WO2007032181A1 - Composition de photoresist negatif, et procede de formation d’un motif de photoresist - Google Patents

Composition de photoresist negatif, et procede de formation d’un motif de photoresist Download PDF

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Publication number
WO2007032181A1
WO2007032181A1 PCT/JP2006/316326 JP2006316326W WO2007032181A1 WO 2007032181 A1 WO2007032181 A1 WO 2007032181A1 JP 2006316326 W JP2006316326 W JP 2006316326W WO 2007032181 A1 WO2007032181 A1 WO 2007032181A1
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group
alkyl group
component
structural unit
atom
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PCT/JP2006/316326
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English (en)
Japanese (ja)
Inventor
Ayako Kusaka
Jun Iwashita
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Tokyo Ohka Kogyo Co., Ltd.
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Publication of WO2007032181A1 publication Critical patent/WO2007032181A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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

Definitions

  • the present invention relates to a negative resist composition and a resist pattern forming method.
  • a resist film having a resist material strength is formed on a substrate, and light, electron beam, etc. are passed through a mask on which a predetermined pattern is formed on the resist film.
  • a step of forming a resist pattern having a predetermined shape on the resist film is performed by performing selective exposure with the radiation and developing. Resist materials that change their properties so that the exposed portion dissolves in the developer are positive types, and resist materials that change their properties so that the exposed portions do not dissolve in the developer are negative types.
  • the wavelength of an exposure light source is generally shortened.
  • the power used in the past typically ultraviolet rays such as g-line and i-line
  • KrF excimer laser and ArF excimer laser have now begun mass production of semiconductor devices using KrF excimer laser and ArF excimer laser.
  • these excimer lasers have shorter wavelength excimer lasers, electron beams, EUV (
  • negative resist materials used in processes using i-line or KrF excimer laser light (248nm) as the light source include acid generators and alkali-soluble resin such as novolac resin polyhydroxystyrene and melamine.
  • alkali-soluble resin such as novolac resin polyhydroxystyrene and melamine.
  • a chemically amplified negative resist composition containing a combination with amino resin such as urea resin is used (for example, Patent Document 1).
  • a resin component having a carboxy group, an alcoholic hydroxyl group having improved transparency with respect to the ArF excimer laser.
  • a cross-linking agent having Negative resist compositions containing a phosphoric acid generator have been proposed. This is a type in which the resin component is changed to insoluble from an alkali-soluble solution by the reaction of the carboxy group of the resin component and the alcoholic hydroxyl group of the crosslinking agent by the action of the acid generated from the acid generator. is there.
  • a negative resist composition comprising a resin component having both a carboxy group or a carboxylic acid ester group and an alcoholic hydroxyl group, and an acid generator, wherein
  • the resin component is made insoluble from an alkali-soluble resin by reacting it with an alcoholic hydroxyl group by the action of an acid generated by an acid generator.
  • Patent Document 1 Japanese Patent Publication No. 8-3635
  • Patent Document 2 JP 2000-206694 A
  • Non-Patent Document 1 Journal ⁇ Ob ⁇ Photopolymer ⁇ Science and Technology (J. Photopolym. Sci. Tech.), No. 10, No. 4, pp. 579-584 (1997)
  • Non-Patent Literature 2 Journal ⁇ Ob ⁇ Photopolymer ⁇ Science ⁇ Technology (J.Photopolym. Sci. Tech.), 11th, No. 3, pp. 507-512 (1998)
  • Non-special literature 3 SPIE Advances in Resist Technology and Processing X
  • Non-Patent Document 4 SPIE Advances in Resist technology and Processing XI X, Vol. 4690 p94- 100 (2002)
  • the bottom of the resist pattern bites at the substrate interface depending on the type of the substrate.
  • the resist pattern shape is likely to be defective, such as a decrease in performance.
  • a so-called “inorganic substrate” is used, such a problem is likely to occur.
  • the “inorganic substrate” has a nitrogen-containing layer such as a so-called SiON substrate.
  • a nitrogen-containing layer such as a so-called SiON substrate.
  • the nitrogen-containing layer is usually provided as an insulating layer, a metal layer or the like on the substrate according to the purpose of use, and contains nitrogen.
  • the insulating layer include silicon oxynitride (SiON), silicon nitride (SiN), and tetratetranitride (SiN).
  • the metal layer examples include titanium nitride (TiN).
  • the nitrogen-containing layer is formed by vapor deposition or the like on a substrate such as a silicon substrate.
  • a substrate having such a nitrogen-containing layer is called, for example, a “nitrogen-containing substrate”.
  • a substrate in which a layer mainly composed of atoms other than silicon is formed on the substrate as described above is called an “inorganic substrate”.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a negative resist composition and a resist pattern forming method capable of forming a resist pattern having a good shape.
  • the present invention employs the following configuration.
  • the first aspect (aspect) of the present invention comprises (A) an alkali-soluble resin component, (B) an acid generator component that generates an acid by exposure, and (C) a negative type resist containing a crosslinking agent component.
  • a negative resist composition characterized in that the (C) crosslinking agent component contains an epoxy crosslinking agent (C1).
  • the second aspect of the present invention includes a step of forming a resist film on a substrate using the negative resist composition of the first aspect, a step of exposing the resist film,
  • exposure is a concept including general irradiation of radiation.
  • the negative resist composition of the present invention comprises (A) an alkali-soluble resin component (hereinafter abbreviated as (A) component), (B) an acid generator component that generates an acid upon exposure (hereinafter referred to as (B) And (C) a crosslinking agent component (hereinafter abbreviated as component (C)).
  • the powerful negative resist composition is alkali-soluble before exposure. When acid is generated from the component (B) by exposure, the acid acts to cause crosslinking between the components (A) and (C). Occurs and becomes insoluble in alkali.
  • a negative resist pattern can be formed by alkali development.
  • the component (A) is not particularly limited, and those conventionally proposed as a resin component for chemically amplified resists can be used.
  • the component (A) examples include a structural unit (al) containing an aliphatic cyclic group having a fluorinated hydroxyalkyl group (hereinafter abbreviated as a structural unit (al)) and a hydroxyl group-containing aliphatic. It is preferable to contain a copolymer containing the structural unit (a2) derived from an acrylate ester containing a cyclic group (hereinafter abbreviated as the structural unit (a2)).
  • the copolymer has a cyclic structure and an acrylic acid power-derived structural unit (a3) having an alcoholic hydroxyl group in the side chain (hereinafter abbreviated as the structural unit (a3)).
  • a copolymer (A1) (hereinafter sometimes referred to as component (A1)).
  • the “structural unit” means a monomer unit (monomer unit) constituting the resin component (polymer).
  • substituents include a halogen atom, an alkyl group, and a halogenoalkyl group.
  • “Acrylic acid esters” are not only acrylic acid esters in which a hydrogen atom is bonded to the carbon atom at the a position, but also hydrogen atoms bonded to the carbon atom at the a position are substituted with other substituents.
  • the concept includes an acrylic ester.
  • other substituents include a halogen atom, an alkyl group, and a halogenoalkyl group.
  • the carbon atom at the arrangement position means a carbon atom to which a carbonyl group is bonded, unless otherwise specified.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
  • “Acrylic acid-derived structural unit” means a structural unit formed by cleavage of an ethylenic double bond of acrylic acid.
  • a structural unit derived from an acrylate ester means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
  • alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
  • the alkyl group is preferably a lower alkyl group having 1 to 5 carbon atoms.
  • alkyl group as the substituent at the ⁇ -position, specifically, methyl group, ethyl group, propyl group, isopropyl group, ⁇ -butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group And a lower linear or branched alkyl group such as a neopentyl group.
  • Bonded to the ⁇ - position of the acrylate ester is preferably a hydrogen atom, a halogen atom, a lower alkyl group or a halogenated lower alkyl group, a hydrogen atom, a fluorine atom, a lower alkyl group or a fluorinated lower group.
  • a hydrogen atom or a methyl group is more preferred in view of industrial availability.
  • “lower” preferably represents 1 to 5 carbon atoms.
  • the structural unit (al) contains an aliphatic cyclic group having a fluorinated hydroxyalkyl group. By including the structural unit (al), resist swelling is suppressed and resolution is improved.
  • a fluorinated hydroxyalkyl group is a group in which a part or all of the hydrogen atoms bonded to the carbon atom of the alkyl group is substituted with a fluorine atom in the alkyl group having a hydroxy group (hydroxyl group). is there. In powerful groups, fluorine atoms can easily release hydrogen atoms of hydroxyl groups!
  • the alkyl group is preferably linear or branched.
  • the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 20 forces S, and most preferably 4 to 12 with 4 to 12 being more preferable.
  • the number of hydroxyl groups is not particularly limited, but it is preferably 1 or 2 and more preferably S.
  • a fluorinated hydroxyalkyl group a carbon atom to which a hydroxyl group is bonded (in this case, the ⁇ -position carbon atom of the hydroxyalkyl group) is bonded to a fluorinated alkyl group and ⁇ or a fluorine atom.
  • the fluorinated alkyl group bonded to the ⁇ -position is preferably such that all of the hydrogen atoms of the alkyl group are substituted with fluorine.
  • aliphatic in the “aliphatic cyclic group having a fluorinated hydroxyalkyl group” is a relative concept to aromaticity, and refers to a group, compound, etc. that does not have aromaticity. Defined as meaning.
  • the aliphatic cyclic group may be monocyclic or polycyclic.
  • “Monocyclic aliphatic cyclic group” means a monocyclic group having no aromaticity
  • “polycyclic aliphatic cyclic group” means a polycyclic group having no aromaticity. Means a group. In the structural unit (al), the aliphatic cyclic group is preferably polycyclic.
  • the aliphatic cyclic group is a hydrocarbon group composed of carbon and hydrogen (alicyclic group), and a part of the carbon atoms constituting the ring of the alicyclic group is an oxygen atom, nitrogen atom, sulfur atom, etc. Heterocyclic groups and the like substituted with a tetro atom are included.
  • an alicyclic group is preferable.
  • the aliphatic cyclic group may be either saturated or unsaturated, but is preferably saturated because it is highly transparent to ArF excimer laser, etc., and has excellent resolution and depth of focus (DOF). .
  • the aliphatic cyclic group preferably has 5 to 15 carbon atoms.
  • aliphatic cyclic group examples include the following.
  • examples of the monocyclic group include groups in which two or more hydrogen atoms have been removed from a cycloalkane including a hydrogen atom substituted with a fluorinated hydroxyalkyl group (hereinafter the same). More specifically, a group obtained by removing two or more hydrogen atoms from cyclopentane or cyclohexane is mentioned, and a group obtained by removing two hydrogen atoms from cyclohexane is preferred.
  • polycyclic group examples include groups in which two or more hydrogen atoms have been removed, such as bicycloalkane, tricycloalkane, and tetracycloalkane. More specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
  • a group in which two hydrogen atoms are removed from norbornane is particularly preferable.
  • the structural unit (al) is a structural unit derived from acrylic acid power.
  • a structure in which the above aliphatic cyclic group is bonded (a structure in which the hydrogen atom of the carboxy group of acrylic acid is substituted with the above aliphatic cyclic group) is preferred.
  • the structural unit (al) more specifically, the structural unit (al 1) represented by the following general formula (I) is preferable.
  • R represents a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group; and s, t and t ′ each independently represents an integer of 1 to 5. ]
  • R is a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group.
  • the halogen atom, alkyl group or halogenated alkyl group of R is the same as the halogen atom, alkyl group or halogenated alkyl group which may be bonded to the ⁇ - position of the acrylate ester.
  • halogen atom for R examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
  • alkyl group for R a lower alkyl group having 5 or less carbon atoms is preferred.
  • Group, neopentyl group and the like, and methyl group is preferable.
  • the halogenated alkyl group of R is preferably a group in which one or more hydrogen atoms of a lower alkyl group having 5 or less carbon atoms are substituted with a halogen atom.
  • Specific examples of the alkyl group are the same as described above.
  • the hydrogen atom substituted with the halogen atom may be a part or all of the hydrogen atoms constituting the alkyl group.
  • R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group from the viewpoint of industrial availability.
  • Each s is independently an integer of 1 to 5, preferably an integer of 1 to 3, with 1 being most preferred.
  • t is an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is most preferable.
  • t ′ is an integer of 1 to 3, preferably an integer of 1 to 2, and 1 is most preferable.
  • a 2-norbornyl group or a 3-norbornyl group is bonded to the terminal of the ruboxy group of (oc-lower alkyl) acrylic acid. It is preferable to!
  • the fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.
  • one type or a mixture of two or more types can be used as the structural unit (al).
  • the amount of the structural unit (al) is, (A1) relative to the combined total of all structural units constituting the component 10-90 Monore 0/0 force S
  • Percentage of structural unit (al) When the ratio is above the lower limit of the above range, the swelling of the resist is suppressed and the resolution is improved. When the ratio is below the upper limit, the balance with other structural units is achieved. Is good.
  • the structural unit (a2) is a structural unit derived from an acrylate ester containing a hydroxyl group-containing aliphatic cyclic group.
  • the hydroxyl group (alcoholic hydroxyl group) of this structural unit (a2) becomes the component (B) of the acid generated. Due to the action, it reacts with the component (C), whereby the component (A1) is changed to an insoluble property that is soluble in an alkali developer.
  • Hydroxyl group-containing aliphatic cyclic group is a group in which a hydroxyl group is bonded to an aliphatic cyclic group.
  • the number of hydroxyl groups bonded to an aliphatic cyclic group is 1 to Three is preferred, more preferably one.
  • the aliphatic cyclic group may be monocyclic or polycyclic, but is preferably a polycyclic group.
  • An alicyclic hydrocarbon group is preferred. Moreover, it is preferable that it is saturated.
  • the aliphatic cyclic group preferably has 5 to 15 carbon atoms.
  • aliphatic cyclic group (the state before the hydroxyl group is bonded) include the same aliphatic cyclic groups as those described above for the structural unit (a1).
  • a cyclohexyl group, an adamantyl group, a norbornyl group, and a tetracyclododecanyl group are preferred because they are commercially available. Yes. Of these, a cyclohexyl group and an adamantyl group are preferred, and an adamantyl group is particularly preferred.
  • a linear or branched alkyl group having 1 to 4 carbon atoms may be bonded to the aliphatic cyclic group.
  • the hydroxyl group-containing aliphatic cyclic group is preferably bonded to the ester group (C (O) 2 O 3) of the acrylate ester.
  • substituents may be bonded to the ⁇ -position ( ⁇ -position carbon atom) of the acrylate ester instead of the hydrogen atom.
  • substituents include an alkyl group, a halogenoalkyl group, and a halogen atom.
  • a structural unit (a2) for example, a structural unit (a21) represented by the following general formula (2) is preferable.
  • R is as defined above; R ′ is a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 5 carbon atoms; q is an integer of 1 to 3].
  • R is the same as described in the general formula (I).
  • the alkyl group of R ′ has the same meaning as the alkyl group of R.
  • R and R ′ are most preferably hydrogen atoms.
  • q is an integer of 1 to 3, and is preferably 1.
  • the bonding position of the hydroxyl group is not particularly limited, but bonded to the position 3 of the adamantyl group. It is preferable.
  • one type or a mixture of two or more types can be used as the structural unit (a2).
  • the proportion of the structural unit (a2), (A1) relative to the combined total of all structural units constituting the component 10-70 Monore 0/0 force S Preferably, 10-50 Monore 0/0 force more preferably S, 20 to 40 Monore 0/0 force S more preferred.
  • Percentage of structural unit (a2) The effect of containing structural unit (a2) is obtained by being above the lower limit of the above range, and the balance with other structural units is good by being below the upper limit. is there.
  • the component (A1) is a structural unit derived from acrylic acid having no cyclic structure and having an alcoholic hydroxyl group in the side chain ( a3).
  • the alcoholic hydroxyl group of the structural unit (a3) is generated from the component (B) together with the hydroxyl group of the structural unit (a2). It reacts with component (C) by the action of acid.
  • the component (A1) is easily changed to an insoluble property in addition to a property soluble in an alkali developer, and an effect of improving the resolution can be obtained. Moreover, film loss can be suppressed.
  • the controllability of the crosslinking reaction during pattern formation is improved. Furthermore, there is a tendency to increase the film density. Thereby, there exists a tendency for heat resistance to improve. Furthermore, etching resistance is improved.
  • No cyclic structure means having no aliphatic cyclic group or aromatic group.
  • the structural unit (a3) is clearly distinguished from the structural unit (a2) by not having a cyclic structure.
  • Examples of the structural unit having an alcoholic hydroxyl group in the side chain include a structural unit having a hydroxyalkyl group.
  • hydroxyalkyl group examples include those similar to the hydroxyalkyl group in the “fluorinated hydroxyalkyl group” mentioned in the structural unit (al).
  • the hydroxyalkyl group may be directly bonded to the ⁇ -position carbon atom of the main chain (the portion where the ethylenic double bond of acrylic acid is cleaved), or may be bonded to the carboxy group of acrylic acid.
  • An ester may be formed by substitution with a hydrogen atom. In the structural unit (a3), it is preferable that at least one or both of these are present.
  • an alkyl group, a halogenated alkyl group, or a halogen atom may be bonded to the ⁇ -position carbon atom in place of the hydrogen atom.
  • a structural unit (a3) a structural unit (a31) represented by the following general formula (3) is preferable because of excellent effects of the present invention.
  • R 1 is a hydrogen atom, an alkyl group, a halogenated alkyl group, a halogen atom or a hydroxyalkyl group
  • R 2 is a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 2 At least one is a hydroxyalkyl group.
  • the hydroxyalkyl group in R 1 is preferably a hydroxyalkyl group having 10 or less carbon atoms, and is desirably linear or branched, and more preferably a C2-C8 hydride.
  • a droxyalkyl group most preferably a hydroxymethyl group or a hydroxyethyl group.
  • the number of hydroxyl groups and the bonding position are not particularly limited, but it is usually one and preferably bonded to the end of the alkyl group.
  • the alkyl group in R 1 is preferably an alkyl group having 10 or less carbon atoms, more preferably an alkyl group having 2 to 8 carbon atoms, and most preferably an ethyl group or a methyl group.
  • the halogenoalkyl group in R 1 is preferably a lower alkyl group having 5 or less carbon atoms (preferably an ethyl group or a methyl group), and a part or all of the hydrogen atoms are halogen atoms (preferably fluorine atoms). A substituted group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom is preferable.
  • Examples of the alkyl group and hydroxyalkyl group for R 2 include the same as the alkyl group and hydroxyalkyl group for R 1 .
  • a structural unit represented by the general formula (3) specifically, a structural unit derived from ⁇ (hydroxyalkyl) acrylic acid (here, a structural unit derived from an acrylate ester) A) (a) a structural unit derived from (hydroxyalkyl) acrylic acid alkyl ester, and (a) a structural unit derived from alkyl) acrylic acid hydroxyalkyl ester.
  • the structural unit (a3) includes a structural unit derived from ⁇ (hydroxyalkyl) alkyl ester ether, it is preferable to improve the effect and improve the film density.
  • a (hydroxymethyl) acrylate ester or ⁇ (hydroxymethyl) -acrylic acid methyl ester is also preferred.
  • crosslinking efficiency it is preferable in terms of crosslinking efficiency to include a structural unit derived from the structural unit (a3) force (a alkyl) acrylic acid hydroxyalkyl ester.
  • a structural unit from which ⁇ -methyl-hydroxyacrylate ester or ⁇ -methyl-hydroxymethyl ester ester is also preferred is preferable.
  • the structural unit (a3) can be used alone or in combination of two or more.
  • Proportional power of structural unit (a3) The effect of containing structural unit (a3) is obtained by being above the lower limit of the above range, and the balance with other structural units is good by being below the upper limit. It is.
  • the component (A1) may have other structural units that can be copolymerized as structural units other than the structural units (al) to (a3).
  • structural units that have been conventionally used in known resin components for chemically amplified resist compositions can be used.
  • acrylate ester power containing a rataton-containing monocyclic or polycyclic group can also be used.
  • the derived structural unit (a4) can be mentioned.
  • the lathetone-containing monocyclic or polycyclic group of the structural unit (a4) is used for forming a resist film, it increases the adhesion of the resist film to the substrate or increases the hydrophilicity with the developer. It is effective above. In addition, the effect of suppressing swelling is improved.
  • Rataton here means one ring containing the -o-c (o) structure, and this is counted as one ring of eyes. Therefore, in the case of only a rataton ring, it is called a monocyclic group, and in the case of having another ring structure, it is called a polycyclic group regardless of the structure.
  • one or more hydrogen atoms of the latatatone-containing monocyclic or polycyclic group are substituted with a fluorinated hydroxyalkyl group! /, To do.
  • any structural unit can be used without any particular limitation as long as it has a rataton ring having both such an ester structure (—O 2 —C (O) —) and a ring structure.
  • the ratatone-containing monocyclic group include groups in which y-peptidone rataton force hydrogen atom is removed.
  • the latatatone-containing polycyclic group include groups in which a bicycloalkane, tricycloalkane, or tetracycloalkane having a latathone ring has one hydrogen atom removed.
  • substituents may be bonded to the ⁇ -position ( ⁇ -position carbon atom) instead of a hydrogen atom.
  • Preferred examples of the substituent include an alkyl group, a halogenated alkyl group, and a halogen atom.
  • examples of the structural unit (a4) include structural units represented by general formulas (a4-l) to (a4-5) shown below.
  • R is the same as described above.
  • R ′ is independently a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is an integer of 0 or 1.
  • R ′ is preferably a hydrogen atom in view of industrial availability.
  • structural unit (a4) units represented by general formulas (a4-2) to (a4-3) are most preferable.
  • one type may be used alone, or two or more types may be used in combination.
  • the proportion of the structural unit (a4) in the component (A1) is 10 to 70 based on the total of all the structural units constituting the component (A1). preferably mol%, and most preferably 10 to 40 mole 0/0, more preferably tool 10-25 mol 0/0.
  • the proportion of the structural unit (a4) is equal to or higher than the lower limit of the above range, the effect of including the structural unit (a4) is obtained, and when the proportion is lower than the upper limit, the balance with other structural units is obtained. Is good.
  • the component (A1) is particularly preferably a copolymer having the structural units (al) to (a3) as main components.
  • the “main component” means that the total of the structural units (al) to (a3) is 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more. is there.
  • (A1) component the structural unit (al)
  • a copolymer also structural unit (a2) and the structural units (a 3) power.
  • component (A1) those containing a combination of structural units such as the following formula (A1-11) are particularly preferable.
  • the mass average molecular weight of component (A1) (Mw; mass average molecular weight in terms of polystyrene by gel permeation chromatography) is preferably 2000 to 30000, more preferably 2000 to 10000, and still more preferably 3000 to 8000. . By setting it within this range, a good dissolution rate with respect to an anodically developing solution can be obtained, which is preferable from the viewpoint of high resolution.
  • the mass average molecular weight is low in this range, and good characteristics tend to be obtained.
  • the dispersity (MwZ number average molecular weight (Mn)) is preferably 1.0 to 5.0 force S, more preferably 1.0 to 2.5 force.
  • the component (A1) can be obtained, for example, by subjecting a monomer for deriving each structural unit to radical polymerization by a conventional method.
  • one or more of the above components (A1) can be mixed and used.
  • component (A1) In addition to the component (A1), other polymer compounds known for use in negative resist compositions, such as hydroxystyrene resin, novolac resin, acrylic resin, and the like must be included in the component (A). Is also possible.
  • the proportion of the component (A1) in the component (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. And 100% by mass is most preferable.
  • the component (B) is not particularly limited, and those that have been proposed as acid generators for chemical amplification resists can be used.
  • an acid generator Sodium salt acid generators such as ododonium salt and sulfo-um salt, oxime sulfonate acid generators, bisalkyl or bisarylsulfol diazomethanes, poly (bissulfol) diazomethanes, etc.
  • diazomethane acid generators nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.
  • an acid generator represented by the following general formula (b-0) can be suitably used.
  • 1 represents a linear, branched, or cyclic alkyl group, or a linear, branched, or cyclic fluorinated alkyl group
  • R 52 represents a hydrogen atom, a hydroxyl group, or a halogen atom
  • R 53 may have a substituent.
  • U is an integer from 1 to 3.
  • R 51 represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • the cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and still more preferably 6 to C: L0.
  • the fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
  • the fluorination rate of the alkyl fluoride group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. In particular, it is preferable to replace all hydrogen atoms with fluorine atoms because the strength of the acid is increased.
  • R 51 is most preferably a linear alkyl group or a fluorinated alkyl group.
  • R 52 is a hydrogen atom, a hydroxyl group, a halogen atom, are straight or branched chain alkyl group, a linear or branched Harogeni spoon alkyl group or a linear or branched ⁇ alkoxy group, .
  • examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms.
  • the alkyl group here are the same as the “alkyl group” in R 52 .
  • the halogen atom to be substituted include the same as those described above for the “norogen atom”.
  • the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
  • R 52 is preferably a hydrogen atom.
  • R 53 may have a substituent but may be an aryl group, and the structure of the basic ring (matrix ring) may be a naphthyl group, a phenyl group, an anthracene group, or the like. From the viewpoint of the effect of the present invention and the absorption of exposure light such as ArF excimer laser, the phenyl group is desirable.
  • substituents examples include a hydroxyl group and a lower alkyl group.
  • the lower alkyl group is linear or branched, and preferably has 5 or less carbon atoms, and particularly preferably a methyl group.
  • aryl group for R 53 those having no substituent are more preferable.
  • u is an integer of 1 to 3, 2 or 3 is preferred and 3 is particularly desirable.
  • Preferred examples of the acid generator represented by the general formula (b-0) include the following.
  • the acid generator represented by the general formula (b-0) can be used alone or in combination of two or more.
  • acid salt generators of the acid generator represented by the general formula (b-0) include, for example, the following general formula (b-1) or (b-2).
  • the compound to be used is also preferably used.
  • R 1 " ⁇ 3 ", R 5 "to R 6 " each independently represents an aryl group or an alkyl group;
  • R 4 " represents a linear, branched or cyclic alkyl group or a fluorinated alkyl. Represents at least one of,, ⁇ "represents an aryl group, and at least one of R 5 " to R 6 "represents an aryl group.
  • the most preferable aryl group is not particularly limited, for example, an aryl group having 6 to 20 carbon atoms.
  • some or all of the hydrogen atoms may or may not be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.
  • an aryl group of 6 to L0 is preferable because it can be synthesized at low cost. Specific examples include a phenyl group and a naphthyl group.
  • alkyl group on which the hydrogen atom of the aryl group may be substituted are a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, which are preferably alkyl groups having 1 to 5 carbon atoms. It is most preferred.
  • alkoxy group that may be substituted with a hydrogen atom of the aryl group, a methoxy group and an ethoxy group are preferred, with an alkoxy group having 1 to 5 carbon atoms being preferred.
  • the halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
  • the “ ⁇ ” alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, A decanyl group and the like can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.
  • R lw to R 3 ′′ are a phenol group.
  • R 4 ′′ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
  • the linear or branched alkyl group preferably has 1 to carbon atoms: LO. it is most preferred that 1-8 is a further and preferred instrument 1 to 4 carbon atoms.
  • the carbon number is 4 to 10 which is preferable to be 15 and the carbon number 6 to 10 is more preferable.
  • the fluorinated alkyl group preferably has 1 to C: LO, preferably 1 to C.
  • the fluorination rate of the alkyl fluoride group is preferably 10 to
  • R 4 ′′ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.
  • R 5 ′′ to R 6 ′′ each independently represents an aryl group or an alkyl group. Of R 5, ⁇ ⁇ R 6 , at least one represents an aryl group. All of R 5 ′′ to R 6 , are preferably aryl groups.
  • Examples of the aryl group of R 5 “to R 6 " include the same as the aryl group of,, ⁇ "
  • Examples of the alkyl group for R 5 ′′ to R 6 ′′ include the same as the alkyl group for R 1 ′′ to R 3 ′′. Among these, R 5 ′′ to R 6 ′′ are all phenyl groups. Most preferred. Those similar to - "(1 b) R 4 in the formula is as" the like R 4 of formula (b-2) in.
  • sodium salt acid generators represented by the formulas (b-1) and (b-2) include trifluoromethanesulfonate or nonafluorobutanesulfonate of diphlo-rhodonium, Bis (4-tert-butylphenol) trifluoromethane sulfonate or nonafluorobutane sulfonate, trifluoromethane sulfonate of trifluorosulfone, heptafluoropropane sulfonate or nonafluorolob Tansusulfonate, tri (4 methylphenol) sulfurium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfotrifluoromethane Lomethanesulfonate and its heptafluoropropanesulfonate Or its non
  • ohmic salts in which the ionic part of these ohmic salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.
  • the anion part is replaced with a caron part represented by the following general formula (b-3) or (b-4).
  • a -um salt-based acid generator can also be used (the cation moiety is the same as (b-1) or (b-2)).
  • X represents a C 2-6 alkylene group in which at least one hydrogen atom is replaced by a fluorine atom; ⁇ ", ⁇ "each independently represents at least one hydrogen atom is fluorine. Represents an alkyl group having 1 to 10 carbon atoms substituted with an atom.
  • X is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5, most preferably 3 carbon atoms.
  • ⁇ "and ⁇ " are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the carbon number of the alkyl group is 1 to: LO, preferably Has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
  • the carbon number of the alkylene group of X "or the carbon number of the alkyl group of ⁇ " and ⁇ " is preferably as small as possible because it has good solubility in the resist solvent within the above carbon number range. ⁇ .
  • an alkylene group of X "or an alkyl group of ⁇ " and ⁇ " is substituted with a fluorine atom.
  • the proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to: L00%, more preferably 90 to: L00%, and most preferably all hydrogen atoms are fluorine atoms.
  • the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and generates an acid upon irradiation with radiation. It is what has.
  • Such oxime sulfonate acid generators are widely used for chemically amplified resist compositions, and can be arbitrarily selected and used.
  • R 31 and R 32 each independently represents an organic group.
  • the organic group of R 31 and R 32 is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc. ) Etc.).
  • an atom other than a carbon atom for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc. ) Etc.
  • a linear, branched or cyclic alkyl group or aryl group is preferable.
  • These alkyl groups and aryl groups may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.
  • “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
  • the alkyl group preferably has 1 to 20 carbon atoms.
  • the carbon number 1 to 10 is more preferable.
  • the carbon number 1 to 8 is more preferable, and the carbon number 1 to 4 is particularly preferable.
  • a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
  • the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is replaced with a halogen atom.
  • a fully halogenated alkyl group means an alkyl group in which all of the hydrogen atoms are replaced with halogen atoms.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group! /.
  • the aryl group is preferably 4 to 20 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, more preferably LO.
  • a partially or completely halogenated aryl group is particularly preferable.
  • a partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and a completely halogenated aryl group means that all hydrogen atoms are halogenated.
  • R 31 is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
  • organic group for R 32 a linear, branched or cyclic alkyl group, aryl group or cyan group is preferable.
  • alkyl group and aryl group for R 32 include the same alkyl groups and aryl groups as those described above for R 31 .
  • R 32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
  • oxime sulfonate-based acid generator More preferred are those represented by the following general formula (
  • Examples thereof include compounds represented by B-2) or (B-3).
  • R 3 -C N ⁇ 0 one S0 two one R 35
  • R 33 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group.
  • R 34 is an aryl group.
  • R 35 represents an alkyl group having no substituent or a halogenated alkyl group.
  • R 36 represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group.
  • R 37 is a divalent or trivalent aromatic hydrocarbon group.
  • R 38 is an alkyl group having no substituent or a halogenated alkyl group.
  • the alkyl group or the halogenated alkyl group has 1 to L0 carbon atoms.
  • a preferred carbon number of 1-8 is more preferred.
  • a carbon number of 1-6 is most preferred.
  • R 33 is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.
  • the fluorinated alkyl group in R 33 is preferably fluorinated with 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more. I like it! /
  • aryl group of R 3 aromatic carbon such as a phenol group, a biphenyl group, a fluoro group, a naphthyl group, an anthracyl group, a phenanthryl group, etc.
  • a fluorenyl group is preferable.
  • the aryl group of R 34 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group.
  • the alkyl group or halogenated alkyl group in the substituent is preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group.
  • the alkyl group or halogenoalkyl group having no substituent of R 35 preferably has 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Most preferred.
  • R 35 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and more preferably a partially fluorinated alkyl group.
  • the fluorinated alkyl group in R 35 preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, and even more preferably 90% or more. This is preferable because the strength of the acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted. [0079] In the general formula (B-3),! / Does not have the substituent of R 36 ! /, And the alkyl group or the halogenated alkyl group does not have the substituent of R 33 described above. And the same as the alkyl group or halogenalkyl group.
  • Examples of the divalent or trivalent aromatic hydrocarbon group for R 37 include groups in which the aryl group strength of R 34 is one or two hydrogen atoms removed.
  • P is preferably 2.
  • oxime sulfonate-based acid generators include ⁇ - (p-toluenesulfo-oxyximino) monobenzyl cyanide, ⁇ - ( ⁇ closed-mouth benzenesulfo-oxyoximino) -benzyl cyanide, ⁇ - ( 4-Nitrobenzenesulfo-luoxyimino) -benzyl cyanide, ichiichi (4-troo 2 trifluoromethylbenzenesulfo-ruximino) benzyl cyanide, ⁇ - (benzenesulfo-ruximino) —4-cyclopentyl cyanide-do , ⁇ (Benzenesulfo-Luximinomino) — 2, 4 Dichlorobenzil cyanide, ⁇ — (Benzenesulfo-Luximinomino) — 2, 6 Dichlorobenzil cyanide, ⁇ - (p-tol
  • bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis (p toluenesulfol) diazomethane, bis (1 , 1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane, and the like.
  • diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552 and JP-A-11-035573 can also be suitably used.
  • poly (bissulfol) diazomethanes include 1,3 bis (phenylsulfol diazomethylsulfol) pronone, 1, 4 disclosed in JP-A-11 322707.
  • one type of these acid generators may be used alone, or two or more types may be used in combination.
  • an ohmic salt having a fluorinated alkyl sulfonate ion as a cation as the component (B). Specifically, it is trifluoromethane sulfonate, etc. of trifluorosulfurium.
  • the content of the component (B) in the negative resist composition of the present invention is 100 masses of the component (A).
  • the amount is preferably 0.5 to 30 parts by mass, more preferably 1 to LO part by mass. By setting the above range, pattern formation is sufficiently performed. In addition, it is preferable because a uniform solution is obtained and storage stability is good.
  • the epoxy-based crosslinking agent (C1) (hereinafter referred to as the (C1) component) is used as an essential component as the (C) component.
  • Component (C1) is not particularly limited as long as it has an epoxy group and forms a crosslinked structure with component (A) by the action of an acid generated from component (B) upon exposure. It can be selected and used.
  • the component (C1) preferably has a saturated hydrocarbon ring.
  • the crosslinking reactivity with the component (A) is improved.
  • a part of the hydrogen atoms may or may not be substituted with a substituent such as a lower alkyl group having 1 to 5 carbon atoms, for example. preferable.
  • the saturated hydrocarbon ring may be monocyclic or polycyclic, but is preferably polycyclic.
  • the number of rings is preferably 2-6, more preferably 3-6, and most preferably 4-6.
  • the saturated hydrocarbon ring preferably has 4 to 20 carbon atoms, more preferably 5 to 18 carbon atoms, and most preferably 6 to 15 carbon atoms.
  • saturated hydrocarbon ring examples include, for example, monocycloalkanes, bicycloalkanes, tricycloalkanes, tetracycloalkanes, pentacycloalkanes that may be substituted with lower alkyl groups or the like.
  • polycycloalkanes can be given.
  • monocycloalkanes such as cyclopentane and cyclohexane
  • polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and pentacyclopentadecane.
  • adamantane norbornane
  • isobornane tricyclodecane
  • tetracyclododecane tetracyclododecane
  • pentacyclopentadecane are preferred.
  • the component (C1) preferably has two or more epoxy groups. By having two or more epoxy groups, cross-linking reactivity with the component (A) is improved.
  • the number of epoxy groups is preferably 2 or more, more preferably 2 to 4, and most preferably 2.
  • the epoxy group is preferably bonded directly to the saturated hydrocarbon ring.
  • TCPD-EP tricyclopentadiene epoxides
  • the TCPD-EP represented by the general formulas (C11) and (C12) has a lower absorbability with respect to the exposure wavelength (preferably 193 nm) than the conventional component (C). It is considered that the alkali insolubility of the exposed part near the substrate interface is improved by the increase in the property.
  • TCPD-EP has a structure with a high carbon density. Therefore, it is considered that the (A) component crosslinked with TCPD-EP by the action of an acid generated from the (B) component upon exposure has a higher molecular weight and is therefore more soluble in the developer.
  • TCPD-EP has a structure with a high carbon density, it is presumed that better etching resistance can be obtained when a resist composition is used.
  • the component (C1) can be used alone or in combination.
  • the content of the component (C1) in the whole component (C) in the negative resist composition of the present invention is preferably 40% by mass or more, more preferably 70% by mass or more, and more preferably 100% by mass. But you can. Most preferably, it is 100 mass%.
  • a crosslinking agent (C2) other than the component (CI) hereinafter referred to as the component (C2) may be used in combination with the component (C1).
  • the component (C2) is not particularly limited as long as it is other than the component (C1), and any of the crosslinking agents known to date and used in chemically amplified negative resist compositions. Can be selected and used.
  • the component (C) is preferably at least one selected from the group consisting of a melamine crosslinking agent, a urea crosslinking agent, an alkylene urea crosslinking agent, and a glycoluril crosslinking agent.
  • glycoluril-based crosslinking agents are preferred.
  • melamine-based cross-linking agent melamine and formaldehyde are reacted, and a compound in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group, or melamine, formaldehyde and lower alcohol are reacted.
  • a compound in which the hydrogen atom of an amino group is substituted with a lower alkoxymethyl group examples include compounds in which a hydrogen atom of an amino group is substituted with a lower alkoxymethyl group.
  • Specific examples include hexamethoxymethyl melamine, hexethoxymethyl melamine, hexapropoxymethyl melamine, hexasuboxybutyl melamine, etc. Among them, hexamethoxymethyl melamine is preferred!
  • urea-based cross-linking agent urea and formaldehyde are reacted to produce a hydrogen atom of an amino group.
  • examples thereof include a compound in which a child is substituted with a hydroxymethyl group, and a compound in which urea, formaldehyde, and a lower alcohol are reacted to replace a hydrogen atom of an amino group with a lower alkoxymethyl group.
  • Specific examples include bismethoxymethylurea, bisethoxymethylurea, bispoxoxymethylurea, bisbutoxymethylurea, and the like. Among them, bismethoxymethylurea is preferable.
  • alkylene urea crosslinking agent examples include compounds represented by the following general formula (C2-1).
  • R 1 ′ and R 2 ′ are each independently a hydroxyl group or a lower alkoxy group
  • R 3 ′ tR 4 ′ is independently a hydrogen atom, a hydroxyl group or a lower alkoxy group
  • V is 0 or 1 to An integer of 2.
  • R 1 'and R 2 ' are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, which may be linear or branched.
  • R 1 ′ and R 2 may be the same or different from each other. More preferably, they are the same.
  • R 3 ′ and are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, which may be linear or branched.
  • R 3 'and R 4 may be the same or different from each other. More preferably, they are the same.
  • V is 0 or an integer of 1 to 2, preferably 0 or 1.
  • alkylene urea cross-linking agent a compound having V of 0 (ethylene urea cross-linking agent) and a compound having Z or V of 1 (propylene urea cross-linking agent) are particularly preferred.
  • the compound represented by the general formula (C2-1) can be obtained by a condensation reaction of alkylene urea and formalin, and by reacting this product with a lower alcohol.
  • alkylene urea crosslinking agent examples include, for example, mono and Z or dihydroxy Chilled Tyleneurea, Mono and Z or Dimethoxymethylated Tyleneurea, Mono and Z or Diethoxymethylated Tyleneurea, Mono and z or Dipropoxymethylated Tyleneurea, Mono and Z or Dibutoxymethylethyleneethyleneurea, etc.
  • glycoluril-based crosslinking agent examples include glycoluril derivatives substituted with one or both of an N-position hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms.
  • Powerful glycoluril derivatives can be obtained by the condensation reaction of glycoluril and formalin and by reacting this product with a lower alcohol.
  • glycoluril-based crosslinking agent examples include, for example, mono-, di-, tri- and Z- or tetra-hydroxymethyl glycol glycol, mono-, di-, tri- and / or tetramethoxymethyl glycoluril, mono-, di-, Examples include tri- and / or tetraethoxymethylated glycoluril, mono-, di-, tri- and / or tetrapropoxymethylethyl glycoluril, mono-, di-, tri- and / or tetrabutoxymethyl-glycoluril and the like.
  • the component (C2) one type may be used alone, or two or more types may be used in combination.
  • the total content of the component (C) in the negative resist composition of the present invention is: A) 3 to 30 parts by mass is preferred with respect to 100 parts by mass of component 3 to 15 parts by mass is more preferred 4 to 12 parts by mass is particularly preferred 5 to 10 parts by mass is most preferred.
  • the content of the component (C) is at least the lower limit value, crosslinking formation proceeds sufficiently and a good resist pattern can be obtained. On the other hand, if it is below this upper limit, the storage stability of the resist coating solution is good, and the deterioration of sensitivity over time is suppressed.
  • the negative resist composition of the present invention is further optional in order to improve the resist pattern shape, post exposure stability of the latent image formed oy the pattern-wise exposure of the resist layer, etc.
  • component (D) a nitrogen-containing organic compound
  • aliphatic amines particularly secondary aliphatic amines and tertiary aliphatic amines are preferred. .
  • Aliphatic amines contain at least one hydrogen atom of ammonia NH and have 12 or more carbon atoms.
  • Examples include amines substituted with the lower alkyl group or hydroxyalkyl group (alkylamines or alkylalcoholamines). Specific examples thereof include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-noramine, n-decylamine; jetylamine, di-n-propylamine, di-n-heptylamine, di- —N-octylamine, dialkylamines such as dicyclohexylamine; trimethylamine, triethylamine, tri- n -propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, Trialkylamines such as tri-n-octylamine, tri-n-no-lamine, tri-n-de-ramine, tri-n-dodecyl
  • Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
  • an organic carboxylic acid is further added as an optional component for the purpose of preventing sensitivity deterioration due to the blending of the component (D) and improving the resist pattern shape, stability with time, etc.
  • phosphorus oxoacid or derivative thereof (E) hereinafter referred to as (E) Component
  • the component (D) and the component (E) can be used in combination, or one force can be used.
  • organic carboxylic acid for example, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Phosphoric acid or its derivatives include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenol ester and other phosphoric acid or derivatives such as those esters, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acid such as n-butyl ester, phenol phosphonic acid, diphosphoric phosphonic acid ester, dibenzyl phosphonic acid ester and derivatives thereof, phosphinic acid such as phosphinic acid, phenol phosphinic acid and the like And derivatives such as esters, of which phosphonic acid is particularly preferred.
  • Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).
  • the negative resist composition of the present invention there are further additives that are miscible as desired, for example, additional grease for improving the performance of the resist film, and a surfactant for improving the coating property. Further, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added and contained.
  • the negative resist composition of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as component (S)).
  • any component can be used among those conventionally known as solvents for chemically amplified resists, as long as it can dissolve each component used to form a uniform solution.
  • One type or two or more types can be appropriately selected and used.
  • latones such as ⁇ -butyrolatatane
  • ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl- ⁇ -amyl ketone, methyl isoamyl ketone, 2-heptanone
  • Polyhydric alcohols such as glycol and derivatives thereof; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; the above polyhydric alcohols or the above Monomethyl ether of a compound having an ester bond
  • Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoethanoloquine ether, monophenyl ether, such as noetinoreethenore, monopropinoreethenore, monobutinoreethenore, etc .; like
  • propylene glycol monomethyl ether acetate PGMEA
  • propylene glycol monomethyl ether PGME
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • PGME propylene glycol monomethyl ether
  • the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.
  • the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: Three.
  • a mixed solvent of at least one selected from among PGMEA and EL and ⁇ -petit-mouth rataton is also preferable.
  • the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
  • the amount of component (S) used is not particularly limited, but it is a concentration that can be applied to a substrate, etc., and can be appropriately set according to the coating film thickness. It is used so as to be in the range of 20% by mass, preferably 5 to 15% by mass.
  • the resist pattern forming method of the present invention includes a step of forming a resist film on a substrate using the negative resist composition, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern. Including.
  • the resist pattern forming method of the present invention can be performed, for example, as follows. That is, first, the negative resist composition is applied onto a substrate with a spinner or the like, and pre-beta is applied for 40 to 120 seconds, preferably 60 to 90 seconds under a temperature condition of 80 to 150 ° C. After selectively exposing ArF excimer laser light through a desired mask pattern using an exposure device, etc., PEB (post-exposure heating) is applied for 40 to 120 seconds, preferably 60 to 60 ° C under a temperature condition of 80 to 150 ° C. Apply for 90 seconds. Next, this is developed with an alkali developer, for example, 0.1 to 10% by mass of tetramethylammonium hydroxide aqueous solution.
  • PEB post-exposure heating
  • a resist pattern faithful to the mask pattern can be obtained.
  • a silicon wafer is used as the substrate.
  • a so-called inorganic substrate having a surface made of SiON, SiN or the like can also be used.
  • An organic or inorganic antireflection film may be provided between the substrate and the coating layer of the resist composition.
  • the wavelength used for the exposure is not particularly limited.
  • the negative resist composition of the present invention is effective for ArF excimer laser.
  • the negative resist composition and the resist pattern forming method of the present invention can form a resist pattern having a good shape.
  • a “inorganic substrate” in which a layer mainly composed of atoms other than silicon (such as nitrogen atoms) is formed on a substrate, particularly in a substrate having a nitrogen-containing layer such as a general SiON substrate. Biting of the skirt is suppressed, and a resist pattern with a good shape is formed. The reason why such a powerful effect can be obtained is estimated as follows.
  • the (C) crosslinking agent component used in the present invention has an epoxy group, it is considered that the alkali insolubility of the exposed area is improved by the possibility of crosslinking with the component (A). Preferably, it is considered that alkali insolubility of the exposed portion near the substrate interface is improved.
  • the negative resist composition and the resist pattern forming method of the present invention are presumed to form a resist pattern having a favorable shape.
  • the etching resistance is good.
  • Example 1 Next, the ability to explain the present invention in more detail by way of examples The present invention is not limited to these examples.
  • NMR was measured using JNM-AL400 (product name, resolution 400 MHz) manufactured by JEOL Ltd.
  • NBHFAA monomer represented by the following chemical formula
  • NBHFAA13 58g, Hydroxyethyl methacrylate (HEMA) 1.76g, 3-Hydoxyl 1-adamantyl acrylate (HAdA) 6.
  • HEMA Hydroxyethyl methacrylate
  • HdA 3-Hydoxyl 1-adamantyl acrylate
  • Og and polymerization initiator dimethyl azobisisobutyrate 0.6 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) and 200 mL of THF (tetrahydrofuran) were dissolved. Nitrogen publishing was performed for about 10 minutes, and the mixture was stirred for 4 hours while heating in an oil bath at 70 ° C, and then cooled to room temperature.
  • rosin (A) 1.
  • the chemical formula of the obtained rosin (A) -1 is as follows.
  • the mass average molecular weight (Mw) was 6000, and the degree of dispersion (MwZMn (Mn is the number average molecular weight)) was 1.67.
  • (C) -1 a cross-linking agent represented by the following chemical formula (C) -1 (tricyclopentadiene epoxide, a compound synthesized based on the description in JP-A-2004-99445).
  • (C) -2 Cross-linking agent represented by the following chemical formula (C) -2 (tetramethoxymethyl glycol glycol, product name: MX270, manufactured by Sanwa Chemical Co., Ltd.).
  • (C) 3 Crosslinking agent represented by the following chemical formula (C) 3 (bismethoxymethylpropylene urea, product name: N-1951, manufactured by Sanwa Chemical Co., Ltd.).
  • the chemical formula (C) 1 includes about 15% by mass of a compound represented by the following chemical formula (C) 4 as a structural isomer.
  • the negative resist composition obtained above is uniformly applied using a spinner on an 8-inch SiON substrate that has been subjected to hexamethyldisilazane (HMDS) treatment, and then heated at 80 ° C on a hot plate.
  • HMDS hexamethyldisilazane
  • a resist film with a thickness of 160 nm was formed by performing a pre-beta (PAB) treatment for 60 seconds.
  • ArF excimer laser (193nm) is selectively selected via mask pattern (norftone) Irradiated.
  • PEB post-exposure heating
  • TMAH tetramethylammonium hydroxide
  • the pattern size was changed, and the limit resolution which is the minimum dimension (nm) of the pattern to be resolved was obtained.
  • Example 1 Using the negative resist composition solutions of Example 1 and Comparative Examples 1 and 2, the following etching resistance was evaluated.
  • a resist film (hereinafter referred to as a resist film) that was subjected to a post-exposure heating (PEB) treatment at 90 ° C. for 90 seconds was formed.
  • PEB post-exposure heating
  • Example 1 had better etching resistance and higher resolution than Comparative Examples 1 and 2.
  • a resist pattern having a good shape can be formed.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L’invention concerne une composition de photorésist négatif capable de former un motif de photorésist présentant une excellente configuration ; et un procédé de formation d’un motif de photorésist. La composition de photorésist négatif selon l’invention comprend une résine soluble dans les alcalis (A), un générateur d’acide (B) capable de générer un acide lors d'une exposition à la lumière, et un agent de réticulation (C), l’agent de réticulation (C) contenant un agent de réticulation époxy (C1).
PCT/JP2006/316326 2005-09-16 2006-08-21 Composition de photoresist negatif, et procede de formation d’un motif de photoresist WO2007032181A1 (fr)

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JP2005270775A JP2007079481A (ja) 2005-09-16 2005-09-16 ネガ型レジスト組成物およびレジストパターン形成方法
JP2005-270775 2005-09-16

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KR20210104165A (ko) * 2016-03-23 2021-08-24 에네오스 가부시키가이샤 경화성 조성물 및 이것을 경화시킨 경화물
KR102304633B1 (ko) 2016-06-10 2021-09-23 에네오스 가부시키가이샤 에폭시 화합물, 이것을 포함하는 경화성 조성물 및 경화성 조성물을 경화시킨 경화물
JP7161323B2 (ja) * 2018-06-26 2022-10-26 東京応化工業株式会社 組成物、硬化物、パターン形成方法、化合物、重合体、及び化合物の製造方法
JP7376346B2 (ja) * 2019-12-25 2023-11-08 東京応化工業株式会社 硬化性組成物、硬化物、（メタ）アクリル樹脂、及び化合物
JP2022161390A (ja) * 2021-04-09 2022-10-21 信越化学工業株式会社 感光性樹脂組成物、感光性樹脂皮膜、感光性ドライフィルム及びパターン形成方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1171363A (ja) * 1997-06-25 1999-03-16 Wako Pure Chem Ind Ltd レジスト組成物及びこれを用いたパターン形成方法並びにレジスト剤用架橋剤
JPH11237741A (ja) * 1998-02-20 1999-08-31 Toshiba Corp ネガ型感光性組成物およびこれを用いたパターン形成方法
JPH11305436A (ja) * 1998-04-16 1999-11-05 Fujitsu Ltd ネガ型レジスト組成物およびレジストパターンの形成方法
JP2000330282A (ja) * 1999-05-24 2000-11-30 Nagase Denshi Kagaku Kk ネガ型感放射線性樹脂組成物
JP2004069855A (ja) * 2002-08-02 2004-03-04 Shin Etsu Chem Co Ltd 化学増幅型ネガ型レジスト材料及びこれを用いたパターン形成方法
JP2004240143A (ja) * 2003-02-05 2004-08-26 Jsr Corp ネガ型感光性樹脂組成物およびその硬化物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1171363A (ja) * 1997-06-25 1999-03-16 Wako Pure Chem Ind Ltd レジスト組成物及びこれを用いたパターン形成方法並びにレジスト剤用架橋剤
JPH11237741A (ja) * 1998-02-20 1999-08-31 Toshiba Corp ネガ型感光性組成物およびこれを用いたパターン形成方法
JPH11305436A (ja) * 1998-04-16 1999-11-05 Fujitsu Ltd ネガ型レジスト組成物およびレジストパターンの形成方法
JP2000330282A (ja) * 1999-05-24 2000-11-30 Nagase Denshi Kagaku Kk ネガ型感放射線性樹脂組成物
JP2004069855A (ja) * 2002-08-02 2004-03-04 Shin Etsu Chem Co Ltd 化学増幅型ネガ型レジスト材料及びこれを用いたパターン形成方法
JP2004240143A (ja) * 2003-02-05 2004-08-26 Jsr Corp ネガ型感光性樹脂組成物およびその硬化物

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