Cyanate ester and use thereof

Abstract

To provide a cyanate ester having an arene ring and a fluorene ring, and a use thereof.SOLUTION: The cyanate ester is represented by the following formula (1). The cyanate ester is suitable as a resist material for forming a resist underlayer film and / or a resist antireflection film. (In the formula, Z1 and Z2 each represent a benzene ring; Ar1 and Ar2 are the same or different and each represent an arene ring; R1, R2, R3 and R4 are the same or different and each represent a substituent; m and n each represent 0 or an integer of 1 or more; and p and q each represent an integer of 0-4.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cyanate ester having an arene ring such as a fused polycyclic arene ring, and uses thereof, particularly to a cyanate ester having high etching resistance and useful as a resist material for forming a resist underlayer film, and uses thereof. [Background technology]

[0002] Cyanate esters undergo trimerization to form triazine rings, resulting in highly heat-resistant polymers. Taking advantage of these properties, cyanate esters are widely used in a variety of fields, including prepregs, composite materials, molding materials, printed wiring boards, electronic component encapsulation, and adhesives.

[0003] WO 2016 / 163456 (Patent Document 1) describes a material for forming an underlayer film for lithography, which contains a compound represented by the following formula (O):

[0004] [ka]

[0005] (In formula (O), X represents an oxygen atom, a sulfur atom, or no crosslinking; R 1 is a 2n-valent group having 1 to 30 carbon atoms or a single bond, and R 2 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, etc., and the alkyl group, the alkenyl group and the aryl group may contain a cyanate group, etc. m1 is an integer of 0 to 4, and at least one m1 is an integer of 1 to 4, and each m2 is independently an integer of 0 to 3, and p is 0 or 1.

[0006] In this document 1, R 1As an example, fluorene-9,9-diyl group is given. In the examples of this document, dibenzoxanthene dicyanate, bis(4,4'-dicyanatobiphenyl-3-yl)biphenylmethane, etc. are used. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2016 / 163456 Summary of the Invention [Problem to be solved by the invention]

[0008] However, this document does not specifically describe cyanate esters containing arene rings and fluorene rings, nor does it describe the use of such cyanate esters as resist materials, particularly as underlayer film materials (underlayer film-forming materials for lithography) having high etching resistance or antireflective film materials.

[0009] Therefore, an object of the present invention is to provide a cyanate ester having an arene ring and a fluorene ring and its use (resist material).

[0010] Another object of the present invention is to provide a resist underlayer film or protective film material, and a resist anti-reflective film material, which have high etching resistance. [Means for solving the problem]

[0011] As a result of extensive research to achieve the above object, the present inventors have found that cyanate esters having arene rings, particularly fused polycyclic arene rings, introduced at the 9,9-positions of a fluorene ring exhibit high heat resistance and high etching resistance and are useful as materials for resist underlayer films (protective films) and / or anti-reflective films, etc., and have completed the present invention.

[0012] That is, the cyanate ester of the present invention is represented by the following formula (1).

[0013] [ka]

[0014] (In the formula, Z 1 and Z 2 each represents the same or different arene ring, and Ar 1 and Ar 2 represent the same or different arene rings, and R 1 , R 2 , R 3 and R 4 each represents the same or different substituent, m and n represent an integer of 0 or 1 or more, and p and q represent an integer of 0 to 4.

[0015] Z 1 and Z 2 may be a fused polycyclic arene ring. The cyanate ester may be a compound represented by the following formula (1a):

[0016] [ka]

[0017] (In the formula, m and n represent integers of 0 to 6, and R 1 , R 2 , R 3 and R 4 and p and q are the same as in formula (1) above.

[0018] The cyanate ester may be at least one selected from 9,9-bis(6-cyanato-2-naphthyl)fluorene and 9,9-bis(5-cyanato-1-naphthyl)fluorene. The cyanate ester may be in a crystalline form.

[0019] The present invention also includes a resist material containing the cyanate ester. This resist material may be a resist underlayer film material and / or a resist anti-reflective film material. The coating material may further include an organic solvent.

[0020] The present invention also encompasses a resist underlayer film and / or a resist antireflective film formed from a resist material containing the cyanate ester (at least one type of resistant film selected from a resist underlayer film and a resist antireflective film, formed from a cured product of the resist material). That is, the resist underlayer film and / or the resist antireflective film can be formed from the resist material. The present invention also encompasses a method for forming the underlayer film and / or the antireflective film, in which the resist material is applied directly or indirectly to a substrate and heated to form the underlayer film and / or the antireflective film.

[0021] The present invention also encompasses a semiconductor device comprising a substrate, an underlayer film and / or an anti-reflective film formed directly or indirectly on the substrate, and at least one photoresist layer formed on the underlayer film and / or the anti-reflective film, wherein at least the photoresist layer is formed in a predetermined pattern, and in this semiconductor device, the underlayer film and / or the anti-reflective film is formed from the resist material.

[0022] Furthermore, the present invention also includes a pattern formation method, in which an underlayer film and / or an anti-reflective film are formed on a substrate directly or indirectly using the resist material, at least one photoresist layer is formed on the underlayer film and / or the anti-reflective film, and the photoresist layer is irradiated (or exposed) to energy rays in a predetermined pattern and developed to form a pattern. In this method, the underlayer film and / or the anti-reflective film are also formed using the resist material.

[0023] In the present specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, an alkyl group with 1 carbon atom is represented as a "C1 alkyl group," and an aryl group with 6 to 10 carbon atoms is represented as a "C 6-10 Aryl group”.

[0024] In addition, in this specification and claims, the term "fluorene skeleton" (or "fluorene ring") is used to mean a skeleton containing an inherent fluorene skeleton, such as a benzofluorene skeleton (benzofluorene ring) or a dibenzofluorene skeleton (dibenzofluorene ring). [Effects of the Invention]

[0025] In the present invention, since the cyanate ester has an arene ring and a fluorene ring, it has high heat resistance and etching resistance and is suitable as a resist material. In particular, it has high etching resistance and is suitable as a material for forming a resist underlayer film (or protective film) and / or a resist anti-reflective film. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a graph showing the relationship between processing time (etching time) and film thickness in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0027] [Cyanate ester] In the formula (1) showing the cyanate ester of the present invention, the ring Z 1 and ring Z 2 Examples of the arene ring represented by the formula (I) include monocyclic arene rings such as a benzene ring, and polycyclic arene rings. Examples of the polycyclic arene ring include fused polycyclic arene rings (fused polycyclic aromatic hydrocarbon rings) and ring-assembled arene rings (ring-assembled polycyclic aromatic hydrocarbon rings). Examples of the fused polycyclic arene ring include fused bicyclic to tetracyclic arene rings. Examples of the fused bicyclic arene ring include fused bicyclic C rings such as a naphthalene ring and an indene ring. 10-16 Examples of the fused tricyclic arene ring include fused tricyclic C arenes such as an anthracene ring and a phenanthrene ring. 14-20 Examples of ring-assembled arene rings include biphenyl rings, phenyl rings, and phenyl rings. Examples of preferred ring-assembled arene rings include biarene rings such as a phenylnaphthalene ring and a binaphthyl ring; and terarene rings such as a terphenyl ring. 12-18 It is a biarene ring.

[0028] Preferred arene rings are C 6-14 C arene ring, preferably benzene ring, naphthalene ring, biphenyl ring, etc. 6-12 C rings such as arene rings, more preferably benzene rings and naphthalene rings 6-10 An arene ring, particularly a naphthalene ring. Particularly preferred arene rings are fused polycyclic arene rings, preferably fused polycyclic C 10-14 The ring Z is preferably an arene ring, and more preferably a naphthalene ring. 1 and ring Z 2 The types may be the same or different from each other, and are preferably the same.

[0029] R 1 and R 2 Examples of the substituent represented by the formula (I) include a halogen atom; a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; an alkoxy group; an acyl group; a nitro group; a cyano group; and a substituted amino group.

[0030] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms. Examples of alkyl groups include linear or branched C alkyl groups such as methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, and t-butyl groups. 1-6 Examples of cycloalkyl groups include C alkyl groups such as cyclopentyl and cyclohexyl groups. 5-8 Examples of aralkyl groups include C cycloalkyl groups such as benzyl groups. 6-10 Aryl-C 1-4 Examples of the aryl group include C alkyl groups such as phenyl groups. 6-10 The alkoxy group includes a linear or branched C alkoxy group such as a methoxy group. 1-10 Examples of acyl groups include C groups such as acetyl groups. 1-6Examples of the substituted amino group include a dialkylamino group and a diacylamino group. Examples of the dialkylamino group include a di-C group such as a dimethylamino group. 1-4 Examples of the diacylamino group include di-C groups such as diacetylamino group. 1-4 acylamino group. 1 and R 2 The substituents represented by the following formula (I) may be the same or different, and are preferably the same.

[0031] Preferred R 1 and R 2 is a linear or branched chain C 1-4 C such as alkyl group and cyclohexyl group 5-8 Cycloalkyl groups, C 6-14 Linear or branched C such as aryl group, methoxy group 1-4 Alkoxy groups; more preferably linear or branched C groups such as methyl groups and ethyl groups. 1-3 Alkyl groups; especially C such as methyl groups 1-2 is an alkyl group. 1 and R 2 The types of R may be the same or different, and are preferably the same. 1 or R 2 is an aryl group, the ring Z to which it is bonded 1 , Z 2 together to form the ring-assembled arene ring.

[0032] R 1 and R 2 The numbers of substitutions m and n can be selected from integers of 0 or 1 or more, for example, integers of 0 to 8, preferably 0 to 6, 0 to 4, 0 to 3, 0 to 2, 0 or 1, in the following stepwise order, and particularly 0. The numbers of substitutions m and n may be the same or different. When the number of substitutions m or n is 2 or more, 2 or more R 1 or R 2 The types may be the same or different from each other.

[0033] Ar 1 and Ar 2Examples of the arene ring (aromatic hydrocarbon ring) represented by the formula include a monocyclic arene ring such as a benzene ring, a condensed polycyclic arene ring, and a ring assembly arene ring.

[0034] The fused polycyclic arene rings include ring Z 1 and ring Z 2 Similar fused polycyclic C 10-14 arene rings, etc. A preferred fused polycyclic arene ring is a naphthalene ring.

[0035] Examples of ring-assembled arene rings include biphenyl rings, binaphthyl rings, and phenylnaphthalene rings. BIC 6-12 A preferred ring-assembly arene ring is a biphenyl ring.

[0036] In addition, Ar 1 and Ar 2 The types of Ar may be the same or different, and are preferably the same. 1 and Ar 2 A preferred arene ring represented by the formula: is a benzene ring, a biphenyl ring or a naphthalene ring.

[0037] Ar 1 and Ar 2 is a benzene ring, the ring Z relative to the 9-position of the fluorene ring 1 and ring Z 2 The bonding (or substitution) position of is not particularly limited, and 1 and ring Z 2 When is a biphenyl ring, it may be at the 3- or 4-position of the biphenyl ring, preferably at the 3-position of the biphenyl ring; 1 and ring Z 2 When is a naphthalene ring, it may be at the 1- or 2-position of the naphthalene ring, preferably at the 2-position of the naphthalene ring (or in a 2-naphthyl relationship).

[0038] R 3 and R 4 Examples of the substituent represented by the formula include a halogen atom, an alkyl group, an aryl group, and a cyano group.

[0039] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms. Examples of alkyl groups include linear or branched C alkyl groups such as methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, and t-butyl groups. 1-6 Examples of aryl groups include C alkyl groups such as phenyl groups. 6-10 aryl groups. 3 and R 4 The substituents represented by may be the same or different.

[0040] Preferred R 3 and R 4 is a halogen atom, a linear or branched C 1-4 A linear or branched C group such as an alkyl group, a cyano group, or more preferably a methyl group or an ethyl group. 1-3 C alkyl groups, especially methyl groups 1-2 is an alkyl group. 3 and R 4 The types may be the same or different from each other, and are preferably the same.

[0041] R 3 and R 4 The substitution numbers p and q are integers of 0 to 4, preferably 0 to 3, 0 to 2, 0 or 1, and particularly 0. The substitution numbers p and q may be the same or different. When the substitution numbers p and q are 2 or more, 2 or more R 3 or R 4 The types of R may be the same or different. 3 and R 4 The substitution position of Ar is not particularly limited. 1 or Ar 2 When is a benzene ring (when is a fluorene ring), it is at the 2- to 7-positions of the fluorene ring, preferably the 2-, 3- or 7-position.

[0042] In the formula (1), ring Z 1 , ring Z 2 The position of the cyanato group (-OCN) on the ring Z is not particularly limited. 1 , ring Z2 is a naphthalene ring, the fluorene ring (Ar 1 and Ar 2 The fluorene ring is substituted at any one of the 5- to 8-positions of the naphthyl group bonded at the 1- or 2-position to the 9-position of the fluorene ring (the fluorene ring is substituted at the 1- or 2-position of the naphthalene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and the fluorene ring is substituted at the 1- or 2-position, preferably at the 1,5- or 2,6-position, and particularly preferably at the 2,6-position.

[0043] Examples of the compound represented by formula (1) include 9,9-bis(cyanatophenyl)fluorenes such as 9,9-bis(4-cyanatophenyl)fluorene; 9,9-bis(cyanato-C) such as 9,9-bis(4-cyanato-3-methylphenyl)fluorene and 9,9-bis(4-cyanato-3,5-dimethylphenyl)fluorene; 1-4 9,9-bis(cyanato-biphenyl)fluorenes such as 9,9-bis(4-cyanato-3-phenylphenyl)fluorene; 9,9-bis[cyanato-C, such as 9,9-bis(5-cyanato-1-naphthyl) and 9,9-bis(6-cyanato-2-naphthyl)fluorene 6-12 An example is aryl]fluorene.

[0044] The preferred compound represented by the formula (1) is a compound having a fluorene ring (Z 1 and Z 2 is a naphthalene ring, and Ar 1 and Ar 2 a compound having a benzofluorene ring (Z 1 and Z 2 is a naphthalene ring, and Ar 1 and Ar 2 wherein one ring is a benzene ring and the other is a naphthalene ring); and a compound having a dibenzofluorene ring (Z 1 and Z 2 is a naphthalene ring, and Ar 1 and Ar 2is a naphthalene ring).

[0045] [ka]

[0046] (In the formula, R 1 , R 2 , R 3 and R 4 and m, n, p and q are the same as in formula (1) above. In the formulas (1a), (1b), (1c), and (1d), the fluorene ring and the ring corresponding to the fluorene ring are assigned position numbers.

[0047] Examples of such compounds include 9,9-bis(cyanatonaphthyl)fluorene represented by the formula (1a), 11,11-bis(cyanatonaphthyl)-2,3-benzofluorene (11,11-bis(cyanatonaphthyl)-11H-benzo[b]fluorene) represented by the formula (1b), 13,13-bis(cyanatonaphthyl)-2,3,6,7-dibenzofluorene (13,13-bis(cyanatonaphthyl)-13H-dibenzo[b,h]fluorene) represented by the formula (1c), and 13,13-bis(cyanatonaphthyl)-1,2,7,8-dibenzofluorene (13,13-bis(cyanatonaphthyl)-13H-dibenzo[a,i]fluorene) represented by the formula (1d). The naphthalene ring is preferably bonded to the fluorene ring and the cyanato group through the relationship of the 1,5-diyl and 2,6-diyl bonds.

[0048] More preferred compounds include compounds represented by the following formula (1a) (in the formula (1), Z 1 and Z 2 is a naphthalene ring, and Ar 1 and Ar 2 is a benzene ring).

[0049] [ka]

[0050] (In the formula, R 1 , R 2 , R 3 and R 4 and m, n, p and q are the same as in formula (1) above.

[0051] In such compounds, m, n, p, and q are preferably each 0. Therefore, preferred cyanate esters include 9,9-bis(cyanatonaphthyl)fluorenes. Examples of the 9,9-bis(cyanatonaphthyl)fluorenes include 9,9-bis(6-cyanato-2-naphthyl)fluorene and 9,9-bis(5-cyanato-1-naphthyl)fluorene. Of these compounds, 9,9-bis(6-cyanato-2-naphthyl)fluorene is particularly preferred.

[0052] Such a cyanate ester may be in a liquid form at room temperature (20°C), but is preferably in a crystalline form. A crystalline cyanate ester is easy to handle and industrially advantageous. For example, in the formula (1), 1 , Ar 2 , Z 1 , and Z 1 The melting point of the cyanate ester in which the ring Ar is a benzene ring is 130 to 170°C, preferably 140 to 160°C, particularly 145 to 150°C. 1 , Ar 2 is a benzene ring, ring Z 1 , and Z 1 The melting point of the cyanate ester in which ring Z is a naphthalene ring is 200 to 240°C, preferably 210 to 235°C, and particularly 220 to 230°C. 1 , and Z 1 However, cyanate esters having polycyclic arene rings, particularly fused polycyclic arene rings, are suitable for forming resistant films having high heat resistance and etching resistance.

[0053] [Method of producing cyanate ester] The cyanate ester represented by formula (1) can be prepared by a conventional method, for example, by reacting a compound represented by formula (2) below with a cyanogen halide represented by formula (3) below in a solvent in the presence of a basic compound (a tertiary amine such as a trialkylamine). The reaction may be carried out in the presence of a solvent that is separable from water. Alternatively, as described in Patent Document 2, the compound represented by formula (2) below may be reacted with a cyanogen halide in the presence of a tertiary amine under acidic conditions in a two-phase solvent system consisting of water and an organic solvent.

[0054] [ka]

[0055] (wherein X represents a halogen atom, and Z 1 , Z 2 , Ar 1 , Ar 2 , R 1 , R 2 , R 3 and R 4 and m, n, p and q are the same as in formula (1) above.

[0056] The cyanogen halide represented by the formula (3) includes cyanogen chloride and cyanogen bromide. The amount of cyanogen halide used is 1 mole of the hydroxyl group of the compound represented by the formula (2). The amount is 0.7 to 5 mol, preferably 1 to 3.5 mol, and more preferably 1.2 to 3 mol, relative to the amount of the hydroxybenzoate.

[0057] The basic compound may be either an organic base or an inorganic base. Examples of the organic base include trialkylamines such as trimethylamine, triethylamine, and tri-n-butylamine; N,N-dialkylanilines such as N,N-dimethylaniline; aromatic heterocyclic amines such as pyridine; and aliphatic heterocyclic amines such as 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonene. Preferred organic bases include tri-C bases such as trimethylamine, triethylamine, tri-n-butylamine, and diisopropylethylamine. 1-4 The organic base is an alkylamine. The amount of the organic base used is 1 to 8 moles, preferably 1.2 to 3.5 moles, relative to 1 mole of the hydroxy group of the compound represented by formula (2).

[0058] Examples of inorganic bases include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; and alkali metal carbonates. A preferred inorganic base is sodium hydroxide. The amount of the inorganic base used is 1 to 5 moles, preferably 1.2 to 3.5 moles, per mole of hydroxy group in the compound represented by formula (2).

[0059] Examples of the solvent include hydrocarbons, halogenated hydrocarbons, ethers, ketones, esters, amides, sulfoxides, nitriles, etc. These solvents can also be used as mixed solvents, and as the mixed solvent, a mixture of water and a separable solvent (a two-phase solvent of water and an organic solvent) can be used.

[0060] Examples of hydrocarbons include aliphatic hydrocarbons such as n-hexane and octane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. Examples of halogenated hydrocarbons include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene, and bromobenzene. Examples of ethers include diethyl ether, dimethyl cellosolve, diglyme, dioxane, and tetrahydrofuran. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of esters include methyl acetate and ethyl acetate. Examples of amides include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. Examples of sulfoxides include dimethyl sulfoxide. Examples of nitriles include acetonitrile and benzonitrile.

[0061] The reaction can be carried out under normal pressure or under pressure at a reaction temperature of −20° C. to 50° C., preferably −15° C. to 25° C., and more preferably −10° C. to 15° C. The reaction may be carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

[0062] After the reaction is complete, the cyanate ester (1) can be separated and purified from the reaction mixture by a conventional separation method, such as filtration, washing, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. For example, the reaction mixture may be concentrated as necessary, and the precipitate may be filtered, washed, and dried, or the precipitate may be crystallized.

[0063] [Uses of cyanate esters] The compound (cyanate ester) represented by formula (1) has film-forming properties by itself and has higher solubility in organic solvents than novolac resins, which are used as materials for resist underlayer films. In particular, it forms a cured film with a high glass transition temperature (heat resistance) and chemical resistance, excellent electrical insulation, low dielectric constant, and small dielectric loss tangent. Therefore, the cyanate ester may be combined with a resin component to form a resin composition. The resin component is a polyolefin resin. Examples of the resin component include thermoplastic resins such as polystyrene resins, polyester resins, polycarbonate resins, polyphenylene ether resins, and polyethersulfone resins, and thermosetting resins such as epoxy resins, vinyl ester resins, phenol resins, bismaleimide resins, oxetane resins, and benzoxazine compounds. These resin components can be used alone or in combination. Preferred resin components are polyphenylene ether resins, epoxy resins, phenol resins, and bismaleimide resins.

[0064] Examples of epoxy resins include glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, alicyclic epoxy resins in which a cyclohexene ring is epoxidized, etc. Examples of glycidyl ether type epoxy resins include bisphenol type epoxy resins, novolac type epoxy resins, and naphthalene type epoxy resins.

[0065] Bisphenol-type epoxy resins include biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol E-type epoxy resins, bisphenol Z-type epoxy resins, and fluorene-type epoxy resins (9,9-bis(glycidyloxy C 6-10 Examples of the bisphenol type epoxy resin include a phenoxy type epoxy resin having a large molecular weight. Examples of the novolac type epoxy resin include a phenol novolac type epoxy resin and a cresol novolac epoxy resin.

[0066] Examples of the phenolic resin include novolac type phenolic resin, resol type phenolic resin, etc. The preferred phenolic resin is novolac type phenolic resin.

[0067] The content of the compound represented by formula (1) (cyanate ester) is 10 to 120 parts by mass, preferably 20 to 100 parts by mass, and more preferably 25 to 75 parts by mass, relative to 100 parts by mass of the resin component.

[0068] The resin composition may contain an elastomer and / or additives. Examples of the elastomer include styrene-based elastomers such as styrene-butadiene block copolymers, styrene-isoprene block copolymers, and styrene-hydrogenated butadiene block copolymers; olefin-based elastomers such as ethylene-propylene elastomers; polyamide-based elastomers; and polyester-based elastomers. The content of the elastomer is 0 to 30 parts by mass, preferably 1 to 25 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the total amount of the cyanate ester and resin components.

[0069] Examples of additives include fillers, silane coupling agents, stabilizers (antioxidants, ultraviolet absorbers, storage stabilizers, etc.), curing agents appropriate for thermosetting resins, antistatic agents, flame retardants, antifoaming agents, leveling agents, and colorants.

[0070] Examples of the filler include inorganic fillers such as carbon black, silica, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, barium sulfate, clay, kaolin, and talc, and fibrous fillers such as glass fiber and carbon fiber. The amount of the filler used is 10 to 250 parts by mass, preferably 25 to 200 parts by mass, and more preferably 50 to 150 parts by mass, per 100 parts by mass of the total amount of the cyanate ester and resin component.

[0071] Examples of the silane coupling agent include epoxy group-containing silane coupling agents such as 3-glycidyloxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyl groups such as 3-(meth)acryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyl-tri(2-methoxyethoxy)silane; Examples of the silane coupling agents include silane coupling agents containing an amino group, such as 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane. These silane coupling agents can be used alone or in combination.

[0072] The amount of the silane coupling agent used is 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total amount of the cyanate ester and resin component.

[0073] Such a resin composition can be effectively used as a prepreg, a laminate (including a metal foil-clad laminate), a printed wiring board (including a multilayer printed wiring board), a sealant, and the like.

[0074] [Resist materials] Furthermore, the cyanate ester forms a cured film (resistant film) having high etching resistance (or radiation resistance and high-energy ray resistance), and this cured film also has antireflection properties. Therefore, the cyanate ester is suitable as a resist material, particularly as a material for forming a protective film, such as a resist underlayer film and / or an antireflection film (at least one resistant film selected from a resist underlayer film and a resist antireflection film), in pattern formation in which a predetermined pattern (or circuit pattern) is formed by lithography.

[0075] The resist material (composition) of the present invention only needs to contain at least the cyanate ester (first cyanate ester) represented by formula (1), and may also contain a second cyanate ester if necessary. Examples of the second cyanate ester include biphenyl-type dicyanate esters, cyanate esters having a bisphenolfluorene skeleton, cyanate esters having a bisphenolalkane skeleton, cyanate esters having a triphenolalkane skeleton, and novolac-type cyanate esters.

[0076] Examples of cyanate esters having a bisphenolfluorene skeleton include 9,9-bis(4-cyanatophenyl)-9H-fluorene, 9,9-bis(3-methyl-4-cyanatophenyl)-9H-fluorene, 9,9-bis(3,5-dimethyl-4-cyanatophenyl)-9H-fluorene, and 9,9-bis[4-cyanato-3-phenylphenyl]fluorene. Examples of cyanate esters having a bisphenolalkane skeleton include bisphenol A-type dicyanate ester, bisphenol AP-type dicyanate ester, bisphenol B-type dicyanate ester, bisphenol C-type dicyanate ester, bisphenol E-type dicyanate ester, bisphenol F-type dicyanate ester, bisphenol AD-type dicyanate ester, bisphenol S-type dicyanate ester, and bisphenol Z-type dicyanate ester. Examples of cyanate esters having a triphenolalkane skeleton include tris(4-cyanatophenyl)methane and tris(4-cyanatophenyl)ethane, and examples of novolac-type cyanate esters include phenol novolac-type cyanate esters and cresol novolac-type cyanate esters.

[0077] The amount of the second cyanate ester used can be selected from the range of 0 to 100 parts by mass, and is 2 to 75 parts by mass, preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the first cyanate ester.

[0078] The cyanate ester containing at least the first cyanate ester may be used as a resist material as it is. A preferred resist material (composition) contains an organic solvent in addition to the cyanate ester.

[0079] The organic solvent may be a hydrocarbon solvent, a ketone solvent, an ester solvent, a cellosolve solvent, or the like. Examples of hydrocarbon solvents include alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as toluene and xylene. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ester solvents include methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, and ethyl lactate. Examples of cellosolve solvents include cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate, carbitols such as methyl carbitol and ethyl carbitol, carbitol acetates such as methyl carbitol acetate, ethyl carbitol acetate, and butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. The organic solvents can be used alone or in combination.

[0080] The compound represented by formula (1) (cyanate ester) can be cured by heating, so the resist material may contain an acid catalyst (acid generator), a crosslinking agent, etc., although this is not always necessary.

[0081] The acid generator accelerates the curing of the cyanate ester and may be either a photoacid generator or a thermal acid generator. Examples of the acid generator include onium salts, diazomethane derivatives, glyoxime derivatives, and sulfonate esters.

[0082] Examples of onium salts include trifluoromethanesulfonate sulfonium salts and p-toluenesulfonate sulfonium salts. Examples of trifluoromethanesulfonate sulfonium salts include triphenylsulfonium, (pt-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(pt-butoxyphenyl)sulfonium trifluoromethanesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, and (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate. Examples of p-toluenesulfonate sulfonium salts include triphenylsulfonium p-toluenesulfonate, (pt-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, and tris(pt-butoxyphenyl)sulfonium p-toluenesulfonate. Examples of diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(naphthalenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, and bis(t-butylsulfonyl)diazomethane.

[0083] Examples of glyoxime derivatives include bis-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-(n-butanesulfonyl)-α-dimethylglyoxime, etc. Examples of sulfonate esters include sulfonate ester derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, and N-hydroxynaphthalimide benzenesulfonate; nitrobenzyl sulfonates such as 2,6-dinitrobenzyl p-toluenesulfonate; Examples include trisulfonyloxybenzenes such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0084] The content of the acid generator is 0 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 2 to 15 parts by mass, relative to 100 parts by mass of the cyanate ester.

[0085] In order to improve storage stability, the resist material containing the acid generator may contain a basic compound, which acts as a quencher to capture trace amounts of acid generated by the acid generator and is effective in improving the crosslinking reaction.

[0086] The basic compound may be either an organic base or an inorganic base, and the organic base may be any of amines (primary amine, secondary amine, tertiary amine). Preferred basic compounds are organic bases, particularly tertiary amines. Examples of amines including tertiary amines include C amines such as trimethylamine and triethylamine. 1-10Alkylamines; tetra C such as N,N,N',N'-tetramethylethylenediamine 1-4 Alkyl alkylenediamines; alkanolamines such as triethanolamine and dimethylaminoethanol; N,N-di-C such as N,N-dimethylaniline 1-4 Alkyl C 6-10 arenes; di-C such as benzyldimethylamine 1-4 Alkylamino C 1-4 Alkyl C 6-10 Examples include heterocyclic amines such as arenes, morpholine, N-methylmorpholine, N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylpyrrolidone, 1,4-diazabicyclo[2.2.2]octane (DABCO), diazabicycloundecene (DBU), and diazabicyclononene (DBN).

[0087] The content of the basic compound is 0 to 2 parts by mass, and preferably 0 to 1 part by mass, per 100 parts by mass of the resist material.

[0088] Examples of the crosslinking agent include melamines, guanamines (benzoguanamines), ureas, epoxies, vinyl ethers, and azides.

[0089] Examples of melamines include hexamethylolmelamine and hexamethoxymethylmelamine; examples of guanamines include tetramethylolguanamine and tetramethoxymethylguanamine; and examples of ureas include tetramethylolurea and tetramethoxymethylurea. Epoxies include compounds having two or more, preferably three to six, epoxy groups, such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and tris(2,3-epoxypropyl)triisocyanurate. Vinyl ethers include compounds having two or more, preferably 3 to 6, vinyl ether groups in one molecule, and examples of such compounds include ethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, 1,4-cyclohexanediol divinyl ether, and pentaerythritol tetravinyl ether.

[0090] The content of the crosslinking agent is 0 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 3 to 15 parts by mass, relative to 100 parts by mass of the cyanate ester.

[0091] The resist material may contain additives as needed. Such additives include stabilizers (antioxidants, storage stabilizers, etc.), ultraviolet absorbers, surfactants, antistatic agents, Flame retardants, colorants, etc.

[0092] A resist film can be formed by applying a resist material directly or indirectly to a base material (or substrate) by a conventional method and heating or baking the resulting coating film, which may be cured. More specifically, a resist pattern can be formed by applying the resist material to a substrate to form an underlayer film (or coating film), forming at least one photoresist layer on this underlayer film, exposing or irradiating this photoresist layer with energy rays or radiation of a predetermined wavelength in a predetermined pattern, and developing the photoresist layer to form a predetermined resist pattern (or circuit pattern).

[0093] The resist film or underlayer film has the property of absorbing the energy rays or radiation and also functions as an anti-reflection film, so the resist material is suitable for forming an underlayer film and / or an anti-reflection film.

[0094] As the substrate (or base material), a known substrate can be used, and examples thereof include substrates formed of silicon, silicon nitride, titanium nitride, aluminum, etc. The substrate may be a laminate in which a film to be processed is laminated on a base material (support).

[0095] An adhesion layer may be formed on the surface of the base material (or substrate) to enhance adhesion to the resist film. The resist material can be applied to the base material (or substrate) by a coating method such as spin coating or a printing method such as screen printing.

[0096] The underlayer film (or coating film) is preferably prepared by applying a resist material to the base material (or substrate), removing the solvent by drying, and then heating or baking to harden the film. The heating or baking temperature can be selected from the range of 80 to 400°C, preferably 100 to 300°C, and more preferably 150 to 250°C. The thickness of the underlayer film is 10 nm to 10 μm, preferably 20 to 1000 nm, and more preferably 50 to 800 nm.

[0097] The intermediate layer may be formed of a resist containing a polysilsesquioxane derivative to enhance oxygen gas etching resistance, or may be formed by PVD (physical vapor deposition) or CVD (chemical vapor deposition). Furthermore, forming a silicon-containing film such as silicon oxide, silicon nitride, or SiON film as the intermediate layer can enhance the light absorption of a specific wavelength and also provide anti-reflection properties.

[0098] The photoresist layer can be a conventional photoresist (positive or negative photoresist), and for fine pattern formation, a positive photoresist, particularly a chemically amplified positive photoresist, can be used. The photoresist can be made of a material that is sensitive to high-energy rays with a wavelength of 300 nm or less, specifically, materials that are sensitive to excimer lasers of 248 nm, 193 nm, or 157 nm, soft X-rays of 3 to 20 nm, electron beams, or X-rays. As described above, a typical photoresist contains an organic solvent and an acid generator, particularly a photoacid generator.

[0099] As described above, the photoresist layer can be formed by applying a photoresist material to an underlayer film or an intermediate layer using a wet method such as spin coating or screen printing, followed by pre-baking (PAB) at 80 to 180°C. The thickness of the coating layer is 20 to 500 nm, preferably 50 to 300 nm. A resist pattern can be formed by pattern-exposing the coating layer, post-baking (PEB), and developing it.

[0100] When etching using a resist pattern as a mask, etching gas can be used. Examples of etching gases include oxygen gas, inert gases such as helium and argon, hydrogen, nitrogen, carbon monoxide, carbon dioxide, ammonia, nitrogen dioxide, and sulfur dioxide. These etching gases can also be used as mixed gases. The preferred etching gas is oxygen gas. [Example]

[0101] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The evaluation methods used in the examples and comparative examples are as follows.

[0102] 1 H-NMR: A nuclear magnetic resonance spectrometer (BRUKER "ADVANCE III HD") was used, tetramethylsilane was used as an internal standard, and CDCl3 was used as a solvent. 1 H-NMR spectrum was measured.

[0103] Melting point: Measurement was performed using a differential scanning calorimeter (SII NanoTechnology, Inc., "EXSTAR DSC6200") under a nitrogen atmosphere at a temperature of 30 to 300°C and a heating rate of 10°C / min. From the obtained DSC chart (DSC curve), the temperature at the top of the endothermic peak due to melting was determined as the melting point.

[0104] (Heat resistance (weight loss temperature)) The 5% weight loss temperature and the 10% weight loss temperature were measured under the following conditions using a differential thermogravimetric analyzer (manufactured by Hitachi High-Tech Science Corporation, "TG / DTA6200").

[0105] Measurement temperature range: 30 to 520°C Temperature rise: 10°C / min Gas atmosphere: Nitrogen atmosphere.

[0106] (heated residue) The sample was heated to 180°C, and the weight loss was measured after leaving it for 1 minute until there was no more weight change.

[0107] (purity) The measurement was carried out using liquid chromatography (LC, Shimadzu Corporation, "LC-2010A"), with an eluent of acetonitrile / water (volume ratio) = 70 / 30 → 95 / 5 → 70 / 30.

[0108] (refractive index) The refractive index was measured at a measurement temperature of 25° C. and a wavelength of 589 nm using a refractometer (manufactured by Atago Co., Ltd., "DR-M2").

[0109] Synthesis Example 1 (Synthesis of 9,9-bis(6-cyanato-2-naphthyl)fluorene) A reactor equipped with a stirrer, a dropping funnel, a thermometer, and a three-way cock was charged with 284 g (0.63 mol) of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF) (Osaka Gas Chemicals Co., Ltd.) and purged with nitrogen gas. Then, 2000 ml of tetrahydrofuran was added and dissolved, and the internal temperature was cooled to 5°C or below.

[0110] 276 g (2.52 mol) of cyanogen bromide was added in portions over 5 minutes to dissolve, and the internal temperature was cooled to below 0°C. While maintaining the internal temperature at 0 to 10°C, 350 ml (2.52 mol) of triethylamine was added over 150 minutes. The temperature was then raised to room temperature and the reaction was continued for 45 hours. The reaction solution was analyzed by high-performance liquid chromatography (HPLC), and it was confirmed that the raw materials had disappeared.

[0111] The precipitate was filtered off and washed with tetrahydrofuran, and the filtrate and washings were combined and concentrated under reduced pressure with heating to give 273 g of an ochre muddy substance (yield of crude product: 86.6%).

[0112] Next, 273 g of the ochre mud was dissolved in 1,000 ml of chloroform at 65° C., after which 600 ml of ethyl acetate was added, and the mixture was cooled to room temperature over 60 minutes with stirring, then allowed to stand at 0° C. for 30 minutes, and then allowed to stand overnight at −20° C. The precipitate was filtered off and washed with a 0.6 L / 0.6 L (volume ratio 1:1) mixture of chloroform and ethyl acetate cooled to −20° C., and then heated to dryness under reduced pressure to obtain 9,9-bis(6-cyanato-2-naphthyl)fluorene (BNF cyanate ester) as crystals, represented by the following formula:

[0113] [ka]

[0114] NMR: 1H-NMR (CDCl3, 300MHz) δ (ppm): 7.3 (m, 2H), 7.5 (d, 6H), 7.6 (d, 2H), 7.7 (s, 2H), 8.0 (m, 8H) Melting point: 224°C.

[0115] Synthesis Example 2 (Synthesis of 9,9-bis(4-cyanatophenyl)fluorene) Crystals of 9,9-bis(4-cyanatophenyl)fluorene (BPF cyanate ester) represented by the following formula were obtained in the same manner as in Synthesis Example 1, except that 9,9-bis(4-hydroxyphenyl)fluorene (BPF) (manufactured by Osaka Gas Chemicals Co., Ltd.) was used instead of 9,9-bis(6-hydroxy-2-naphthyl)fluorene (BNF).

[0116] [ka]

[0117] NMR: 1 H-NMR (CDCl3, 300MHz) δ (ppm): 7.2-7.4 (m, 14H), 7.9 (d, 2H) Melting point: 147°C.

[0118] [Examples 1 and 2 and Comparative Examples 1 and 2] Each resist composition having the following composition was applied to a silicon substrate using a spin coater, and then heated (pre-baked; PAB) at a predetermined temperature for a predetermined time, as described below, to form a cured film having a predetermined film thickness.

[0119] Example 1: Cyclohexanone solution containing the BNF cyanate ester of Synthesis Example 1 at a concentration of 10% by mass (cured film thickness: 400 nm, PAB: 200°C / 90 seconds) Example 2: Cyclohexylbenzene containing the BPF cyanate ester of Synthesis Example 2 at a concentration of 10% by mass Non-solvent (cured film thickness: 250 nm, PAB: 120°C / 90 seconds) Comparative Example 1: BisA cyanate ester: 2,2-bis(4-cyanatophenyl)propane (Kanto Chemical Co., Ltd.) Comparative Example 2: ArF resist (TArF-P6111, polymer having an acrylic lactone skeleton: Tokyo Ohka Kogyo Co., Ltd.) (cured film thickness: 260 nm, PAB: 130°C / 60 seconds)

[0120] In Comparative Example 1, attempts were made to cure BisA cyanate ester under various temperature conditions, but it did not cure; instead, it melted, crystallized, and sublimated upon heating, making it difficult to form a cured film by itself. In contrast, cyanate esters having a fluorene skeleton (BNF cyanate ester and BPF cyanate ester) easily formed a cured film upon heating.

[0121] Reactive ion etching (RIE) test A reactive ion etching (RIE) test was then performed under the following conditions, and the etching rate of Comparative Example 2 (ArF resist) was designated "1" to evaluate the etching rates of the cyanate esters of Examples 1 and 2. That is, three silicon wafers on which a cured film of each resist composition was formed were prepared as described above. Masking tape was applied across the center of each silicon wafer to create test pieces. All test pieces were placed in the chamber of a reactive ion etching (RIE) apparatus, and reactive ion etching was performed under the following conditions. In Example 1 and Comparative Example 2, one test piece was sequentially removed from the cured film of each resist composition 30 seconds, 60 seconds, and 120 seconds after the start of etching, and in Example 2, one test piece was sequentially removed from the cured film of each resist composition 60 seconds, 90 seconds, and 120 seconds after the start of etching. The test was terminated when visual inspection confirmed that the bottom of the chamber was colored or that the cured film had disappeared, exposing the silicon substrate. This procedure was repeated four times.

[0122] [RIE dry etching conditions] Gas type: CF4 = 100 ml / min, O2 = 2 ml / min RF output: 150W Pressure: 10Pa Time: 30 seconds → 60 seconds → 120 seconds

[0123] Film thickness T (nm) and etching time ET The etching rate equation was derived from the relationship between the etching time (processing time) and the film thickness. Figure 1 shows the relationship between the etching time (processing time) and the film thickness.

[0124] The etching rate formula and etching rate were as follows: Example 1 (BNF cyanate ester): T = -0.848 x E T +400 Etching rate: 0.848 nm / sec Example 2 (BPF cyanate ester): T = -1.08 x E T +254 Etching rate: 1.08 nm / sec Comparative Example 2 (ArF resist): T = -1.50 × E T +269 Etching rate: 1.50 nm / sec

[0125] When the etching rate of Comparative Example 2 (ArF resist) was taken as "1.0", the etching rate ratios of Example 1 (BNF cyanate ester) and Example 2 (BPF cyanate ester) were as follows.

[0126] Comparative Example 2 (ArF resist) / Example 2 (BPF cyanate ester) / Example 1 (BNF cyanate ester)=1.0 / 0.72 / 0.56

[0127] As is clear from this etching rate ratio and the slope of the graph in FIG. 1, Example 2 (BPF cyanate ester) exhibits higher etching resistance than Comparative Example 2 (ArF resist), and it was confirmed that Example 1 (BNF cyanate ester) has particularly high etching resistance. [Industrial Applicability]

[0128] The cyanate ester of the present invention forms cured films with high heat resistance and chemical resistance. Therefore, the cyanate ester can be used as a modifier for various thermosetting resins. It can also be used in combination with epoxy resins, phenolic resins, bismaleimide resins, etc. to form paints, inks, adhesives, etc., and is also suitable for forming resin compositions (including flame-retardant resin compositions) suitable for structural materials. In particular, due to their high electrical insulation properties and small dielectric loss tangent (dielectric constant), the cyanate ester and resin compositions are suitable for electrical and electronic materials, and compositions containing the cyanate ester can be used for prepregs, composite materials, molding materials, printed wiring boards, and sealants for electronic components. Furthermore, it can form cured films with high etching resistance. Therefore, the cyanate ester can be used as a component of resist materials (compositions) and is advantageous for forming resistant films such as underlayer films (protective films) and antireflective films in the manufacture of semiconductor devices in which microfabrication or predetermined patterns (circuit patterns) are formed by lithography using photoresist materials.

Claims

1. A resist material containing a cyanate ester represented by the following formula (1): 【Chemical 1】 (In the formula, Z １ and Z ２ each represents a benzene ring, and Ar １ and Ar ２ each represents the same or different arene ring, R １ , R ２ , R ３ and R ４ each represents the same or different substituent, m and n represent an integer of 0 or 1 or more, and p and q represent an integer of 0 to 4.

2. 2. The resist material of claim 1, wherein the cyanate ester is in a crystalline form.

3. 3. The resist material according to claim 1, which is at least one material selected from the group consisting of a resist underlayer film material and a resist anti-reflective film material.

4. The resist material according to any one of claims 1 to 3, further comprising an organic solvent.

5. 5. At least one type of resist film selected from a resist underlayer film and a resist anti-reflective film, which is formed from the resist material according to claim 1.

6. A method for forming an underlayer film and / or an anti-reflective film, comprising applying the resist material according to any one of claims 1 to 4 directly or indirectly to a substrate and heating the applied resist material.

7. A semiconductor device comprising a substrate, an underlayer film and / or an anti-reflective film formed directly or indirectly on the substrate, and at least one photoresist layer formed on the underlayer film and / or the anti-reflective film, wherein at least the photoresist layer is formed in a predetermined pattern, and the underlayer film and / or the anti-reflective film is formed from the resist material according to any one of claims 1 to 4.

8. A pattern formation method comprising the steps of directly or indirectly forming an underlayer film and / or an antireflective film on a substrate, forming at least one photoresist layer on the underlayer film and / or the antireflective film, and irradiating the photoresist layer with energy rays in a predetermined pattern and developing the photoresist layer, wherein the underlayer film and / or the antireflective film is formed from the resist material according to any one of claims 1 to 4.

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