JP2013140342A - Radiation-sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition having high solubility in a safe solvent, high sensitivity, small roughness, and a favorable resist pattern shape.SOLUTION: A radiation-sensitive composition includes: two or more kinds of compounds that are useful as acid amplification-type low molecule-based resist material, have 70 mol% or more of specific stereoisomers, and are represented by specific chemical constitution formulas; and a solvent. The solid component is in the range of 1-80 mass% and the solvent is in the range of 20-99 mass%, and the total ratio of the compounds in the solid component is 20-99.9 mass%.

Description

  The present invention relates to a radiation-sensitive composition containing two or more kinds of compounds mainly composed of a specific stereoisomer, which is useful as an acid amplification type low molecular weight resist material.

Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, a resist thin film prepared by applying a solution of a polymer resist material such as polymethyl methacrylate, polyhydroxystyrene having an acid-dissociable reactive group or polyalkyl methacrylate on a substrate, ultraviolet rays, far ultraviolet rays, electron beams, extreme A line pattern of about 45 to 100 nm is formed by irradiating with ultraviolet rays (EUV), X-rays or the like.

  However, the polymer resist has a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution. Therefore, in lithography using a polymer resist, roughness is generated on the surface of the fine pattern, making it difficult to control the pattern dimension and lowering the yield. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material, and various low molecular weight resist materials have been proposed in order to produce finer patterns.

  For example, an alkali developing negative radiation-sensitive composition (see Patent Document 1 and Patent Document 2) using a low molecular weight polynuclear polyphenol compound as a main component has been proposed, but these have insufficient heat resistance. There is a drawback that the shape of the resulting resist pattern is deteriorated.

  As a candidate for a low molecular weight resist material, an alkali development type negative radiation sensitive composition (see Patent Document 3 and Non-Patent Document 1) using a low molecular weight cyclic polyphenol compound as a main component has been proposed. Since these low molecular weight cyclic polyphenol compounds have a low molecular weight, it is expected to provide a resist pattern having a small molecular size, high resolution, and low roughness. Further, the low molecular weight cyclic polyphenol compound has a rigid cyclic structure in its skeleton, and thus provides high heat resistance despite its low molecular weight.

  However, currently known low molecular weight cyclic polyphenol compounds have problems such as low solubility in safety solvents used in semiconductor manufacturing processes, low sensitivity, and poor resist pattern shape. Improvement of polyphenol compounds is desired. Further, with the cyclic phenol compound disclosed in Patent Document 3, although a good pattern can be obtained, the material properties such as solubility characteristics are slightly unstable, and a good pattern shape cannot be stably obtained.

JP 2005-326838 A JP 2008-145539 A JP 2009-173623 A

T.A. Nakayama, M .; Nomura, K .; Haga, M .; Ueda: Bull. Chem. Soc. Jpn. 71, 2979 (1998)

  An object of the present invention is to provide a radiation-sensitive composition having high solubility in a safe solvent, high sensitivity, low roughness, and stably providing a good resist pattern shape.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have at least two kinds of compounds mainly having a specific stereoisomer having a specific structure useful as an acid amplification type low molecular weight resist material. By including the above, it is surprisingly effective in solving the above-described problems, and has high solubility in a safe solvent, high sensitivity, low roughness, and stably obtaining a better resist pattern shape. The headline and the present invention were reached. Patent Document 3 does not have a specific description showing this effect.

That is, the present invention is as follows.
1. A radiation-sensitive composition comprising two or more compounds represented by formula (1) having a specific stereoisomer of 70 mol% or more and a solvent,
Radiation sensitivity, wherein the solid component is in the range of 1 to 80% by mass, the solvent is in the range of 20 to 99% by mass, and the total proportion of the compound in the solid component is 20 to 99.9% by mass. Composition.
(1)
(In the formula (1), each R is independently a hydrogen atom, a heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted group. A branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms. Group, substituted or unsubstituted acyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkyloxyl group having 1 to 20 carbon atoms, substituted or unsubstituted Is an unsubstituted aryloyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or these groups and a divalent group (substituted or unsubstituted alkylene group, substituted or R ′ and X are each independently a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, a complex, or a group to which one or more groups selected from the group consisting of an unsubstituted arylene group and an ether group are bonded. A cyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted group A C3-C20 cycloaliphatic hydrocarbon group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted carbon number 1 to 1 20 Alkoxy group, substituted or unsubstituted amino group having 0 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted acyl group having 1 to 20 carbon atoms, substituted or unsubstituted An alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkyloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted carbon number 1 ~ 20 alkylsilyl groups, or these groups and a divalent group (one or more groups selected from the group consisting of a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group and an ether group) bonded to each other. Group.)
2. 2. The radiation-sensitive composition according to 1 above, wherein the compound is represented by the formula (2).
(2)
(In Formula (2), R is the same as the above. R ¹² is independently a hydrogen atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted straight chain having 1 to 14 carbon atoms. Or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 14 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 14 carbon atoms, or the following formula (3 Is a group represented by
(3)
In formula (3), each R ⁴ independently represents a cyano group, a nitro group, a heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or Unsubstituted C3-C14 branched aliphatic hydrocarbon group, substituted or unsubstituted C3-C14 cyclic aliphatic hydrocarbon group, substituted or unsubstituted C6-C14 aryl group, substituted Or it is an unsubstituted C1-C14 alkoxy group or a substituted or unsubstituted C1-C14 alkylsilyl group, p is an integer of 0-4, q is an integer of 0-5. )
3. 3. The radiation-sensitive composition according to 1 or 2 above, wherein at least one of the stereoisomers is a (ccc) isomer.
4). 3. The radiation-sensitive composition as described in 1 or 2 above, wherein at least one of the stereoisomers is a (ctt) isomer.
5. 3. The radiation-sensitive composition according to 1 or 2 above, wherein at least one of the stereoisomers is a (cct) isomer.
6). 3. The radiation-sensitive composition according to 1 or 2 above, wherein at least one of the stereoisomers is a (tct) isomer.
7. 3. The radiation-sensitive composition according to 2 above, wherein at least one of the stereoisomers is represented by any one of formulas (4) to (7).
8). 3. The radiation-sensitive composition according to 2 above, wherein at least one of the stereoisomers is represented by any one of formulas (8) to (11).
9. A compound having one of the stereoisomers represented by the formula (4) to the formula (7) and a compound having one of the stereoisomers represented by the formula (8) to the formula (11). 9. The radiation sensitive composition as described in 7 or 8 above, which comprises the composition.
10. Acid generation that generates acid directly or indirectly by irradiation with any one of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray and ion beam The radiation-sensitive composition according to any one of 1 to 9, further comprising an agent (C).
11. 11. The radiation sensitive composition according to any one of 1 to 10 above, further comprising an acid crosslinking agent (G).
12 The radiation-sensitive composition according to any one of the above 1 to 11, further comprising an acid diffusion controller (E).
13. The ratio of all the compounds / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) in the solid component is 50 to 99. The radiation-sensitive composition as described in 12 above, which is in the range of 498 / 0.001-49 / 0.5 to 49 / 0.001-49 / 0-49.
14 14. The radiation sensitive composition according to any one of items 1 to 13, wherein an amorphous film can be formed by spin coating.
15. 15. The radiation-sensitive composition according to any one of 1 to 14 above, wherein the dissolution rate of the amorphous film in a developing solution at 23 ° C. is 10 Å / sec or more.
16. The dissolution rate of the amorphous film after irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-rays, or the amorphous film after heating at 20 to 250 ° C. is 5 Å / sec or less. 16. The radiation-sensitive composition as described in 15 above.
17. The process of apply | coating the radiation sensitive composition of any one of said 1-16 on a board | substrate, forming a resist film, the process of exposing the said resist film, The process of developing the exposed resist film, A resist pattern forming method comprising:

  INDUSTRIAL APPLICABILITY According to the present invention, a radiation-sensitive composition containing at least two kinds of compounds having high solubility in a safety solvent, high sensitivity, low roughness, and good resist pattern shape, and the radiation-sensitive composition are used. A resist pattern forming method can be provided.

Hereinafter, the present invention will be described in detail.
(Compound, mixture (A))
The radiation sensitive composition of the present invention includes a mixture (A) composed of two or more kinds of compounds represented by the formula (1) mainly composed of a specific stereoisomer.
The mixture (A) here is an expression collectively showing two or more kinds of compounds contained in the radiation-sensitive composition of the present invention, and actually produces the radiation-sensitive composition. In this case, a mixture of two or more kinds of compounds and a solvent can be mixed, or a mixture of a mixture of each compound and a solvent can be mixed. Moreover, it can also manufacture by adding another compound to the liquid mixture of a compound and a solvent.

(1)
(In the formula (1), each R is independently a hydrogen atom, a heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted group. A branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms. Group, substituted or unsubstituted acyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkyloxyl group having 1 to 20 carbon atoms, substituted or unsubstituted Is an unsubstituted aryloyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or these groups and a divalent group (substituted or unsubstituted alkylene group, substituted or R ′ and X are each independently a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, a complex, or a group to which one or more groups selected from the group consisting of an unsubstituted arylene group and an ether group are bonded. A cyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted group A C3-C20 cycloaliphatic hydrocarbon group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted carbon number 1 to 1 20 Alkoxy group, substituted or unsubstituted amino group having 0 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted acyl group having 1 to 20 carbon atoms, substituted or unsubstituted An alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkyloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted carbon number 1 ~ 20 alkylsilyl groups, or these groups and a divalent group (one or more groups selected from the group consisting of a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group and an ether group) bonded to each other. Group.)

  Effective in solving the above problems by using a mixture (A) having a specific structure useful as an acid amplification type low molecular weight resist material and containing at least two compounds mainly composed of a specific stereoisomer In addition, it has high solubility in a safe solvent, high sensitivity, low roughness, and a stable resist pattern shape can be stably obtained.

Here, “consisting mainly of a specific stereoisomer” means that the majority of one compound is composed of a specific stereoisomer, specifically 70 mol% or more in the compound, preferably 80 mol%, more preferably 90 mol%, more preferably 95 mol% or more, particularly preferably 99 mol% or more, and most preferably 100 mol% consists of a specific stereoisomer. When the specific stereoisomer contained in the compound is less than 70 mol%, a good resist pattern shape cannot be stably obtained.
In addition, methods for obtaining compounds mainly comprising specific stereoisomers include recrystallization, separation by column chromatography or preparative liquid chromatography, optimization of reaction solvent and reaction temperature during production, etc., recrystallization, known methods Can be done.

Examples of stereoisomers constituting the compound include (ccc) isomer, (ctt) isomer, (cct) isomer, and (tct) isomer.
The compound used in the present invention is a 16-membered ring oligomer in which an aromatic ring having two ROs represented by the formula (1) is wound through a methine group at the para position of the two ROs. Therefore, the substituents attached to the four methine groups with respect to the plane of the 16-membered ring each have an upward and downward bond, and therefore each has a cis-trans isomer (stereoisomer).
(Ccc) is a compound having a structure in which a substituent attached to one methine group is sterically bonded in the cis-cis-cis direction in the clockwise order.
(Ctt) is a compound having a structure in which a substituent attached to one methine group is sterically bonded in the cis-trans-trans direction in the clockwise order.
(Cct) is a compound having a structure in which a substituent attached to one methine group is sterically bonded in the cis-cis-trans direction in the clockwise order.
(Tct) is a compound having a structure in which a substituent on one methine group is sterically bonded in the trans-cis-trans direction in the clockwise order.

Moreover, it is preferable that the compound shown by said Formula (1) is shown by Formula (2).
(2)
(In Formula (2), R is the same as the above. R ¹² is independently a hydrogen atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted straight chain having 1 to 14 carbon atoms. Or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 14 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 14 carbon atoms, or the following formula (3 Is a group represented by
(3)
In formula (3), each R ⁴ independently represents a cyano group, a nitro group, a heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or Unsubstituted C3-C14 branched aliphatic hydrocarbon group, substituted or unsubstituted C3-C14 cyclic aliphatic hydrocarbon group, substituted or unsubstituted C6-C14 aryl group, substituted Or it is an unsubstituted C1-C14 alkoxy group or a substituted or unsubstituted C1-C14 alkylsilyl group, p is an integer of 0-4, q is an integer of 0-5. )

More preferably, the compound represented by the formula (2) preferably has any stereoisomer represented by the formula (4) to the formula (7).

More preferably, the compound represented by the formula (2) preferably has any stereoisomer represented by the formula (8) to the formula (11).

Further, the mixture (A) includes a compound having one of the stereoisomers represented by the formulas (4) to (7) and the stereoisomer represented by the formulas (8) to (11). It is preferable to mix with the compound which has 1 type of these. As a result, it is possible to provide an excellent resist pattern shape with high sensitivity and low roughness.
Furthermore, the mixture (A) is preferably composed of compounds mainly composed of the same kind of stereoisomers from the viewpoint of solubility characteristics in a resist solvent.

  In this specification, “substitution” means that, unless otherwise defined, one or more hydrogen atoms in a functional group are a halogen atom, a hydroxyl group, a cyano group, a nitro group, a heterocyclic group, or a carbon number of 1 -20 linear aliphatic hydrocarbon group, branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon number 7-30 aralkyl group, C1-C20 alkoxy group, C0-20 amino group, C2-C20 alkenyl group, C1-C20 acyl group, C2-C20 alkoxy It means that it is substituted with a carbonyl group, an alkylyl group having 1 to 20 carbon atoms, an aryloyloxy group having 7 to 30 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

An unsubstituted C1-C20 linear aliphatic hydrocarbon group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, or a hexadecyl group. Group, octadecyl group and the like.
Examples of the substituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include a fluoromethyl group, a 2-hydroxyethyl group, a 3-cyanopropyl group, and a 20-nitrooctadecyl group.

An unsubstituted C3-C20 branched aliphatic hydrocarbon group is, for example, isopropyl group, isobutyl group, tertiary butyl group, neopentyl group, 2-hexyl group, 2-octyl group, 2-decyl group, 2 -Dodecyl group, 2-hexadecyl group, 2-octadecyl group, etc. are mentioned.
Examples of the substituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms include 1-fluoroisopropyl group and 1-hydroxy-2-octadecyl group.

The unsubstituted C3-C20 cyclic aliphatic hydrocarbon group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, a cyclohexadecyl group, a cyclo An octadecyl group etc. are mentioned.
Examples of the substituted C3-C20 cyclic aliphatic hydrocarbon group include a 2-fluorocyclopropyl group and a 4-cyanocyclohexyl group.

Examples of the unsubstituted aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the substituted aryl group having 6 to 20 carbon atoms include 4-isopropylphenyl group, 4-cyclohexylphenyl group, 4-methylphenyl group, 6-fluoronaphthyl group and the like.

Examples of the unsubstituted aralkyl group having 7 to 30 carbon atoms include a 4-methylphenyl group, a 4-ethylphenyl group, a 6-methylnaphthyl group, and a 2,6-dimethylnaphthyl group.
Examples of the substituted aralkyl group having 7 to 30 carbon atoms include a 4-fluoro-3-methylphenyl group.

Examples of the unsubstituted C1-C20 alkoxy group include, for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, hexadecyloxy group Group, octadecyloxy group and the like.
Examples of the substituted alkoxy group having 1 to 20 carbon atoms include a chloromethoxy group and a bromoethoxy group.

Examples of the unsubstituted amino group having 0 to 20 carbon atoms include an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a dipropylamino group, and a dibutylamino group.
Examples of the substituted amino group having 0 to 20 carbon atoms include a chloromethylamino group and a dibromomethylamino group.

Examples of the unsubstituted alkenyl group having 2 to 20 carbon atoms include vinyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, octynyl group, decynyl group, dodecynyl group, hexadecynyl group, and octadecynyl group.
Examples of the substituted alkenyl group having 2 to 20 carbon atoms include a chloropropynyl group.

Examples of the unsubstituted acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, hexadecanoyl group, and benzoyl group. Etc.
Examples of the substituted acyl group having 1 to 20 carbon atoms include a chloroacetyl group.

Examples of the unsubstituted C2-C20 alkoxycarbonyl group include, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxy A carbonyl group, a dodecyloxycarbonyl group, a hexadecyloxycarbonyl group, etc. are mentioned.
Examples of the substituted C2-C20 alkoxycarbonyl group include a chloromethoxycarbonyl group.

Examples of the unsubstituted alkyloyloxy group having 1 to 20 carbon atoms include methoxycarbonyloxy group, ethoxycarbonyloxy group, propoxycarbonyloxy group, butoxycarbonyloxy group, pentyloxycarbonyloxy group, hexyloxycarbonyloxy group, Examples include octyloxycarbonyloxy group, decyloxycarbonyloxy group, dodecyloxycarbonyloxy group, hexadecyloxycarbonyloxy group and the like.
Examples of the substituted alkyloyloxy group having 1 to 20 carbon atoms include a chloromethoxycarbonyloxy group.

Examples of the unsubstituted aryloyloxy group having 7 to 30 carbon atoms include a benzoyloxy group and a naphthylcarbonyloxy group.
Examples of the substituted aryloyloxy group having 7 to 30 carbon atoms include a chlorobenzoyloxy group.

Examples of the unsubstituted alkylsilyl group having 1 to 20 carbon atoms include methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group, hexylsilyl group, octylsilyl group, decylsilyl group, dodecylsilyl group, hexa A decylsilyl group, an octadecylsilyl group, etc. are mentioned.
Examples of the substituted alkylsilyl group having 1 to 20 carbon atoms include a chloromethylsilyl group.

  The molecular weight of the mixture (A) is 500 to 5000, preferably 800 to 2000, and more preferably 1000 to 2000. Within the above range, the resolution is improved while maintaining the film formability required for the resist.

  Calixarene is a non-polymeric phenolic compound. Calixarene was discovered in the 1950s and a synthetic method was devised. With respect to the use of calixarene as a radiation sensitive composition, calixarenes partially protected primarily by acid labile groups have been widely evaluated as positive resist materials. In these resist material applications, calix [4] resorcinarene was required to be structurally monomodal, but on the contrary it actually showed a very multimodal isomeric structure distribution.

  Specifically, the compound having 70 mol% or more of the single stereoisomer represented by the above formula (1) and the mixture (A) containing two or more kinds of the compound are composed of the aldehyde compound (A1). It is obtained by a condensation reaction between one or more compounds selected from the group and one or more compounds selected from the group consisting of the phenolic compound (A2).

  More preferably, the aldehyde compound (A1) is a compound having 2 to 59 carbon atoms having a monovalent group containing 1 to 4 formyl groups, and 1 to 3 phenolic compounds (A2). It is a C6-C15 compound which has the phenolic hydroxyl group of this.

  The aldehyde compound (A1) has 3 to 59 carbon atoms and has a monovalent group containing 1 to 4 formyl groups, and includes an aromatic aldehyde compound (A1A) and an aliphatic aldehyde compound (A1B). Selected from. The aromatic aldehyde compound (A1A) is preferably a benzaldehyde compound having 7 to 24 carbon atoms. For example, in addition to the aromatic ring of benzaldehyde, the benzaldehyde having 7 to 24 carbon atoms having a substituent containing at least one alicyclic ring or aromatic ring. For example, methylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclopropylbenzaldehyde, cyclobutanebenzaldehyde, cyclopentanebenzaldehyde, cyclohexanebenzaldehyde, phenylbenzaldehyde, naphthylbenzaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde, lactylbenzaldehyde, etc. Propyl benzaldehyde, cyclohexyl benzaldehyde, phenyl benzaldehyde 'S aldehyde are preferred, propyl benzaldehyde, cyclohexyl benzaldehyde is more preferable. The aromatic aldehyde compound (A1A) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. The aromatic aldehyde compound (A1A) may be used alone or in combination of two or more. The aliphatic aldehyde compound (A1B) may have a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. The aliphatic aldehyde compound (A1B) may be used alone or in combination of two or more.

  It is preferable that carbon number of a phenolic compound (A2) is 6-15, and it is preferable to have 1-3 phenolic hydroxyl groups. Examples of the phenolic compound (A2) include phenol, catechol, resorcinol, hydroquinone, pyrogallol, 3-methoxyphenol, 3-ethoxyphenol, 3-cyclohexyloxyphenol, 1,3-dimethoxybenzene, 1,3-diethoxy. Benzene, 1,3-dicyclohexyloxybenzene and the like, resorcinol, pyrogallol, 3-methoxyphenol, 3-ethoxyphenol, 3-cyclohexyloxyphenol, 1,3-dimethoxybenzene, 1,3-diethoxybenzene, 1,3-dicyclohexyloxybenzene is preferred, and resorcinol is more preferred. The phenolic compound (A2) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen or the like as long as the effects of the present invention are not impaired. You may use a phenolic compound (A2) individually or in combination of 2 or more types.

  The compound having 70 mol% or more of the single stereoisomer represented by the above formula (1) and the mixture (A) containing two or more kinds of the compound are, for example, an acid catalyst in an organic solvent such as methanol and ethanol. In the presence of (hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, etc.), 0.1 to 10 moles of phenolic compound (A2) at 40 to 150 ° C. is 0.5 to 1 mole relative to 1 mole of aldehyde compound (A1). React for about 20 hours. Subsequently, after filtration, washing with alcohols such as methanol, washing with water, separation by filtration, and drying, a compound having each stereoisomer having a molecular weight of 500 to 5000 and a blend of the compounds are obtained. In place of the acid catalyst, a basic catalyst (sodium hydroxide, barium hydroxide or 1,8-diazabicyclo [5.4.0] undecene-7, etc.) is used, and each stereoisomer may be reacted by reacting in the same manner. Compounds with body and blends of the compounds are obtained. Further, the compound having each stereoisomer of the present invention and the blend of the compound are obtained by converting the aldehyde compound (A1) into a dihalide with hydrogen halide or a halogen gas, and then isolating the isolated dihalide and the phenolic compound (A2). Can also be produced.

  You may refine | purify as needed for the purpose of improving the purity of the said mixture (A) and reducing the amount of residual metals. If the acid catalyst and the cocatalyst remain, generally, the storage stability of the radiation-sensitive composition is lowered, or if the basic catalyst remains, generally the sensitivity of the radiation-sensitive composition is lowered. The intended purification may be performed.

  The purification method can be carried out by a known method as long as the compound having each stereoisomer and the blend of the compound are not modified, and is not particularly limited. For example, a method of washing with water, a method of washing with an acidic aqueous solution , A method of washing with a basic aqueous solution, a method of treating with an ion exchange resin, a method of treating with silica gel column chromatography, a method using recrystallization, and the like. These purification methods are more preferably performed in combination of two or more.

  Acidic aqueous solution, basic aqueous solution, ion exchange resin, and silica gel column chromatography are optimal depending on the metal to be removed, the amount and type of acidic compound and basic compound, and the type and stereoisomer of the compound to be purified. Can be selected as appropriate. For example, as acidic aqueous solution, hydrochloric acid, nitric acid, acetic acid aqueous solution having a concentration of 0.01 to 10 mol / L, aqueous ammonia solution having a concentration of 0.01 to 10 mol / L as basic aqueous solution, cation exchange resin as ion exchange resin, For example, Amberlyst 15J-HG Dry made by Organo can be mentioned.

  You may dry after refinement | purification. The drying can be performed by a known method, and is not particularly limited, and examples thereof include a method of vacuum drying, hot air drying, and air drying under the condition that the compound having each stereoisomer and the blend of the compound are not denatured.

  The mixture (A) can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.

  The mixture (A) containing two or more compounds having a single stereoisomer represented by the above formula (1) of 70 mol% or more is irradiated with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, It is useful as a negative resist material that becomes a compound that is hardly soluble in a developer. By irradiating a compound having each configuration and a blend of the compound with KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, a condensation reaction between the compounds is induced, and a compound which is hardly soluble in an alkali developer It is thought to be. The resist pattern thus obtained has a very low LER.

  The mixture (A) can be used as a main component of the negative radiation-sensitive composition, and can be added to the radiation-sensitive composition as an additive for improving sensitivity and etching resistance, for example. In this case, the compound having each configuration and the blend of the compound are used in an amount of 1 to 49.999% by mass based on the total weight of the solid components of the radiation-sensitive composition.

  The compound and the mixture (A) are preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape, and performance such as high resolution is improved.

  It is preferable that the crystallization calorific value calculated | required by the differential scanning calorimetry of the glass transition temperature of the said compound and the said mixture (A) is less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, further preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is in the above range, it is easy to form an amorphous film by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

  In the present invention, the crystallization calorific value, the crystallization temperature, and the glass transition temperature can be obtained by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is put in an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 mL / min). After the rapid cooling, the temperature is raised again to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). Further, after rapid cooling, the temperature is raised again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 mL / min). The temperature at the midpoint of the step difference of the baseline that has changed in a step shape (where the specific heat has changed to half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.

  The compound and the mixture (A) have low sublimation properties under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, more preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. Is preferred. The low sublimation property means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be obtained with low LER.

  The compound and the mixture (A) preferably satisfy F <3.0 (F represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms)), and more preferably satisfy F <2.5. . By satisfying the above conditions, the dry etching resistance is excellent.

  The compound and the mixture (A) are propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, propionic acid. A solvent selected from ethyl and ethyl lactate and having the highest solubility in a compound having each configuration and a blend of the compound at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass % Or more, more preferably 10% by mass or more, and particularly preferably a solvent selected from PGMEA, PGME, and CHN and having the highest solubility in a compound having each configuration and a blend of the compound, 20 mass% or more at 23 ° C., particularly preferably PGM Against A, at 23 ° C., to dissolve more than 20 wt%. By satisfying the above conditions, the semiconductor manufacturing process can be used in actual production.

  Nitrogen atoms may be introduced into the mixture (A) as long as the effects of the present invention are not impaired. The ratio of the number of nitrogen atoms to the total number of constituent atoms of the mixture (A) is preferably 0.1 to 40%, more preferably 0.1 to 20%, and preferably 0.1 to 10%. More preferably, it is 0.1 to 5%. Within the above range, the line edge roughness of the resulting resist pattern can be reduced. The introduced nitrogen atom is preferably a secondary or tertiary nitrogen atom, and more preferably a tertiary nitrogen atom.

  To the extent that the effects of the present invention are not impaired, the compound and the mixture (A) are irradiated with visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray and ion beam, or chemical induced thereby. A crosslinking reactive group that causes a crosslinking reaction by reaction may be introduced. The introduction is performed, for example, by reacting a compound having each configuration and a blend of the compound with a crosslinking reactive group introduction reagent in the presence of a base catalyst. Examples of the crosslinking reactive group include a carbon-carbon multiple bond, an epoxy group, an azide group, a halogenated phenyl group, and a chloromethyl group. Examples of the crosslinking reactive group introduction reagent include acids, acid chlorides, acid anhydrides, carboxylic acid derivatives such as dicarbonates and alkyl halides having such a crosslinking reactive group. A radiation-sensitive composition comprising a compound having each configuration having a crosslinking reactive group and a blend of the compound is also useful as a non-polymeric radiation-sensitive composition having high resolution, high heat resistance and solvent solubility. .

  A non-acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group of the compound as long as the effect of the present invention is not impaired. The non-acid-dissociable functional group refers to a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. For example, C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxyl group, cyano group, nitro group, hydroxyl group, Examples thereof include a functional group selected from the group consisting of a cyclic group, a halogen, a carboxyl group, a C1-20 alkylsilane, and derivatives thereof.

  A naphthoquinonediazide ester group may be introduced into the phenolic hydroxyl group of the compound within a range not impairing the effects of the present invention. A compound having each configuration in which a naphthoquinone diazide ester group is introduced into at least one phenolic hydroxyl group of the compound having each configuration and the blend of the compound, and the blend of the compound, have a negative type In addition to being used as a main component of a radiation composition, it can be used as a main component of a positive radiation-sensitive composition, or can be added to a radiation-sensitive composition as an acid generator or additive.

  As long as the effects of the present invention are not impaired, an acid-generating functional group that generates an acid upon irradiation with radiation may be introduced into at least one phenolic hydroxyl group of the blend of the compounds. The compound having each configuration in which an acid-generating functional group is introduced into at least one phenolic hydroxyl group of the compound having each configuration and the blend of the compound and the blend of the compound are negatives based on themselves. In addition to being used as the main component of the type radiation sensitive composition, it can be added to the radiation sensitive composition as an additive.

  As long as the effects of the present invention are not impaired, an acid dissociable functional group that dissociates upon irradiation with radiation may be introduced into at least one phenolic hydroxyl group of the blend of the compounds. A compound having each configuration in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of the compound having each configuration and the blend of the compound, and a blend of the compound include a ketone solvent and an ester described later. When a polar solvent such as a solvent, an alcohol solvent, an amide solvent or an ether solvent, or a hydrocarbon solvent is used as a developer, it can be used as a negative radiation-sensitive composition with itself as a main component. Moreover, when using an alkali developing solution, it can be used as a positive radiation sensitive composition by itself as a main component. In either case, it can be added as an additive to the radiation-sensitive composition.

In the present invention, the acid dissociable functional group means a characteristic group that is cleaved in the presence of an acid to generate an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. A phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable. The acid-dissociable functional group is appropriately selected from those proposed for hydroxystyrene-based resins and (meth) acrylic acid-based resins used in chemically amplified resist compositions for KrF and ArF. be able to. For example, substituted methyl group, 1-substituted ethyl group, 1-substituted-n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group, alkoxycarbonyl group, alkoxycarbonyl An alkyl group etc. are mentioned. The acid dissociable functional group preferably has no crosslinkable functional group.

The substituted methyl group is usually a substituted methyl group having 2 to 20 carbon atoms, preferably a substituted methyl group having 4 to 18 carbon atoms, and more preferably a substituted methyl group having 6 to 16 carbon atoms. For example, methoxymethyl group, methylthiomethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, t-butoxymethyl group, 2-methylpropoxymethyl group, ethylthiomethyl group, methoxy Ethoxymethyl group, phenyloxymethyl group, 1-cyclopentyloxymethyl group, 1-cyclohexyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl group, and the following formula ( The substituent etc. which are shown by 13-1) can be mentioned. In addition, as R < ² > in following formula (13-1), a methyl group, an ethyl group, isopropyl group, n-propyl group, t-butyl group, n-butyl group etc. are mentioned, for example.

(13-1)
(In formula (13-1), R ² is an alkyl group having 1 to 4 carbon atoms.)

  The 1-substituted ethyl group is usually a 1-substituted ethyl group having 3 to 20 carbon atoms, preferably a 1-substituted ethyl group having 5 to 18 carbon atoms, and more preferably a substituted ethyl group having 7 to 16 carbon atoms. . For example, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, n-propoxyethyl group, Isopropoxyethyl group, n-butoxyethyl group, t-butoxyethyl group, 2-methylpropoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-cyclopentyloxy Examples thereof include an ethyl group, a 1-cyclohexyloxyethyl group, a 1-phenylethyl group, a 1,1-diphenylethyl group, and a substituent represented by the following formula (13-2).

(13-2)
(In formula (13-2), R ² is the same as described above.)

The 1-substituted-n-propyl group is usually a 1-substituted-n-propyl group having 4 to 20 carbon atoms, preferably a 1-substituted-n-propyl group having 6 to 18 carbon atoms, and having 8 carbon atoms. More preferred are ˜16 1-substituted-n-propyl groups. For example, a 1-methoxy-n-propyl group and a 1-ethoxy-n-propyl group can be exemplified.
The 1-branched alkyl group is usually a 1-branched alkyl group having 3 to 20 carbon atoms, preferably a 1-branched alkyl group having 5 to 18 carbon atoms, and more preferably a branched alkyl group having 7 to 16 carbon atoms. . For example, isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, 2-methyladamantyl group, 2-ethyladamantyl group, etc. Can be mentioned.

The silyl group is usually a silyl group having 1 to 20 carbon atoms, preferably a silyl group having 3 to 18 carbon atoms, and more preferably a silyl group having 5 to 16 carbon atoms. For example, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group and triphenylsilyl Groups and the like.
The acyl group is usually an acyl group having 2 to 20 carbon atoms, preferably an acyl group having 4 to 18 carbon atoms, and more preferably an acyl group having 6 to 16 carbon atoms. Examples include acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, adamantylcarbonyl group, benzoyl group and naphthoyl group.

The 1-substituted alkoxymethyl group is usually a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms, preferably a 1-substituted alkoxymethyl group having 4 to 18 carbon atoms, and a 1-substituted alkoxy group having 6 to 16 carbon atoms. More preferred are alkoxymethyl groups. For example, 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group, 1-adamantylmethoxymethyl group and the like can be mentioned. .
The cyclic ether group is usually a cyclic ether group having 2 to 20 carbon atoms, preferably a cyclic ether group having 4 to 18 carbon atoms, and more preferably a cyclic ether group having 6 to 16 carbon atoms. Examples thereof include a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 4-methoxytetrahydropyranyl group, a 4-methoxytetrahydrothiopyranyl group, and the like.

  The alkoxycarbonyl group is usually an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonyl group having 6 to 16 carbon atoms. For example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, or acid dissociation property represented by n = 0 in the following formula (13-3) A functional group etc. can be mentioned.

  The alkoxycarbonylalkyl group is usually an alkoxycarbonylalkyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonylalkyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonylalkyl group having 6 to 16 carbon atoms. For example, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, or acid dissociation represented by n = 1 to 4 in the following formula (13-3) Sexual functional groups and the like.

(13-3)
(In formula (13-3), R ³ is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 4.)

Of these acid dissociable functional groups, a substituted methyl group, a 1-substituted ethyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group are preferable. An ethyl group, an alkoxycarbonyl group and an alkoxycarbonylalkyl group are more preferable because of high sensitivity, and further an acid-dissociable functional group having a structure selected from a cycloalkane having 3 to 12 carbon atoms, a lactone and an aromatic ring having 6 to 12 carbon atoms. Is more preferable. The cycloalkane having 3 to 12 carbon atoms may be monocyclic or polycyclic, but is preferably polycyclic. Specific examples include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane and the like. More specifically, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, Examples include polycycloalkanes such as isobornane, tricyclodecane, and tetracyclodecane. Among these, adamantane, tricyclodecane, and tetracyclodecane are preferable, and adamantane and tricyclodecane are particularly preferable. The cycloalkane having 3 to 12 carbon atoms may have a substituent. Examples of the lactone include butyrolactone or a cycloalkane group having 3 to 12 carbon atoms having a lactone group. Examples of the 6-12 aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring, and a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is particularly preferable.
In particular, an acid dissociable functional group selected from the group consisting of groups represented by the following formula (13-4) is preferable because of high resolution.

(13-4)

(In Formula (13-4), R ⁵ is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, R ⁶ is hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, cyano. A group, a nitro group, a heterocyclic group, a halogen, and a carboxyl group, n ₁ is an integer of 0 to 4, n ₂ is an integer of 1 to 5, and n ₀ is an integer of ₀ to 4.)

(Radiation sensitive composition)
The radiation sensitive composition by this invention contains each compound (mixture (A)) mentioned above, and a solvent.
The radiation-sensitive composition of the present invention comprises 1 to 80% by mass of a solid component and 20 to 99% by mass of a solvent, and the content of each compound (mixture (A)) is 20 to 99 of the total mass of the solid component. .9% by mass.

  The radiation-sensitive composition of the present invention can form an amorphous film by spin coating. The dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present invention in a developing solution at 23 ° C. is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and more preferably 100 to 1000 Å / sec. Further preferred. It can melt | dissolve in a developing solution as it is 10 tons / sec or more, and can be set as a resist. In addition, when the dissolution rate is 10000 kg / sec or less, the resolution may be improved. This is because the contrast of the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer increases in contrast due to the change in the solubility of the compound having each configuration and the blend of the compound before and after exposure. It is guessed from. Further, there is an effect of reducing LER and reducing defects.

  The dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present invention in a developer at 23 ° C. at a portion exposed to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray is 5 Å / sec or less is preferable, 0.05 to 5 Å / sec is more preferable, and 0.0005 to 5 Å / sec is more preferable. If it is 5 kg / sec or less, it is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed to be due to the fact that the micro surface parts of the compounds having the respective configurations and the blends of the compounds are dissolved to reduce LER. There is also an effect of reducing defects.

  The radiation sensitive composition of the present invention is preferably 1 to 80% by mass of a solid component and 20 to 99% by mass of a solvent, more preferably 1 to 50% by mass of a solid component and 50 to 99% by mass of a solvent, and further preferably. The solid component is 2 to 40% by mass and the solvent is 60 to 98% by mass, particularly preferably 2 to 10% by mass and the solvent is 90 to 98% by mass.

  The amount of the mixture (A) is determined based on the total mass of the solid component (a blend of compounds having each configuration, an acid generator (C), an acid crosslinking agent (G), an acid diffusion controller (E), and other components ( F) to 209.9% by weight, preferably 30 to 90% by weight, more preferably 40 to 80% by weight, and most preferably 50 to 50% by weight. 70% by mass. When the blending ratio is as described above, high resolution is obtained and the line edge roughness is reduced.

  The radiation-sensitive composition of the present invention can directly or indirectly produce an acid by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray and ion beam. It is preferable that at least one acid generator (C) to be generated is included. The amount of the acid generator (C) used is preferably 0.001 to 49 mass%, more preferably 1 to 40 mass%, further preferably 3 to 30 mass%, and 10 to 25 mass% of the total weight of the solid component. Particularly preferred. By using within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In the present invention, the acid generation method is not limited as long as an acid is generated in the system. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing is possible, and if high-energy rays are used, electron beam, extreme ultraviolet rays, X-rays, ion beam, further fine processing Is possible.

The acid generator (C) is preferably at least one selected from the group consisting of compounds represented by the following formulas (7-1) to (7-8).
(7-1)
(In formula (7-1), R ¹³ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. group, a hydroxyl group or a halogen atom; X ^- is an alkyl group, an aryl group, a sulfonic acid ion or halide ion having a halogen-substituted alkyl group or halogen-substituted aryl group).

  The compound represented by the formula (7-1) includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-. Octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanes Phonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri ( 4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylben Zensulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6 -Trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo (1,3-perfluoropropanedisulfone) at least one selected from the group consisting of imidates It is preferable that a class.

(7-2)
(In formula (7-2), R ¹⁴ may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. A group, a hydroxyl group or a halogen atom, X ⁻ is the same as defined above.)

  The compound represented by the formula (7-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodoniumbenzenesulfonate, bis (4-t-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis ( 4-t Butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, Diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4-difluorobenzene Sulfonate, diphenyl Iodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium per From fluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate Preferably, at least one selected from the group consisting of:

(7-3)
(In formula (7-3), Q represents an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ represents an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

  The compound represented by the formula (7-3) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) Succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-Dicarboximide, N- 10-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept It is preferably at least one selected from 5-En 2,3-dicarboximide, and N- (perfluoro--n- C1-12alkyl oxy) group consisting naphthylimide.

(7-4)
(In Formula (7-4), R ¹⁶ may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

  The compound represented by the formula (7-4) is diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone. , Di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-trifluoromethylphenyl) disulfone It is preferable.

(7-5)
(In Formula (7-5), R ¹⁷ may be the same or different, and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

  The compound represented by the formula (7-5) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino). -Phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile And at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

(7-6)
(In the formula (7-6), R ^{18 s} may be the same or different, and are each independently a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The number of carbon atoms is preferably 1 to 5.)

In formulas (7-7) and (7-8), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, or cyclopentyl. Group, cycloalkyl group such as cyclohexyl group, alkoxyl group having 1 to 3 carbon atoms such as methoxy group, ethoxy group, propoxy group, or aryl group such as phenyl group, toluyl group, naphthyl group, preferably 6 carbon atoms -10 aryl groups. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (7-7-1), a carbonyl group, an ester group, an amide group or an ether group. Y ¹⁹ is a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ is independently a group represented by the following formula (7-8-1).

(In the formula (7-8-1), Z ²² each independently represents an alkyl group, a cycloalkyl group or an aryl group, R ²² represents an alkyl group, a cycloalkyl group or an alkoxyl group, and r represents 0-3. Is an integer.)

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1, 4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyla) Bissulfonyldiazomethanes such as methylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6 Halogen-containing triazine derivatives such as-(bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate Etc.

Among the acid generators, an acid generator having an aromatic ring is preferable, and an acid generator represented by the formula (7-1) or (7-2) is more preferable. The acid generator having a sulfonate ion having X ^{− in} formula (7-1) or (7-2) having an aryl group or a halogen-substituted aryl group is more preferable, and the acid generator having a sulfonate ion having an aryl group Are particularly preferable, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferable. LER can be reduced by using the acid generator.
The acid generator (C) may be used alone or in combination of two or more.

  The radiation-sensitive composition of the present invention preferably contains one or more acid crosslinking agents (G). The acid cross-linking agent (G) can cross-link a compound having each configuration of formula (1) and a blend of the compound in the molecule or inter-molecularly in the presence of an acid generated from the acid generator (C). A compound. Examples of such an acid crosslinking agent (G) include one or more groups (hereinafter referred to as “crosslinkable groups”) capable of crosslinking a compound having each configuration of formula (1) and a blend of the compounds. The compound which has can be mentioned.

  Specific examples of such a crosslinkable group include (i) hydroxyalkyl groups such as hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like. Or a group derived therefrom; (ii) a carbonyl group such as formyl group or carboxy (C1-C6 alkyl group) or a group derived therefrom; (iii) dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl; Groups, nitrogen-containing groups such as diethylolaminomethyl groups, morpholinomethyl groups; (iv) glycidyl group-containing groups such as glycidyl ether groups, glycidyl ester groups, glycidylamino groups; (v) benzyloxymethyl groups, benzoyloxy C1-C6 allyloxy (C1-C6 alkyl group) such as methyl group, C1-C A group derived from an aromatic group such as 6-aralkyloxy (C1-C6 alkyl group); and (vi) a polymerizable multiple bond-containing group such as a vinyl group or isopropenyl group. As the crosslinkable group of the acid crosslinking agent (G) of the present invention, a hydroxyalkyl group, an alkoxyalkyl group, and the like are preferable, and an alkoxymethyl group is particularly preferable.

  Examples of the acid crosslinking agent (G) having a crosslinkable group include (i) a methylol group-containing melamine compound, a methylol group-containing benzoguanamine compound, a methylol group-containing urea compound, a methylol group-containing glycoluril compound, and a methylol group-containing phenol compound. (Ii) alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing glycoluril compound, alkoxyalkyl group-containing phenolic compound and the like Compound; (iii) Carboxymethyl group-containing melamine compound, Carboxymethyl group-containing benzoguanamine compound, Carboxymethyl group-containing urea compound, Carboxymethyl group-containing grease Carboxymethyl group-containing compounds such as alluryl compounds and carboxymethyl group-containing phenol compounds; (iv) bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resole resin-based epoxy compounds, Examples thereof include epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds.

  As the acid crosslinking agent (G), compounds having phenolic hydroxyl groups, and compounds and resins imparted with crosslinking properties by introducing the crosslinking groups into acidic functional groups in alkali-soluble resins can be used. . In this case, the introduction rate of the crosslinkable group is usually 5 to 100 mol%, preferably 10 to 60 mol%, more preferably based on the total acidic functional group in the compound having a phenolic hydroxyl group and the alkali-soluble resin. Is adjusted to 15-40 mol%. Within the above range, the cross-linking reaction occurs sufficiently, and a decrease in the remaining film ratio, a pattern swelling phenomenon, meandering, and the like can be avoided.

  In the radiation-sensitive composition of the present invention, the acid crosslinking agent (G) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof. Particularly preferred acid crosslinking agents (G) include compounds represented by the following formulas (8-1) to (8-3) and alkoxymethylated melamine compounds (acid crosslinking agent (G1)).

(In the above formulas (8-1) to (8-3), R ⁷ each independently represents a hydrogen atom, an alkyl group or an acyl group; R ^{8 to} R ¹¹ each independently represents a hydrogen atom or a hydroxyl group. And represents an alkyl group or an alkoxyl group; X ² represents a single bond, a methylene group or an oxygen atom.)

The alkyl group represented by R ⁷ preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The acyl group represented by R ⁷ preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and examples thereof include an acetyl group and a propionyl group. The alkyl group represented by R ^{8 to} R ¹¹ preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxyl group represented by R ^{8 to} R ¹¹ preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² is preferably a single bond or a methylene group. R ^{7 to} R ¹¹ and X ² may be substituted with an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a hydroxyl group, or a halogen atom. The plurality of R ⁷ and R ^{8 to} R ¹¹ may be the same or different.

Specific examples of the compound represented by the formula (8-1) include the compounds shown below.

  Specific examples of the compound represented by the formula (8-2) include, for example, N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril. N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (isopropoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) ) Glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, and the like. Among these, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferable.

Specific examples of the compound represented by the formula (8-3) include the compounds shown below.

Specific examples of the alkoxymethylated melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxymethyl) melamine N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (isopropoxymethyl) melamine, N, N, N, N, Examples thereof include N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.
The acid cross-linking agent (G1) is obtained by, for example, condensing a urea compound or glycoluril compound and formalin to introduce a methylol group, and then ether with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Then, the reaction solution is cooled and the precipitated compound or its resin is recovered. The acid cross-linking agent (G1) can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicalac (manufactured by Sanwa Chemical Co., Ltd.).

  Further, as other particularly preferable acid crosslinking agent (G), the molecule has 1 to 6 benzene rings, and has at least two hydroxyalkyl groups and / or alkoxyalkyl groups in the molecule. And / or a phenol derivative in which an alkoxyalkyl group is bonded to any one of the benzene rings (acid crosslinking agent (G2)). Preferably, the molecular weight is 1500 or less, the molecule has 1 to 6 benzene rings, and the hydroxyalkyl group and / or alkoxyalkyl group has 2 or more in total, and the hydroxyalkyl group and / or alkoxyalkyl group is the benzene. Mention may be made of phenol derivatives formed by bonding to any one or a plurality of benzene rings.

  As a hydroxyalkyl group couple | bonded with a benzene ring, C1-C6 things, such as a hydroxymethyl group, 2-hydroxyethyl group, and 2-hydroxy-1-propyl group, are preferable. As an alkoxyalkyl group couple | bonded with a benzene ring, a C2-C6 thing is preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 2-methoxyethyl Group or 2-methoxy-1-propyl group is preferred.

Among these phenol derivatives, particularly preferable ones are listed below.

In the above formula, L ^{1 to} L ⁸ may be the same or different and each independently represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group. A phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, they can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.
A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in EP632003A1 and the like.

  A phenol derivative having a hydroxymethyl group and / or an alkoxymethyl group synthesized in this manner is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. preferable. The acid crosslinking agent (G2) may be used alone or in combination of two or more.

Another particularly preferable acid crosslinking agent (G) is a compound having at least one α-hydroxyisopropyl group (acid crosslinking agent (G3)). The structure is not particularly limited as long as it has an α-hydroxyisopropyl group. In addition, the hydrogen atom of the hydroxyl group in the α-hydroxyisopropyl group is one or more acid dissociable groups (R—COO— group, R—SO ₂ — group, etc., R is a straight chain having 1 to 12 carbon atoms) A hydrocarbon group having 3 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a 1-branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms (Represents a substituent selected from the group). Examples of the compound having the α-hydroxyisopropyl group include one or two kinds such as a substituted or unsubstituted aromatic compound, diphenyl compound, naphthalene compound, and furan compound containing at least one α-hydroxyisopropyl group. The above is mentioned. Specifically, for example, a compound represented by the following general formula (9-1) (hereinafter referred to as “benzene compound (1)”), a compound represented by the following general formula (9-2) (hereinafter referred to as “benzene compound (1)”). , “Diphenyl compound (2)”), a compound represented by the following general formula (9-3) (hereinafter referred to as “naphthalene compound (3”)), and the following general formula (9-4). And the like (hereinafter referred to as “furan compound (4)”).

In the general formulas (9-1) to (9-4), each A ² independently represents an α-hydroxyisopropyl group or a hydrogen atom, and at least one A ² is an α-hydroxyisopropyl group. In General Formula (9-1), R ⁵¹ is a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched group having 2 to 6 carbon atoms. An alkoxycarbonyl group is shown. Furthermore, in the general formula (9-2), R ⁵² represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —CO— or —COO—. Moreover, in general formula (9-4), ^R53 and ^R54 show a hydrogen atom or a C1-C6 linear or branched alkyl group mutually independently.

  Specific examples of the benzene compound (1) include α-hydroxyisopropylbenzene, 1,3-bis (α-hydroxyisopropyl) benzene, 1,4-bis (α-hydroxyisopropyl) benzene, and 1,2. , 4-Tris (α-hydroxyisopropyl) benzene, α-hydroxyisopropylbenzenes such as 1,3,5-tris (α-hydroxyisopropyl) benzene; 3-α-hydroxyisopropylphenol, 4-α-hydroxyisopropylphenol , 3,5-bis (α-hydroxyisopropyl) phenol, α-hydroxyisopropylphenols such as 2,4,6-tris (α-hydroxyisopropyl) phenol; 3-α-hydroxyisopropylphenyl methyl ketone, 4-α -Hydroxyisopropyl Nyl methyl ketone, 4-α-hydroxyisopropylphenyl ethyl ketone, 4-α-hydroxyisopropylphenyl n-propyl ketone, 4-α-hydroxyisopropylphenyl isopropyl ketone, 4-α-hydroxyisopropylphenyl n-butyl ketone, 4-α-hydroxyisopropylphenyl · t-butylketone, 4-α-hydroxyisopropylphenyl · n-pentylketone, 3,5-bis (α-hydroxyisopropyl) phenyl · methylketone, 3,5-bis (α-hydroxyisopropyl) ) Α-hydroxyisopropylphenyl alkyl ketones such as phenyl ethyl ketone, 2,4,6-tris (α-hydroxyisopropyl) phenyl methylketone; methyl 3-α-hydroxyisopropylbenzoate , Methyl 4-α-hydroxyisopropyl benzoate, ethyl 4-α-hydroxyisopropyl benzoate, n-propyl 4-α-hydroxyisopropyl benzoate, isopropyl 4-α-hydroxyisopropyl benzoate, 4-α-hydroxyisopropyl benzoate N-butyl acid, t-butyl 4-α-hydroxyisopropylbenzoate, n-pentyl 4-α-hydroxyisopropylbenzoate, methyl 3,5-bis (α-hydroxyisopropyl) benzoate, 3,5-bis ( Alkyl 4-α-hydroxyisopropylbenzoate such as ethyl α-hydroxyisopropyl) benzoate and methyl 2,4,6-tris (α-hydroxyisopropyl) benzoate.

  Specific examples of the diphenyl compound (2) include 3-α-hydroxyisopropylbiphenyl, 4-α-hydroxyisopropylbiphenyl, 3,5-bis (α-hydroxyisopropyl) biphenyl, 3,3 ′. -Bis (α-hydroxyisopropyl) biphenyl, 3,4'-bis (α-hydroxyisopropyl) biphenyl, 4,4'-bis (α-hydroxyisopropyl) biphenyl, 2,4,6-tris (α-hydroxyisopropyl ) Biphenyl, 3,3 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 3,4 ′, 5-tris (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,6, -tetrakis (α-hydroxy) Isopropyl) biphenyl, 2,4,4 ′, 6, -tetrakis (α-hydroxyisopropyl) (Lopyl) biphenyl, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) biphenyl, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) biphenyl, 2,2 ′, 4 , 4 ′, 6,6′-hexakis (α-hydroxyisopropyl) biphenyl and the like α-hydroxyisopropylbiphenyls; 3-α-hydroxyisopropyldiphenylmethane, 4-α-hydroxyisopropyldiphenylmethane, 1- (4-α-hydroxy) Isopropylphenyl) -2-phenylethane, 1- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 2- (4-α-hydroxyisopropylphenyl) -2-phenylpropane, 1- (4-α- Hydroxyisopropylphenyl) -3-phenylpropane, 1- ( -Α-hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-α-hydroxyisopropylphenyl) -5-phenylpentane, 3,5-bis (α-hydroxyisopropyldiphenylmethane, 3,3'-bis (α -Hydroxyisopropyl) diphenylmethane, 3,4'-bis (α-hydroxyisopropyl) diphenylmethane, 4,4'-bis (α-hydroxyisopropyl) diphenylmethane, 1,2-bis (4-α-hydroxyisopropylphenyl) ethane, 1,2-bis (4-α-hydroxypropylphenyl) propane, 2,2-bis (4-α-hydroxypropylphenyl) propane, 1,3-bis (4-α-hydroxypropylphenyl) propane, 2, 4,6-Tris (α-hydroxyisopropyl) dipheny Methane, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) Diphenylmethane, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenylmethane, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenylmethane, 2,3 ′, 4,5 ′, 6 Α-hydroxyisopropyldiphenylalkanes such as pentakis (α-hydroxyisopropyl) diphenylmethane, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenylmethane; 3-α-hydroxyisopropyldiphenyl ether 4-alpha-hydroxyisopropyl Diphenyl ether, 3,5-bis (α-hydroxyisopropyl) diphenyl ether, 3,3′-bis (α-hydroxyisopropyl) diphenyl ether, 3,4′-bis (α-hydroxyisopropyl) diphenyl ether, 4,4′-bis ( α-hydroxyisopropyl) diphenyl ether, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ether, 3,4 ′, 5-tris (α-hydroxy) Isopropyl) diphenyl ether, 2,3 ′, 4,6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ether, 3,3 ′, 5,5′- Tetrakis ( -Hydroxyisopropyl) diphenyl ether, 2,3 ′, 4,5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ether, 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ether Α-hydroxyisopropyl diphenyl ethers such as 3-α-hydroxyisopropyl diphenyl ketone, 4-α-hydroxyisopropyl diphenyl ketone, 3,5-bis (α-hydroxyisopropyl) diphenyl ketone, 3,3′-bis (α- Hydroxyisopropyl) diphenyl ketone, 3,4'-bis (α-hydroxyisopropyl) diphenyl ketone, 4,4′-bis (α-hydroxyisopropyl) diphenyl ketone, 2,4,6-tris (α-hydroxyisopropyl) diphenyl ketone 3,3 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 3,4 ′, 5-tris (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4,6-tetrakis (α-hydroxy) Isopropyl) diphenyl ketone, 2,4,4 ′, 6-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 3,3 ′, 5,5′-tetrakis (α-hydroxyisopropyl) diphenyl ketone, 2,3 ′, 4 , 5 ′, 6-pentakis (α-hydroxyisopropyl) diphenyl ketone, α-hydroxyisopropyl diphenyl ketones such as 2,2 ′, 4,4 ′, 6,6′-hexakis (α-hydroxyisopropyl) diphenyl ketone; 3-α-hydroxyisopropylbenzoate phenyl, 4-α-hydroxyisopropylbenzoate Acid phenyl, benzoic acid 3-α-hydroxyisopropylphenyl, benzoic acid 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid phenyl, 3-α-hydroxyisopropylbenzoic acid 3-α- Hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 4-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoate 3-α-hydroxyisopropylphenyl, 4-α-hydroxyisopropylbenzoate 4-α-hydroxyisopropyl Phenyl, 3,5-bis (α-hydroxyisopropyl) phenyl benzoate, phenyl 2,4,6-tris (α-hydroxyisopropyl) benzoate, 3,5-bis (α-hydroxyisopropyl) benzoic acid 3-α -Hydroxy Propylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoate 4-α-hydroxyisopropylphenyl, 3-α-hydroxyisopropylbenzoate 3,5-bis (α-hydroxyisopropyl) phenyl, 4-α-hydroxy Isopropyl benzoate 3,5-bis (α-hydroxyisopropyl) phenyl, benzoate 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoate 3- α-hydroxyisopropylphenyl, 2,4,6-tris (α-hydroxyisopropyl) benzoate 4-α-hydroxyisopropylphenyl, 3,5-bis (α-hydroxyisopropyl) benzoate 3,5-bis (α- Hydroxyisopropyl) phenyl, 3-α-hydroxyisopro 2,4,6-Tris (α-hydroxyisopropyl) phenyl 4-benzoate, 2,4,6-tris (α-hydroxyisopropyl) phenyl 4-benzoate, 2,4,6-tris (α -Hydroxyisopropyl) benzoic acid 3,5-bis (α-hydroxyisopropyl) phenyl, 3,5-bis (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl, 2,4 , 6-tris (α-hydroxyisopropyl) benzoic acid 2,4,6-tris (α-hydroxyisopropyl) phenyl and the like α-hydroxyisopropylbenzoic acid phenyls and the like.

  Further, specific examples of the naphthalene compound (3) include 1- (α-hydroxyisopropyl) naphthalene, 2- (α-hydroxyisopropyl) naphthalene, 1,3-bis (α-hydroxyisopropyl) naphthalene, 1,4-bis (α-hydroxyisopropyl) naphthalene, 1,5-bis (α-hydroxyisopropyl) naphthalene, 1,6-bis (α-hydroxyisopropyl) naphthalene, 1,7-bis (α-hydroxyisopropyl) Naphthalene, 2,6-bis (α-hydroxyisopropyl) naphthalene, 2,7-bis (α-hydroxyisopropyl) naphthalene, 1,3,5-tris (α-hydroxyisopropyl) naphthalene, 1,3,6-tris (Α-hydroxyisopropyl) naphthalene, 1,3,7-tris (α- Droxyisopropyl) naphthalene, 1,4,6-tris (α-hydroxyisopropyl) naphthalene, 1,4,7-tris (α-hydroxyisopropyl) naphthalene, 1,3,5,7-tetrakis (α-hydroxyisopropyl) ) Naphthalene and the like.

  Specific examples of the furan compound (4) include 3- (α-hydroxyisopropyl) furan, 2-methyl-3- (α-hydroxyisopropyl) furan, 2-methyl-4- (α- Hydroxyisopropyl) furan, 2-ethyl-4- (α-hydroxyisopropyl) furan, 2-n-propyl-4- (α-hydroxyisopropyl) furan, 2-isopropyl-4- (α-hydroxyisopropyl) furan, 2 -N-butyl-4- (α-hydroxyisopropyl) furan, 2-t-butyl-4- (α-hydroxyisopropyl) furan, 2-n-pentyl-4- (α-hydroxyisopropyl) furan, 2,5 -Dimethyl-3- (α-hydroxyisopropyl) furan, 2,5-diethyl-3- (α-hydroxyisopropyl) furan 3,4-bis (α-hydroxyisopropyl) furan, 2,5-dimethyl-3,4-bis (α-hydroxyisopropyl) furan, 2,5-diethyl-3,4-bis (α-hydroxyisopropyl) Examples include francs.

  The acid crosslinking agent (G3) is preferably a compound having two or more free α-hydroxyisopropyl groups, the benzene compound (1) having two or more α-hydroxyisopropyl groups, and two or more α-hydroxyisopropyl groups. The diphenyl compound (2) having, and the naphthalene compound (3) having two or more α-hydroxyisopropyl groups are more preferable, α-hydroxyisopropylbiphenyls having two or more α-hydroxyisopropyl groups, α-hydroxy A naphthalene compound (3) having two or more isopropyl groups is particularly preferred.

The acid cross-linking agent (G3) is usually obtained by a method in which an acetyl group-containing compound such as 1,3-diacetylbenzene is reacted with a Grignard reagent such as CH ₃ MgBr to be methylated, and then hydrolyzed. It can be obtained by a method in which an isopropyl group-containing compound such as diisopropylbenzene is oxidized with oxygen or the like to generate a peroxide and then reduced.

  In the present invention, the amount of the acid crosslinking agent (G) used is preferably 0.5 to 49 mass%, more preferably 0.5 to 40 mass%, still more preferably 1 to 30 mass%, based on the total weight of the solid component. -20% by weight is particularly preferred. When the blending ratio of the acid cross-linking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the resist film in an alkaline developer is improved, the remaining film ratio is decreased, pattern swelling and meandering are caused. It is preferable because it can be prevented from occurring. On the other hand, when it is 50% by mass or less, it is preferable because a decrease in heat resistance as a resist can be suppressed.

  Further, the blending ratio of at least one compound selected from the acid crosslinking agent (G1), the acid crosslinking agent (G2), and the acid crosslinking agent (G3) in the acid crosslinking agent (G) is not particularly limited. Various ranges can be used depending on the type of substrate used when forming the pattern.

  In the total acid crosslinking agent component, the alkoxymethylated melamine compound and / or the compound represented by (9-1) to (9-3) is 50 to 99% by mass, preferably 60 to 99% by mass, more preferably 70%. It is preferable that it is -98 mass%, More preferably, it is 80-97 mass%. Since the resolution can be improved by setting the alkoxymethylated melamine compound and / or the compound represented by (9-1) to (9-3) to 50% by mass or more of the total acid crosslinking agent component, 99 is preferable. It is preferable that the content be less than or equal to mass% because the cross-sectional shape of the pattern is easily a rectangular cross-sectional shape.

  In the present invention, an acid diffusion control agent (E) having an action of controlling undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. You may mix | blend with a radiation sensitive composition. By using such an acid diffusion controller (E), the storage stability of the radiation-sensitive composition is improved. In addition, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before irradiation and the holding time after irradiation can be suppressed, and the process stability is extremely excellent. Examples of such an acid diffusion controller (E) include radiolytically decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller (E) can be used alone or in combination of two or more.

Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (10) (hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (I)”). , "Nitrogen-containing compound (II)"), polyamino compounds and polymers having 3 or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (III)"), amide group-containing compounds, urea compounds, and And nitrogen heterocyclic compounds. In addition, an acid diffusion control agent (E) may be used individually by 1 type, and may use 2 or more types together.
(10)

In the general formula (10), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group or an aralkyl group. The alkyl group, aryl group or aralkyl group may be unsubstituted or substituted with a hydroxyl group or the like. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group , N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Moreover, as said aryl group, a C6-C12 thing is mentioned, Specifically, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, 1-naphthyl group, etc. are mentioned. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

  Specific examples of the nitrogen-containing compound (I) include mono-cyclohexane such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine and cyclohexylamine. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and the like di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, -Tri (cyclo) alkylamines such as n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine; Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine , Aromatic amines such as triphenylamine and 1-naphthylamine.

  Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) ) Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl)- 2- (4-Hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

  Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.

  Specific examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.

  Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole; pyridine, 2-methylpyridine. 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane etc. It can gel.

  Examples of the radiation-decomposable basic compound include a sulfonium compound represented by the following general formula (11-1) and an iodonium compound represented by the following general formula (11-2). .

In the general formulas (11-1) and (11-2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. -6 alkoxy groups, hydroxyl groups or halogen atoms. Z ⁻ represents HO ⁻ , R—COO ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, or an alkaryl group having 7 to 12 carbon atoms) or the following general formula. (11-3):

(11-3)
An anion represented by

  Specific examples of the radiolytic basic compound include, for example, triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium. Acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydroxide Bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butylphenyl 4-hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.

  The blending amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, further preferably 0.01 to 5% by mass, based on the total weight of the solid component. 0.01 to 3% by mass is particularly preferable. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Moreover, the fall of a sensitivity, the developability of an unexposed part, etc. can be prevented as a compounding quantity is 10 mass% or less. Further, by using such an acid diffusion control agent, the storage stability of the radiation-sensitive composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.

  The composition of the present invention includes, as necessary, other components (F), a dissolution accelerator, a dissolution controller, a sensitizer, a surfactant, and an organic carboxylic acid as long as the object of the present invention is not impaired. Alternatively, one or more of various additives such as oxo acid of phosphorus or a derivative thereof can be added.

(1) Solubility Accelerator A low molecular weight solubilizer enhances the solubility of a compound having each configuration represented by formula (1) and a blend of the compound in a developer when the solubility in the developer is too low. , A component having an action of appropriately increasing the dissolution rate of a compound having each configuration at the time of development and a blend of the compound, and can be used within a range not impairing the effects of the present invention. Examples of the dissolution accelerator include low molecular weight phenolic compounds such as bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more. The blending amount of the dissolution accelerator is appropriately adjusted depending on the compound having each configuration to be used and the kind of blend of the compound, but is preferably 0 to 49% by mass of the total weight of the solid component, and 0 to 5% by mass. % Is more preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.

(2) Dissolution control agent A dissolution control agent is developed by controlling the solubility of a compound having each configuration represented by formula (1) and a blend of the compound when the solubility in the developer is too high. It is a component having an action of moderately reducing the dissolution rate. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable.

Examples of the dissolution control agent include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. be able to. These dissolution control agents can be used alone or in combination of two or more.
The blending amount of the dissolution control agent is appropriately adjusted according to the compound having each configuration used and the kind of blend of the compound, but is preferably 0 to 49% by mass of the total weight of the solid component, and 0 to 5% by mass. % Is more preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.

(3) Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated, and resist. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more. The blending amount of the sensitizer is appropriately adjusted according to the compound having each configuration used and the kind of blend of the compound, but is preferably 0 to 49% by mass of the total weight of the solid component, and 0 to 5% by mass. % Is more preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.

(4) Surfactant The surfactant is a component having an action of improving the coating property and striation of the radiation-sensitive composition of the present invention, the developability of the resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products include the following product names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass) Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), and the like. The compounding amount of the surfactant is appropriately adjusted according to the compound having each configuration used and the kind of blend of the compound, and is preferably 0 to 49% by mass of the total weight of the solid component, and 0 to 5% by mass. % Is more preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.

(5) Organic carboxylic acid or phosphorus oxo acid or derivative thereof For the purpose of preventing sensitivity deterioration or improving resist pattern shape, retention stability, etc., organic carboxylic acid or phosphorus oxo acid or derivative thereof as an optional component Can be contained. In addition, it can be used in combination with an acid diffusion controller, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and the like, and derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Derivatives such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, etc., phosphonic acid or their esters, phosphinic acid, phosphinic acid such as phenylphosphinic acid, and derivatives thereof. Of these, phosphonic acid is particularly preferred.
The organic carboxylic acid or phosphorus oxo acid or derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately adjusted depending on the compound having each configuration used and the type of blend of the compound, but it is 0 to 49 mass of the total weight of the solid component. % Is preferable, 0 to 5% by mass is more preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.

(6) The above dissolution control agent, sensitizer, surfactant, and other additives other than organic carboxylic acid or phosphorus oxo acid or derivatives thereof. One or more additives other than the above-mentioned dissolution control agent, sensitizer, and surfactant can be blended as necessary within a range not inhibiting the purpose. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

  The total amount of the optional component (F) is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 1% by mass, and particularly preferably 0% by mass based on the total weight of the solid components.

  The ratio of the mixture (A) (all compounds) / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) in the solid component is preferably , By mass%, 50-99.498 / 0.001-49 / 0.5-49 / 0.001-49 / 0-49, more preferably 55-90 / 1-40 / 0.5-40 /0.01 to 10/0 to 5, more preferably 60 to 80/3 to 30/1 to 30 / 0.01 to 5/0 to 1, particularly preferably 60 to 70/10 to 25/2. -20 / 0.01 to 3/0. The blending ratio of each component is selected from each range so that the sum is 100% by mass. When the above composition is used, the performance such as sensitivity, resolution and developability is excellent.

  The radiation-sensitive composition of the present invention is usually prepared by dissolving each component in a solvent at the time of use to make a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, if necessary. The

  Examples of the solvent used for preparing the radiation-sensitive composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n- Ethylene glycol monoalkyl ether acetates such as butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n- Propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc. Lopylene glycol monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; lactic acid such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate Esters; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; 3-methoxypropionic acid Methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyrate Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone Lactones such as γ-lactone can be mentioned, but there is no particular limitation. These solvents can be used alone or in combination of two or more.

  The radiation-sensitive composition of the present invention can contain a resin as long as the object of the present invention is not impaired. Examples of the resin include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or derivatives thereof. Can be mentioned. The compounding amount of the resin is appropriately adjusted according to the compound having each configuration of formula (1) used and the kind of blend of the compound, but the compound having each configuration and blend of the compound 100 weight The amount is preferably 30 parts by weight or less per part, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and particularly preferably 0 parts by weight.

(Method for forming resist pattern)
The resist pattern forming method of the present invention comprises a step of coating a substrate using the radiation-sensitive composition of the present invention to form a resist film, a step of exposing the resist film, and an exposed resist film. Developing. The resist pattern can also be formed as an upper layer resist in a multilayer process.

  In order to form a resist pattern, first, a resist film is formed by applying the radiation-sensitive composition of the present invention on a conventionally known substrate by a coating means such as spin coating, cast coating or roll coating. . The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

  Next, the coated substrate is heated as necessary. Although heating conditions change with the compounding composition etc. of a radiation sensitive composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. Although heating conditions change with the compounding composition etc. of a radiation sensitive composition, 20-250 degreeC is preferable, More preferably, it is 20-150 degreeC.

  Next, the exposed resist film is developed with a developer to form a predetermined resist pattern. As the developer, it is preferable to select a solvent having a solubility parameter (SP value) close to the compound having each configuration of the formula (1) to be used and a blend of the compound, a ketone solvent, an ester solvent A polar solvent such as a solvent, an alcohol solvent, an amide solvent, an ether solvent, a hydrocarbon solvent, or an alkaline aqueous solution can be used.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. Methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, and the like.

  Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3. -Ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like can be mentioned.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene Recall monoethyl ether, and triethylene glycol monoethyl ether and methoxymethyl butanol.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

  Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

  A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than the above or water within the range having performance. However, in order to fully achieve the effects of the present invention, the water content of the developer as a whole is less than 70% by mass, preferably less than 50% by mass, and more preferably less than 30% by mass. Preferably, it is more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no water. That is, the content of the organic solvent with respect to the developer is 30% by mass to 100% by mass, preferably 50% by mass to 100% by mass, and preferably 70% by mass to 100% by mass with respect to the total amount of the developer. More preferably, it is 90 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less, It is especially preferable that it is 95 mass% or more and 100 mass% or less.

  Examples of the alkaline aqueous solution include alkaline compounds such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. Can be mentioned.

  In particular, the developer is a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, such as resist pattern resolution and roughness. It is preferable for improving the resist performance.

  The vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is improved. It improves.

  Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate Agent, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl Alcohol solvents such as alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl Glycol ether solvents such as ether, triethylene glycol monoethyl ether, methoxymethyl butanol, etc. , Ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, amide solvents of N, N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, octane, decane, etc. And aliphatic hydrocarbon solvents.

  Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol, alcohol solvents such as ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol , Glycol solvents such as triethylene glycol, and glycols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol Ether solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl Formamide amide solvents, aromatic hydrocarbon solvents such as xylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the developer as necessary.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-334540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.

  The usage-amount of surfactant is 0.001-5 mass% normally with respect to the whole quantity of a developing solution, Preferably it is 0.005-2 mass%, More preferably, it is 0.01-0.5 mass%.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) ) Etc. can be applied. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

  Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

After the development, it is preferable to include a step of washing with a rinse solution containing an organic solvent.
The rinsing liquid used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution or water containing a general organic solvent can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. . More preferably, after the development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. Even more preferably, after the development, a washing step is performed using a rinse solution containing an alcohol solvent or an ester solvent. Even more preferably, after the development, a washing step using a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a washing step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms. The time for rinsing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Here, examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4 -Use methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. Rukoto can.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

  The vapor pressure of the rinsing liquid used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and the swelling due to the penetration of the rinsing liquid is further suppressed, and the dimensions in the wafer surface are reduced. Uniformity is improved.

  An appropriate amount of a surfactant can be added to the rinse solution.

  In the rinsing step, the developed wafer is cleaned using a rinsing solution containing the organic solvent. The method of the cleaning treatment is not particularly limited. For example, a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

  After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.

  After the resist pattern is formed, plating can be performed thereon. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

  The residual resist pattern after etching can be peeled off with an organic solvent. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate) and the like. Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

  The wiring board obtained by the present invention can also be formed by a method of depositing a metal in vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following synthesis examples and comparative examples, the structures of the compounds were confirmed by ¹ H-NMR measurement.

(Synthesis Example 1 (Synthesis of CR-1))
An autoclave with an electromagnetic stirrer with an internal volume of 500 ml (manufactured by SUS316L) capable of controlling the temperature was charged with 74.3 g (3.71 mol) of anhydrous HF and 50.5 g (0.744 mol) of BF ₃ , and the contents were stirred. The pressure was increased to 2 MPa with carbon monoxide while maintaining the liquid temperature at −30 ° C. Thereafter, while maintaining the pressure at 2 MPa and the liquid temperature at −30 ° C., a raw material mixed with 570 g (0.248 mol) of 4-cyclohexylbenzene and 50.0 g of n-heptane was supplied and maintained for 1 hour. The contents were collected in ice, diluted with benzene and neutralized, and the oil layer obtained was analyzed by gas chromatography to obtain the reaction results. As a result, 4-cyclohexylbenzene conversion was 100%, 4 The selectivity for cyclohexylbenzaldehyde was 97.3%.
The target component was isolated by simple distillation and analyzed by GC-MS. As a result, the molecular weight 188 of the target 4-cyclohexylbenzaldehyde (hereinafter referred to as CHBAL) was shown. Moreover, the chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated chloroform solvent is 1.0 to 1.6 (m, 10H), 2.6 (m, 1H), 7.4 (d , 2H), 7.8 (d, 2H), 10.0 (s, 1H).

(CHBAL)

  To a four-necked flask (500 ml) equipped with a well-dried dropping funnel purged with nitrogen, Jim Roth condenser, thermometer, stirring blade, under a nitrogen stream, resorcinol (23.1 g, 0 .2 mol) and ethanol (190 g) were added to prepare an ethanol solution. The solution was ice-cooled, concentrated sulfuric acid (97%, 18.5 g, 0.2 mol) and 23.9 g of pure water were added dropwise by a dropping funnel over 10 minutes while cooling and stirring at 5 to 15 ° C. The 4-cyclohexylbenzaldehyde (37.7 g, 0.2 mol) and ethanol (21 g) were added dropwise. Then, it heated to 80 degreeC with the mantle heater and stirred for 5 hours. After the completion of the reaction, the mixture was allowed to cool and allowed to reach room temperature, and then cooled in an ice bath. After standing for 1 hour, pale yellow target crude crystals were produced, which were filtered off. The crude crystals were washed 3 times with 500 ml of methanol and 5 times with 500 ml of pure water, filtered and vacuum dried to obtain 42.5 g of a product (hereinafter referred to as CR-1). As a result of analyzing this product by high performance liquid chromatography (hereinafter referred to as HPLC), the composition ratio of (ccc) isomer / (ctt) isomer / (cct) isomer was 49.9 / 49.9 / 0. .2. 40 g of this product was recrystallized twice with a mixed solution of 8 L of tetrahydrofuran / 8 L of hexane.

11 g of the filtrate concentrate obtained from the second recrystallization was recrystallized for the third time with 100 ml of ethyl acetate to obtain 9 g of a crystal containing a large amount of the (ctt) isomer of CR-1.
As a result of analyzing the crystal by HPLC, the composition ratio of (ccc) isomer / (ctt) isomer / (cct) isomer was 3.1 / 96.9 / 0.0.

As a result of analysis by GPC, the structure of the (ctt) isomer of CR-1 showed a styrene-equivalent number average molecular weight Mn979 and a weight average molecular weight Mw986. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated acetonitrile solvent is 0.8 to 1.9 (m, 44H), 5.5 (s, 4H), 6.0 to 6. 4 (d, 8H), 6.6 to 6.7 (m, 16H), 8.4, 8.5 (m, 8H).
From these results, the obtained product was identified as the (ctt) isomer of the target compound (CR-1) (hereinafter referred to as CR-1t).

((Ctt) isomer of CR-1)

  22 g of the crystal obtained from the second recrystallization was recrystallized for the third time with 800 ml of ethyl acetate to obtain 10 g of a crystal containing a large amount of the (ccc) isomer of CR-1. As a result of analyzing the crystal by HPLC, the composition ratio of (ccc) isomer / (ctt) isomer / (cct) isomer was 97.6 / 2.4 / 0.0.

As a result of analysis by GPC, the structure of the (ccc) isomer of this product showed a number average molecular weight Mn979 and a weight average molecular weight Mw986 in terms of styrene. The chemical shift values (δ ppm, TMS standard) of ¹ H-NMR in deuterated acetonitrile solvent are 0.8 to 1.9 (m, 44H), 5.6 (s, 4H), 6.1 to 6. 5 (d, 8H), 6.7 to 6.9 (m, 16H), and 8.5 (m, 8H).
From these results, the obtained product was identified as the (ccc) isomer of the target compound (CR-1) (hereinafter referred to as CR-1c).

((Ccc) isomer of CR-1)

  In a four-necked flask (500 ml) equipped with a well-dried dropping funnel purged with nitrogen, Jim Roth condenser, thermometer and stirring blade, resorcinol (16.5 g, 0 .2 mol) and ethanol (255 g) were added to prepare an ethanol solution. The solution was ice-cooled, concentrated sulfuric acid (97%, 13.9 g, 0.2 mol) and 17.9 g of pure water were added dropwise by a dropping funnel over 10 minutes while cooling and stirring at 5 to 15 ° C. The 4-cyclohexylbenzaldehyde (29.7 g, 0.2 mol) and ethanol (26 g) were added dropwise. Then, it heated to 40 degreeC with the mantle heater and stirred for 5 hours. After the completion of the reaction, the mixture was allowed to cool and allowed to reach room temperature, and then cooled in an ice bath. 1 L of ethyl acetate was added to make a uniform solvent, and the mixture was washed 3 times with 200 ml of pure water and twice with saturated brine, water was removed with magnesium sulfate, and ethyl acetate was distilled off. It vacuum-dried at 40 degree | times and the product (henceforth CR-1) 38.3g was obtained. As a result of analyzing this product by HPLC, the composition ratio of (ccc) isomer / (ctt) isomer / (cct) isomer was 18.5 / 10.1 / 71.4.

As a result of analysis by GPC, the structure of the (cct) isomer of this product showed a number average molecular weight Mn979 and a weight average molecular weight Mw986 in terms of styrene. The chemical shift value (δ ppm, TMS standard) of ¹ H-NMR in deuterated acetonitrile solvent is 0.8 to 1.9 (m, 44H), 5.6, 5.7, 5.7 (m, 4H). ), 6.2 to 6.5 (d, 8H), 6.5 to 70 (m, 16H), and 7.1 (m, 8H).
From these results, the obtained product was identified as the (cct) isomer of the target compound (CR-1) (hereinafter referred to as CR-1a).

((Cct) isomer of CR-1)

(Synthesis Example 2 (Synthesis of CR-2A))
An autoclave with an electromagnetic stirrer with an internal volume of 500 ml (manufactured by SUS316L) capable of controlling the temperature was charged with 74.3 g (3.71 mol) of anhydrous HF and 50.5 g (0.744 mol) of BF ₃ , and the contents were stirred. The pressure was increased to 2 MPa with carbon monoxide while maintaining the liquid temperature at −30 ° C. Then, while maintaining the pressure at 2 MPa and the liquid temperature at −30 ° C., a raw material mixed with 29.8 g (0.248 mol) of cumene and 50.0 g of n-heptane was supplied, and after maintaining for 1 hour, The contents were collected, diluted with benzene, neutralized and the oil layer obtained was analyzed by gas chromatography to obtain the reaction results. Cumene conversion 100%, 4-isopropylbenzene selected The rate was 97.3%.

(CUMAL)

To a four-necked flask (500 ml) equipped with a well-dried dropping funnel substituted with nitrogen, Jim Roth condenser, thermometer, stirring blade, under a nitrogen stream, resorcinol (11.6 g, 0 0.1 mol) and ethanol (70 g) were added to prepare an ethanol solution. This solution was ice-cooled, concentrated sulfuric acid (97%, 9.2 g, 0.1 mol) and 12.0 g of pure water were added dropwise by a dropping funnel over 10 minutes while cooling and stirring at 5 to 15 ° C. The CUMAL (14.8 g, 0.1 mol) and ethanol (35 g) were added dropwise. Then, it heated to 80 degreeC with the mantle heater and stirred for 5 hours. After the completion of the reaction, the mixture was allowed to cool and allowed to reach room temperature, and then cooled in an ice bath. After standing for 1 hour, pale yellow target crude crystals were produced, which were filtered off. The crude crystals were washed twice with 500 ml of methanol, filtered and vacuum dried to obtain 13 g of a product (hereinafter referred to as CR-2A). As a result of analyzing this product by HPLC, the composition ratio of (ccc) isomer / (ctt) isomer / (cct) isomer was 0.8 / 99.2 / 0.0.
As a result of analysis by GPC, the structure of this product showed a number average molecular weight Mn931 in terms of styrene and a weight average molecular weight Mw935. Moreover, the chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated dimethyl sulfoxide solvent is 1.1 (t, 24H), 2.7 (m, 4H), 5.5 (s, 4H), It was 6.0, 6.1, 6.4 (m, 8H), 6.6 to 6.8 (m, 16H), 8.4, 8.5 (s, 8H).
From these results, the obtained product was identified as the (ctt) isomer of the target compound (CR-2A) (hereinafter referred to as CR-2t).

((Ctt) isomer of CR-2A)

(Synthesis Comparative Example 1)
The product CR-1 synthesized and purified in Synthesis Example 1 was used. As a result of analyzing this product by HPLC, the composition ratio of (ccc) isomer / (ctt) isomer / (cct) isomer was 49.9 / 49.9 / 0.2.

<Examples 1-4 and Comparative Examples 1-4>
(1) Patterning test The ingredients listed in Table 1 were prepared to form a uniform solution, and then filtered through a pore system 0.1 μm Teflon (registered trademark) membrane filter to prepare a radiation-sensitive composition. Evaluation was performed. The evaluation results are shown in Table 2.

Acid generator (C)
P-1: Triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Chemical Co., Ltd.)
Acid crosslinking agent (G)
C-1: Nicarak MW-100LM (Sanwa Chemical Co., Ltd.)
Acid diffusion controller (E)
Q-1: Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
Solvent S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

After spin-coating a resist on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven at 110 ° C. to form a resist film having a thickness of 60 nm. The resist film was irradiated with an electron beam with a line and space setting of 1: 1 of 50 nm, 40 nm, 30 nm, 25 nm, 20 nm and intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.). . After the irradiation, each film was heated at a predetermined temperature for 90 seconds and immersed in a TMAH 2.38 wt% alkaline developer for 60 seconds for development. Thereafter, it was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern.
The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation). The dose amount (μC / cm ² ) at that time was defined as sensitivity.
1: Dose amount ≦ 45 μC / cm ² (excellent sensitivity)
2: 45 μC / cm ² <dose amount ≦ 60 μC / cm ² (good sensitivity)
3: 60 μC / cm ² <dose (sensitivity failure)

The line edge roughness of the pattern is SEM terminal PC V5 offline length measurement software for Hitachi Semiconductor (manufactured by Hitachi Science Systems, Ltd.) at an arbitrary 300 points in the length direction (0.75 μm) of 1: 1 line and space. Was used to measure the distance between the edge and the reference cent. The standard deviation (3σ) was calculated from the measurement result.
A: LER ≦ 3.0nm (Excellent LER)
B: 3.0 nm <LER ≦ 70 nm (good LER)
C: 70 nm <LER (including a pattern with collapse)
D: No pattern

Example 9
Using the resist having the composition of Example 5 obtained with good results in the above example, spin-coated on a clean silicon wafer, followed by pre-exposure baking (PB) in an oven at 110 ° C., and having a thickness of 40 nm A resist film was formed. Using the electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.), the resist film is electron with 50 nm, 40 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, and 1: 1 line and space setting at intervals. Irradiated with rays. After the irradiation, each film was heated at a predetermined temperature for 90 seconds and immersed in a TMAH 2.38 wt% alkaline developer for 60 seconds for development. Thereafter, it was washed with ultrapure water for 30 seconds and dried to form a negative resist pattern.
The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation). The dose amount (μC / cm ² ) at that time was defined as sensitivity.

  The resist of Example 5 was able to obtain a good resist pattern with a resolution of 25 nm with excellent sensitivity. Although the 20 nm resist pattern also fell, it was resolved, the roughness of the pattern was small, and the shape was good.

  From the results of the patterning test, it was confirmed that the radiation-sensitive composition using the compound of the present invention had better sensitivity and LER than the radiation-sensitive composition having a compound composed of a plurality of isomers of Comparative Examples.

  Further, the compounds of the present invention can be easily produced with a purity of 100%, and can be prepared by simply mixing them, so that quality control is easy. On the other hand, the compound consisting of the mixture of the comparative example is a radiation-sensitive composition having a compound consisting of a plurality of isomers, and the composition varies from production to production, making quality control difficult.

  As described above, the radiation-sensitive composition containing the compound having each configuration according to the present invention and the blend of the compound has higher sensitivity, lower roughness, and better shape than the composition containing the comparative compound. This resist pattern can be formed. As long as the above-described requirements of the present invention are satisfied, compounds other than those described in the examples also show the same effect.

  The present invention is suitably used in a radiation-sensitive composition useful as a resist material, comprising two or more compounds mainly composed of a specific stereoisomer, and a resist pattern forming method using the radiation-sensitive composition.

Claims (17)

A radiation-sensitive composition comprising two or more compounds represented by formula (1) having a specific stereoisomer of 70 mol% or more and a solvent,
Radiation sensitivity, wherein the solid component is in the range of 1 to 80% by mass, the solvent is in the range of 20 to 99% by mass, and the total proportion of the compound in the solid component is 20 to 99.9% by mass. Composition.
(1)
(In the formula (1), each R is independently a hydrogen atom, a heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted group. A branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms. Group, substituted or unsubstituted acyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkyloxyl group having 1 to 20 carbon atoms, substituted or unsubstituted Is an unsubstituted aryloyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, or these groups and a divalent group (substituted or unsubstituted alkylene group, substituted or R ′ and X are each independently a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, a complex, or a group to which one or more groups selected from the group consisting of an unsubstituted arylene group and an ether group are bonded. A cyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted group A C3-C20 cycloaliphatic hydrocarbon group, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted carbon number 1 to 1 20 Alkoxy group, substituted or unsubstituted amino group having 0 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted acyl group having 1 to 20 carbon atoms, substituted or unsubstituted An alkoxycarbonyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkyloyloxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloyloxy group having 7 to 20 carbon atoms, a substituted or unsubstituted carbon number 1 ~ 20 alkylsilyl groups, or these groups and a divalent group (one or more groups selected from the group consisting of a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group and an ether group) bonded to each other. Group.) The radiation sensitive composition according to claim 1, wherein the compound is represented by the formula (2).
(2)
(In Formula (2), R is the same as the above. R ¹² is independently a hydrogen atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted straight chain having 1 to 14 carbon atoms. Or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 14 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 14 carbon atoms, or the following formula (3 Is a group represented by
(3)
In formula (3), each R ⁴ independently represents a cyano group, a nitro group, a heterocyclic group, a halogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 14 carbon atoms, a substituted or Unsubstituted C3-C14 branched aliphatic hydrocarbon group, substituted or unsubstituted C3-C14 cyclic aliphatic hydrocarbon group, substituted or unsubstituted C6-C14 aryl group, substituted Or it is an unsubstituted C1-C14 alkoxy group or a substituted or unsubstituted C1-C14 alkylsilyl group, p is an integer of 0-4, q is an integer of 0-5. )   The radiation-sensitive composition according to claim 1 or 2, wherein at least one of the stereoisomers is a (ccc) isomer.   The radiation-sensitive composition according to claim 1 or 2, wherein at least one of the stereoisomers is a (ctt) isomer.   The radiation-sensitive composition according to claim 1 or 2, wherein at least one of the stereoisomers is a (cct) isomer.   The radiation-sensitive composition according to claim 1 or 2, wherein at least one of the stereoisomers is a (tct) isomer. The radiation-sensitive composition according to claim 2, wherein at least one of the stereoisomers is represented by any one of formulas (4) to (7).
The radiation-sensitive composition according to claim 2, wherein at least one of the stereoisomers is represented by any one of formulas (8) to (11).
  A compound having one of the stereoisomers represented by the formula (4) to the formula (7) and a compound having one of the stereoisomers represented by the formula (8) to the formula (11). The radiation sensitive composition of Claim 7 or 8 characterized by the above-mentioned.   Acid generation that generates acid directly or indirectly by irradiation with any one of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray and ion beam The radiation-sensitive composition according to any one of claims 1 to 9, further comprising an agent (C).   The radiation-sensitive composition according to any one of claims 1 to 10, further comprising an acid crosslinking agent (G).   The radiation sensitive composition according to any one of claims 1 to 11, further comprising an acid diffusion control agent (E).   The ratio of all the compounds / acid generator (C) / acid crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) in the solid component is 50 to 99. It is the range of 498 / 0.001-49 / 0.5-49 / 0.001-49 / 0-49, The radiation sensitive composition of Claim 12 characterized by the above-mentioned.   The radiation-sensitive composition according to claim 1, wherein an amorphous film can be formed by spin coating.   The radiation sensitive composition according to any one of claims 1 to 14, wherein the dissolution rate of the amorphous film in a developer at 23 ° C is 10 Å / sec or more.   The dissolution rate of the amorphous film after irradiation with KrF excimer laser, extreme ultraviolet light, electron beam or X-rays, or the amorphous film after heating at 20 to 250 ° C. is 5 Å / sec or less. The radiation sensitive composition of Claim 15 characterized by these.   The process of apply | coating the radiation sensitive composition of any one of Claims 1-16 on a board | substrate, forming a resist film, the process of exposing the said resist film, and the process of developing the exposed resist film And a resist pattern forming method.