed on the entire surface of the wafer with this optimum exposure amount to obtain a defect inspection wafer.
- a scanning electron microscope (trade name “CC-4000”, manufactured by Hitachi High-Technologies Corporation) was used.
- the number of defects on the defect inspection wafer was measured using a high-resolution wafer defect measuring apparatus (trade name “KLA2810”, manufactured by KLA-Tencor). Furthermore, the measured defects were classified into those judged to be resist-derived and foreign matters derived from the outside. After classification, when the total number of defects (number of defects) determined to be from resist is 100 / wafer or more, it is evaluated as “C (slightly good)”, and 50 / wafer or more, less than 100 / wafer Was evaluated as “B (good)”, and the case of less than 50 / wafer was evaluated as “A (very good)”.
- [Development defect 2] The upper layer film-forming composition (H) is spin-coated on the film formed of the radiation-sensitive resin composition, and PB (90 ° C., 60 seconds) is performed to form an upper layer of 90 nm in thickness. A wafer for defect inspection was obtained in the same manner as in [Development defect 1] except that a film was formed.
- the number of defects on the defect inspection wafer was measured using the high resolution wafer defect measuring apparatus. Furthermore, the measured defects were classified into those judged to be resist-derived and foreign matters derived from the outside. After classification, when the total number of defects (number of defects) determined to be from resist is 100 / wafer or more, it is evaluated as “C (slightly good)”, and 50 / wafer or more, less than 100 / wafer Was evaluated as “B (good)”, and the case of less than 50 / wafer was evaluated as “A (very good)”.
- the radiation-sensitive resin compositions prepared in Examples 6 to 9 were excellent in the resist pattern cross-sectional shape rectangularity after development, and no scum was produced (Examples 24 to 27). Further, even when an upper layer film was formed and used for immersion exposure, development defects did not easily occur (Examples 28 to 31). Furthermore, the radiation-sensitive resin compositions prepared in Examples 10 to 21 have excellent resist pattern cross-sectional shape rectangularity after development, do not cause scum, and develop even if used for immersion exposure without forming an upper layer film. Defects were hardly generated (Examples 32 to 43).
- the resist pattern cross-sectional shape after development was not rectangular and scum was generated as compared with the radiation sensitive resin compositions prepared in Examples 10 to 21. It could be used as a radiation sensitive resin composition (Example 44).
- an upper layer film was formed and used for immersion exposure, development defects occurred more than the radiation-sensitive resin compositions prepared in Examples 10 to 21, but they could be used as radiation-sensitive resin compositions. (Example 45).
- the radiation sensitive resin composition prepared in Example 23 was used for immersion exposure without forming an upper layer film, the resist pattern cross-sectional shape after development was not rectangular and scum was generated.
- the radiation sensitive resin composition prepared in Example 22 was used for immersion exposure without forming an upper layer film, the resist pattern cross-sectional shape after development was not rectangular and scum was generated.
- Example 46 the radiation-sensitive resin composition prepared in Example 46.
- the radiation-sensitive resin composition of the present invention can be suitably used in semiconductor manufacturing processes that require increasingly finer patterns in the future.
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Abstract
Description
本発明のスルホニウム化合物は、後述する本発明の感放射線性樹脂組成物において酸発生剤として作用する成分、即ち、感放射線性樹脂組成物によって形成されたフォトレジスト膜が液浸露光用液体を介して露光された際に、露光部で酸を発生させる成分である。このスルホニウム化合物は、従来の酸発生剤に用いられる化合物と比較してアルカリ解離性基を有する点で大きく異なる。アルカリ解離性基は、アルカリ現像液と反応して極性基を生じる。この極性基が発生することで、現像液及びリンス液による当該スルホニウム化合物の凝集が抑えられ、溶け残りに由来する欠陥が生じ難くなると考えられる。
前記一般式(2)で表される基は、水酸基、アミノ基、カルボキシル基又はスルホキシル基がアルカリ解離性基によって修飾された基である。この一般式(2)で表される基はアルカリ水溶液と下記反応式(3)に示すような反応を生じ、極性基-AHを生じる。
前記一般式(1)中、R1~R3として表される基のうち、炭素数6~30の芳香族炭化水素基としては、ベンゼン、ナフタレンに由来する基等がある。また、脂肪族鎖状炭化水素基としては、メタン、エタン、n-ブタン、2-メチルプロパン、1-メチルプロパン、tert-ブタン、n-ペンタン等の直鎖状又は分岐状のアルキル基に由来する基等がある。更に、脂環式炭化水素基としては、シクロブタン、シクロペンタン、シクロヘキカン、シクロオクタン、ノルボルニル基、トリシクロデカン、テトラシクロドデカン、アダマンタン等の脂環式炭化水素に由来する基がある。
R10CpF2pSO3 - ・・・(4)
(一般式(4)中、R10は、水素原子、フッ素原子又は炭素数1~12の炭化水素基を示す。pは、1~10の整数を示す。)
R11SO3 - ・・・(5)
(一般式(5)中、R11は、水素原子、フッ素原子又は炭素数1~12の炭化水素基を示す。)
本発明の感放射線性樹脂組成物は、酸発生剤としての(A)化合物と、(B)重合体と、を含有するものである。本発明の感放射線性樹脂組成物は、現像後のレジストパターン断面形状の矩形性に優れ、スカムを生じにくい。特に、(A)化合物は、アルカリ解離性基を有することで現像液及びリンス液による凝集が抑えられ、欠陥の核となり難いと考えられるため、本発明の感放射線性樹脂組成物は、特に液浸露光に用いた場合でも現像欠陥を生じにくいという優れた効果を奏する。
酸発生剤は、放射線の照射により露光部で酸を発生するものである。本発明の感放射線性樹脂組成物は、酸発生剤として(A)化合物を含有している。なお、本発明の感放射線性樹脂組成物は、酸発生剤として(A)化合物のみを含有してもよいし、(A)化合物と他の酸発生剤(以下、「他の酸発生剤」ともいう)を組み合わせて含有してもよい。
(B)重合体としては、例えば、酸解離性基を有するアルカリ不溶性又はアルカリ難溶性の重合体であって、酸解離性基が解離したときにアルカリ易溶性となる重合体(以下、「(B1)重合体」ともいう)や、アルカリ現像液と親和性を示す官能基を1種以上有するアルカリ現像液に可溶な重合体(以下、「(B2)重合体」ともいう)がある。前記アルカリ現像液と親和性を示す官能基としては、例えば、フェノール性水酸基、アルコール性水酸基、カルボキシル基等の酸素原子含有官能基等が挙げられる。前記(B1)重合体は、ポジ型感放射線性樹脂組成物のベース樹脂として好適に用いることができる。また、前記(B2)重合体は、ネガ型感放射線性樹脂組成物のベース樹脂として好適に用いることができる。
(B1)重合体における酸解離性基とは、例えば、フェノール性水酸基、カルボキシル基、スルホン酸基等の酸性官能基中の水素原子を置換した基をいい、酸の存在下で解離する基をいう。このような酸解離性基の例としては、置換メチル基、1-置換エチル基、1-置換-n-プロピル基、1-分岐アルキル基、アルコキシカルボニル基、アシル基、環式酸解離性基等がある。
(一般式(9)~(11)中、R15は、水素原子、メチル基又はトリフルオロメチル基を示す。
一般式(9)中、複数のR16は、相互に独立に、水素原子、ヒドロキシル基、シアノ基又は-COOR19基を示す。但し、R19は、水素原子、炭素数1~4の直鎖状若しくは分岐状のアルキル基、又は炭素数3~20のシクロアルキル基を示す。
一般式(10)中、R17は、単結合、エーテル基、エステル基、カルボニル基、炭素数1~30の2価の脂肪族鎖状炭化水素基、炭素数3~30の2価の脂環式炭化水素基、炭素数6~30の2価の芳香族炭化水素基、又はこれらを組み合わせた2価の基を示す。RLcは、ラクトン構造を有する1価の有機基を示す。
一般式(11)中、複数のR18は、相互に独立に、炭素数4~20の1価の脂環式炭化水素基若しくはその誘導体、又は炭素数1~4の直鎖状若しくは分岐状のアルキル基を示す。但し、R18の少なくとも1つは脂環式炭化水素基又はその誘導体である。また、いずれか2つのR18が相互に結合してそれぞれが結合している炭素原子と共に炭素数4~20の2価の脂環式炭化水素基又はその誘導体を形成してもよい。)
本発明の感放射線性樹脂組成物は、高分子添加剤として(C)重合体を含有するものであることが好ましい。(B)重合体と(C)重合体を含有する感放射線性樹脂組成物を用いてフォトレジスト膜を形成した場合、(C)重合体の撥油性に起因して、フォトレジスト膜の表面に(C)重合体の分布が高くなる傾向がある。即ち、(C)重合体がフォトレジスト膜表面に偏在する。従って、フォトレジスト膜と液浸媒体を遮断することを目的とした上層膜を別途形成する必要がなく、液浸露光法に好適に用いることができる。
一般式(C1-1)中のRf1の例としては、少なくとも1つの水素原子がフッ素原子で置換された炭素数1~6の直鎖状又は分岐状の脂肪族炭化水素基や、少なくとも1つの水素原子がフッ素原子で置換された炭素数4~20の脂環式炭化水素基又はそれから誘導される基がある。
一般式(C1-2)及び(C1-3)中、R31は、水素原子又は1価の有機基を示す。1価の有機基としては炭素数1~30の1価の炭化水素基、酸解離性基やアルカリ解離性基等を挙げることができる。
-C(R32)3 ・・・(12)
(一般式(12)中、3つのR32は、一般式(11)中のR18と同じである。)
本発明の感放射線性樹脂組成物には、必要に応じて従来公知の添加剤を配合してもよい。添加剤としては、露光により酸発生剤から生じる酸のフォトレジスト膜中における拡散現象を制御し、非露光領域での好ましくない化学反応を抑制する作用を有する酸拡散制御剤が好ましい。このような酸拡散制御剤を配合することにより、感放射線性樹脂組成物の貯蔵安定性を向上させることができるとともに、解像度を更に向上させることができる。また、露光から現像処理までの引き置き時間(PED)の変動によるレジストパターンの線幅変化を抑えることもできる。そのため、プロセス安定性に極めて優れた感放射線性樹脂組成物を得ることができる。
X+Z- ・・・(D1-0)
(一般式(D1-0)中、X+は、一般式(D1-1)で表されるカチオン、又は一般式(D1-2)で表されるカチオンを示す。Z-は、OH-、RD1-COO-で表されるアニオン、RD1-SO3 -で表されるアニオン、又はRD1-N--SO2-RD21で表されるアニオンを示す。但し、RD1は、置換されていてもよいアルキル基、1価の脂環式炭化水素基、又はアリール基を示す。RD21は、置換されていてもよいフッ素化脂肪族鎖状炭化水素基、又は1価のフッ素化脂環式炭化水素基を示す。)
本発明の感放射線性樹脂組成物は、通常、使用時に各成分を溶剤(E)に溶解して均一溶液とし、その後、必要に応じて、例えば孔径0.2μm程度のフィルター等でろ過することにより、組成物溶液として調製される。
本発明のレジストパターン形成方法は、先ず、前記のようにして調製した組成物溶液を、回転塗布、流延塗布、ロール塗布等の適宜の塗布手段によって、例えば、シリコンウエハー、アルミニウムで被覆されたウエハー等の基板上に塗布することにより、フォトレジスト膜を形成する。その後、場合により予め加熱処理(以下、「PB」ともいう)を行った後、所定のマスクパターンを介して、フォトレジスト膜を露光する。
(A)スルホニル化合物の前駆体として、下記式(a1)に示す化合物(ジフェニル(4-(3,3,3-トリフルオロプロパノイルオキシ)フェニル)スルホニウムクロライド)を以下の方法により合成した。
下記式(A-1)に示す化合物ジフェニル(4-(3,3,3-トリフルオロプロパノイルオキシ)フェニル)スルホニウム-1,1,2,2,3,3,4,4,4-ノナフルオロブタン-1-スルホナートを以下の方法により合成した。
出発原料として1,1,2,2,3,3,4,4,4-ノナフルオロブタン-1-スルホン酸ナトリウムの代わりに2-(ビシクロ[2.2.1]2-ヘプタニル)-1,1,2,2-テトラフルオロエタンスルホン酸ナトリウムを用いて、実施例1と同様の方法で下記式(A-2)に示すジフェニル(4-(3,3,3-トリフルオロプロパノイルオキシ)フェニル)スルホニウム-2-(ビシクロ[2.2.1]2-ヘプタニル)-1,1,2,2-テトラフルオロエタンスルホナートを合成した。
出発原料として1,1,2,2,3,3,4,4,4-ノナフルオロブタン-1-スルホン酸ナトリウムの代わりに1,1-ジフルオロ-2-(1-アダマンチル)エタン-1-スルホン酸ナトリウムを用いて、実施例1と同様の方法で下記式(A-3)に示すジフェニル(4-(3,3,3-トリフルオロプロパノイルオキシ)フェニル)スルホニウム-1,1-ジフルオロ-2-(1-アダマンチル)エタン-1-スルホナートを合成した。
出発原料として1,1,2,2,3,3,4,4,4-ノナフルオロブタン-1-スルホン酸ナトリウムの代わりに6-(1-アダマンタンカルボニルオキシ)-1,1,2,2-テトラフルオロヘキサン-1-スルホン酸ナトリウムを用いて、実施例1と同様の方法で下記式(A-4)に示すジフェニル(4-(3,3,3-トリフルオロプロパノイルオキシ)フェニル)スルホニウム-6-(1-アダマンタンカルボニルオキシ)-1,1,2,2-テトラフルオロヘキサン-1-スルホナートを合成した。
出発原料としてジフェニル(4-(3,3,3-トリフルオロプロパノイルオキシ)フェニル)スルホニウムクロライドと1,1,2,2,3,3,4,4,4-ノナフルオロブタン-1-スルホン酸ナトリウムの代わりにそれぞれ、4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-ヘプタデカフルオロノナノイルオキシ)フェニル)ジメチルスルホニウムクロライドとトリフルオロメタンスルホン酸ナトリウムを用いて、実施例1と同様の方法で、下記式(A-5)に示す4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-ヘプタデカフルオロノナノイルオキシ)フェニル)ジメチルスルホニウム-トリフルオロメタンスルホナートを合成した。
下記式に示す化合物(M-1)~(M-4)を用いて(B)重合体を調製した。
化合物(M-1)16.4g(98mmol)、化合物(M-2)5.73g(24mmol)及び、化合物(M-4)21.74(98mmol)を、2-ブタノン100gに溶解し、更にジメチル2,2’-アゾビス(2-メチルプロピオネート)2.01gを投入した単量体溶液を準備した。50gの2-ブタノン及び化合物(M-3)6.07g(24mmol)を投入した500mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を、滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。
下記式に示す化合物(S-1)~(S-9)を用いて(C)重合体を調製した。
化合物(S-1)35.01g(208mmol)、及び化合物(S-4)14.99g(89mmol)を、2-ブタノン100gに溶解し、更にジメチル2,2’-アゾビス(2-メチルプロピオネート)3.91gを投入した単量体溶液を準備した。一方、500mLの三口フラスコに30gの2-ブタノンを投入し、30分窒素パージした後、反応釜を攪拌しながら80℃に加熱した。次いで、滴下漏斗を用い、予め準備しておいた単量体溶液を3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。
化合物の配合処方を表1に記載したこと以外は合成例3と同様にして(C-2)重合体及び(C-3)重合体を調製した。(C-2)重合体及び(C-3)重合体の物性値を併せて表1に記す。
化合物(S-5)22.26gと2,2-アゾビス(2-メチルイソプロピオン酸メチル)4.64gをメチルエチルケトン25gに予め溶解させた単量体溶液(i)、及び化合物(S-8)27.74gをメチルエチルケトン25gに予め溶解させた単量体溶液(ii)をそれぞれ準備した。一方、温度計及び滴下漏斗を備えた500mLの三口フラスコにメチルエチルケトン100gを投入し、30分間窒素パージした。窒素パージ後、フラスコ内をマグネティックスターラーで撹拌しながら80℃になるように加熱した。
化合物(S-8)46.95g(85mol%)と、2,2’-アゾビス-(2-メチルプロピオン酸メチル)6.91gをイソプロピルアルコール100gに溶解した単量体溶液を準備した。一方、温度計及び滴下漏斗を備えた500mLの三つ口フラスコにイソプロピルアルコール50gを投入し、30分間窒素パージした。窒素パージの後、フラスコ内をマグネティックスターラーで攪拌しながら80℃になるように加熱した。滴下漏斗を用い、予め準備しておいた単量体溶液を2時間かけて滴下した。
合成例6で調製した上層膜用重合体(1)7部、合成例7で調製した上層膜用重合体(2)93部、ジエチレングリコールモノエチルエーテルアセテート10部、4-メチル-2-ヘキサノール(以下、「MIBC」ともいう)10部、及びジイソアミルエーテル(以下、「DIAE」ともいう)90部を混合することで上層膜形成組成物(H)を調製した。
合成例2で調製した(B-1)重合体100部、実施例1で合成した(A-1)スルホニル化合物12.1部、(D-1)酸拡散制御剤1.5部、(E-1)溶剤1800部、(E-2)溶剤770部、及び(G-1)添加剤30部を混合して感放射線性樹脂組成物の組成物溶液(T-1)を調製した。
表2又は表3に示す配合処方にしたこと以外は実施例5と同様にして各感放射線性樹脂組成物の組成物溶液(T-2)~(T-18)を調製した。
(D-1):下記式(D-1)で表される化合物
(D-1):下記式(D-2)で表される化合物
(E-1):プロピレングリコールモノメチルエーテルアセテート
(E-2):シクロヘキサノン
(G-1):γ-ブチロラクトン
8インチのシリコンウエハー表面に、下層反射防止膜形成剤(商品名「ARC29A」、日産化学社製)を用いて、膜厚77nmの下層反射防止膜を形成した。この基板の表面に、感放射線性樹脂組成物をスピンコートにより塗布し、ホットプレート上にて、100℃で60秒間SB(SoftBake)を行い、膜厚120nmのフォトレジスト膜を形成した。
パターン形成方法(P-1)と同様に下層反射防止膜を形成した12インチシリコンウェハ上に、感放射線性樹脂組成物によって、膜厚75nmのフォトレジスト膜を形成し、120℃で60秒間ソフトベーク(SB)を行った。次に、形成したフォトレジスト膜上に、上層膜形成用組成物(H)をスピンコートし、PB(90℃、60秒)を行うことにより膜厚90nmの上層膜を形成した。その後、ArFエキシマレーザー液浸露光装置(商品名「NSR S610C」、NIKON社製)を用い、NA=1.3、ratio=0.800、Annularの条件により、マスクパターンを介して露光した。露光後、95℃で60秒間ポストベーク(PEB)を行った。その後、2.38%のTMAH水溶液により現像し、水洗し、乾燥して、ポジ型のレジストパターンを形成した。なお、このポジ型のレジストパターンは、ターゲット寸法が50nmライン100nmピッチ形成用のマスクを介して形成した線幅50nmの1:1のラインアンドスペースである。この方法で形成したレジストパターンの測長には走査型電子顕微鏡(商品名「CG-4000」、日立ハイテクノロジーズ社製)を用いた。このパターン形成方法を(P-2)とする。
パターン形成方法(P-1)と同様に下層反射防止膜を形成した12インチシリコンウェハ上に、感放射線性樹脂組成物によって、膜厚75nmのフォトレジスト膜を形成し、120℃で60秒間ソフトベーク(SB)を行った。次に、このフォトレジスト膜を、前記ArFエキシマレーザー液浸露光装置を用い、NA=1.3、ratio=0.800、Annularの条件により、マスクパターンを介して露光した。露光後、95℃で60秒間ポストベーク(PEB)を行った。その後、2.38%のTMAH水溶液により現像し、水洗し、乾燥して、ポジ型のレジストパターンを形成した。なお、このポジ型のレジストパターンは、ターゲット寸法が50nmライン100nmピッチ形成用のマスクを介して形成した線幅50nmの1:1のラインアンドスペースである。この方法で形成したレジストパターンの測長には走査型電子顕微鏡(「CG-4000」、日立ハイテクノロジーズ社製)を用いた。このパターン形成方法を(P-3)とする。
実施例6で調製した感放射線性樹脂組成物(T-1)を用い、パターン形成方法(P-1)によりレジストパターンを形成した。形成したレジストパターンについてのパターン形状及びスカムの評価を以下に示す方法にて行った。結果を表4に併せて示す。
感放射線性樹脂組成物及びパターン形成方法を表4に示す事とした以外は、実施例24と同様にレジストパターンの形成を行った。なお、実施例28~31及び実施例45については下記[現像欠陥2]に示す方法を用いて、実施例32~43及び実施例46については下記[現像欠陥1]に示す方法を用いて、液浸露光に用いた場合の現像欠陥の評価を行った。これらの評価結果をパターン形状及びスカムの評価結果と併せて表4に示す。
Claims (12)
- (A)下記一般式(1)で表されるスルホニウム化合物と、
(B)ベース樹脂となる重合体と
を含有する感放射線性樹脂組成物。
- (C)フッ素原子を有する重合体を更に含有する請求項1に記載の感放射線性樹脂組成物。
- 前記(C)フッ素原子を有する重合体の配合量が、前記(B)重合体100質量部に対して0.1~20質量部である請求項5に記載の感放射線性樹脂組成物。
- (1)請求項1に記載の感放射線性樹脂組成物を用いて基板上にフォトレジスト膜を形成する工程と、
(2)前記フォトレジスト膜を露光する工程と、
(3)露光された前記フォトレジスト膜を現像してレジストパターンを形成する工程とを有するレジストパターン形成方法。 - 前記(2)工程が、前記フォトレジスト膜を液浸露光する工程である請求項7に記載のレジストパターン形成方法。
- 下記一般式(1)で表されるスルホニウム化合物。
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JP2013041269A (ja) * | 2011-07-19 | 2013-02-28 | Sumitomo Chemical Co Ltd | レジスト組成物及びレジストパターンの製造方法 |
JP2013166748A (ja) * | 2012-01-19 | 2013-08-29 | Sumitomo Chemical Co Ltd | 塩、レジスト組成物及びレジストパターンの製造方法 |
JP2014122204A (ja) * | 2012-10-26 | 2014-07-03 | Rohm & Haas Electronic Materials Llc | 光酸発生化合物およびそれを含むフォトレジスト組成物、そのフォトレジストを含むコーティングされた物品、並びに物品を製造する方法 |
US20150093703A1 (en) * | 2013-09-30 | 2015-04-02 | Jsr Corporation | Radiation-sensitive resin composition and resist pattern-forming method |
JP2018048117A (ja) * | 2016-09-07 | 2018-03-29 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
JP7489221B2 (ja) | 2019-04-19 | 2024-05-23 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
JP7489222B2 (ja) | 2019-04-19 | 2024-05-23 | 住友化学株式会社 | カルボン酸塩、カルボン酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
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JP2013041269A (ja) * | 2011-07-19 | 2013-02-28 | Sumitomo Chemical Co Ltd | レジスト組成物及びレジストパターンの製造方法 |
JP2013166748A (ja) * | 2012-01-19 | 2013-08-29 | Sumitomo Chemical Co Ltd | 塩、レジスト組成物及びレジストパターンの製造方法 |
JP2014122204A (ja) * | 2012-10-26 | 2014-07-03 | Rohm & Haas Electronic Materials Llc | 光酸発生化合物およびそれを含むフォトレジスト組成物、そのフォトレジストを含むコーティングされた物品、並びに物品を製造する方法 |
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JP2018048117A (ja) * | 2016-09-07 | 2018-03-29 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
JP6991786B2 (ja) | 2016-09-07 | 2022-02-03 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
JP7489221B2 (ja) | 2019-04-19 | 2024-05-23 | 住友化学株式会社 | 塩、酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
JP7489222B2 (ja) | 2019-04-19 | 2024-05-23 | 住友化学株式会社 | カルボン酸塩、カルボン酸発生剤、レジスト組成物及びレジストパターンの製造方法 |
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US20130045446A1 (en) | 2013-02-21 |
KR20130006431A (ko) | 2013-01-16 |
JPWO2011108667A1 (ja) | 2013-06-27 |
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