CN108008600B

CN108008600B - Radiation-sensitive composition

Info

Publication number: CN108008600B
Application number: CN201711363964.2A
Authority: CN
Inventors: 越后雅敏; 小黑大
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2006-11-02
Filing date: 2007-11-01
Publication date: 2021-02-09
Anticipated expiration: 2027-11-01
Also published as: CN101528653B; CN101528653A; JP2008116677A; JP5109338B2; CN108008600A

Abstract

The present invention provides a radiation-sensitive composition containing a cyclic compound B and a low-molecular-weight dissolution promoter D in such an amount that the total amount of the cyclic compound B and the low-molecular-weight dissolution promoter D is 50 to 99.999% by weight based on the total amount of solid components. The radiation-sensitive composition of the present invention has the advantages of high sensitivity, high resolution, high etching resistance, low outgassing amount, and good shape of the resulting resist pattern.

Description

Radiation-sensitive composition

RELATED APPLICATIONS

The present application is a divisional application of a chinese invention patent application having an application number of 201410350098.3, an application date of 2007 at 11/1/2007 and an invention name of "radiation-sensitive composition", wherein the application having an application number of 201410350098.3 is a divisional application of a chinese invention patent application having an application number of 201210519762.3, an application date of 2007 at 11/1/2007 and an invention name of "radiation-sensitive composition", and the application having an application number of 201210519762.3 is a divisional application of a chinese invention patent application having an application number of 200780040498.2, an application date of 2007 at 11/1/2007 and an invention name of "radiation-sensitive composition".

Technical Field

The present invention relates to a cyclic compound represented by a specific chemical structural formula and used as an acid-proliferating non-polymer-based resist material, a radiation-sensitive composition containing the cyclic compound, a composition for forming an underlayer film, a method for forming a resist pattern using the composition, and a method for forming an underlayer film.

Background

A conventional general resist material is a polymer material capable of forming an amorphous film. For example, a resist film is formed by applying a solution of a polymer resist material such as polymethyl methacrylate, polyhydroxystyrene having an acid-dissociable reactive group, or polyalkylmethacrylate onto a substrate, and then irradiating the film with ultraviolet light, far ultraviolet light, electron beam, extreme ultraviolet light (EUV), X-ray, or the like to form a linear pattern of about 45 to 100 nm.

However, since the polymer resist has a large molecular weight of about 1 to 10 ten thousand and a wide molecular weight distribution, roughness is generated on the surface of a fine pattern in a photolithography method using the polymer resist, it is difficult to control the pattern size, and the yield is lowered. Therefore, the conventional photolithography using a polymer resist has a limitation in miniaturization. Various low molecular weight resist materials are disclosed for making finer patterns.

For example, there have been proposed a positive resist composition containing a low-molecular-weight polynuclear polyphenol compound having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group as a main component (see patent document 1) and an alkali-developable negative resist composition containing a low-molecular-weight polynuclear polyphenol compound as a main component (see patent document 2).

As a candidate for a low-molecular-weight resist material, a positive-type resist composition mainly composed of a low-molecular-weight cyclic polyphenol compound having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group has been proposed (see patent documents 3 to 10 and non-patent documents 1 and 2), or an alkali-developable negative-type resist composition mainly composed of a low-molecular-weight cyclic polyphenol compound (see non-patent document 3).

Since these low molecular weight cyclic polyphenol compounds have a small molecular weight, it is expected to provide a resist pattern having a small molecular size, high resolution, and small roughness. In addition, the low molecular weight cyclic polyphenol compound can impart high heat resistance while maintaining a low molecular weight by having a rigid cyclic structure in its skeleton.

However, the low molecular weight cyclic polyphenol compounds disclosed at present have problems such as low etching resistance, large amount of outgas, poor solubility of safe solvents used in semiconductor production processes, and poor shape of the resulting resist pattern, and improvement of the low molecular weight cyclic polyphenol compounds is desired.

In addition, in view of the influence of the uniformity of the solid content of the positive resist composition on the resolution and roughness of the resist pattern, it is desirable to use a low molecular weight cyclic polyphenol compound having an acid-dissociable functional group as a single-component positive resist composition having high uniformity. However, in a positive resist composition using a cyclic polyphenol having a low molecular weight as a single component, since the introduction rate of an acid-dissociable functional group is generally 100%, the sensitivity is low, and a cyclic polyphenol having a high sensitivity and a low molecular weight has not been disclosed.

Patent document 1: japanese laid-open patent publication No. 2005-369761

Patent document 2: japanese unexamined patent publication No. 2005-326838

Patent document 3: japanese unexamined patent publication No. 11-153863

Patent document 4: japanese unexamined patent publication No. 11-322656

Patent document 5: japanese unexamined patent application publication No. 2002-328473

Patent document 6: japanese unexamined patent publication No. 2003-321423

Patent document 7: japanese laid-open patent publication No. 2005-170902

Patent document 8: japanese unexamined patent publication No. 2006-276459

Patent document 9: japanese unexamined patent publication No. 2006-276742

Patent document 10: japanese laid-open patent publication No. 2007-8875

Non-patent document 1: seung Wook Chang et al, "" Materials for Future lipid "", Proc. SPIE, Vol.5753, p.1

Non-patent document 2: daniel Bratton et al, "" Molecular Glass resins for Next Generation Lithographics "", Proc. SPIE, Vol.6153,61531D-1

Non-patent document 3: T.Nakayama, M.Nomura, K.Haga, M.Ueda: Bull.chem.Soc.Jpn.,71,2979(1998)

Disclosure of Invention

The invention aims to:

(1) to provide a radiation-sensitive composition containing a resist compound, which has high sensitivity, high resolution, high etching resistance, low outgassing amount, and good shape of the resulting resist pattern, and a method for forming a resist pattern using the radiation-sensitive composition;

(2) to provide a radiation-sensitive composition containing a resist compound and having a good resist pattern shape, and a method for forming a resist pattern using the radiation-sensitive composition;

and (3) a composition for forming a novel photoresist underlayer film, which is excellent in optical characteristics and etching resistance and substantially free from sublimates, an underlayer film formed from the composition, and a method for forming a resist pattern using the underlayer film.

The present invention relates to:

(1) a cyclic compound represented by the following formula (1),

[ chemical formula 1]

(wherein L is independently selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a cycloalkylene group having 3 to 20 carbon atomsA C6-24 arylene group, -O-, -OC (-O) -, -OC (-O) O-, -N (R)⁵)-C(＝O)-、-N(R⁵)-C(＝O)O-、-S-、-SO-、-SO₂-and any combination thereof; r¹Independently a functional group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof, or a functional group selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, An acid-dissociable functional group selected from the group consisting of an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxycarbonylalkyl group, or a hydrogen atom; r' is independently alkyl with 2-20 carbon atoms, or aryl with 6-24 carbon atoms shown in the following formula or derivatives thereof:

[ chemical formula 2]

R⁴Is a functional group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms (but not a t-butyl group), a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof; r⁵Is hydrogen or alkyl with 1-10 carbon atoms; m is an integer of 1 to 4; p is an integer of 0 to 5. ) (ii) a

(2) A radiation-sensitive composition comprising the cyclic compound according to the above (1) and a solvent;

(3) an underlayer coating forming composition comprising the radiation-sensitive composition according to (2) above;

(4) a process for producing a cyclic compound B0, which comprises reacting, as a first-stage reaction, an acid-dissociable functional group-introducing reagent with an aldehyde compound A1B having 2 to 59 carbon atoms and having a reactive functional group and 1 to 4 formyl groups to synthesize an acid-dissociable functional group-introduced aldehyde compound A1 c; as the second-stage reaction, condensation reaction of the aldehyde compound A1c and the phenol compound a2 is performed;

(5) A process for producing a cyclic compound B0, wherein, as a first-stage reaction, a condensation reaction of an aldehyde compound A1d having 2 to 59 carbon atoms and having 1 to 2 carboxyl groups or ester groups and 1 to 4 formyl groups with a phenol compound A2 is carried out to synthesize a cyclic compound A0 having 1 to 8 carboxyl groups in the molecule and having a molecular weight of 800-5000; as the reaction of the second stage, a reaction of a cyclic compound a0 having a carboxyl group with a compound A3 having a halomethyl ether group is carried out;

(6) an underlayer coating formed from the composition for forming an underlayer coating according to (3) above;

and (7) a method of forming a resist pattern, wherein the method comprises: forming a resist film on a substrate using the radiation-sensitive composition according to (2) above; exposing the resist film; and a step of developing the resist film to form a resist pattern.

The present invention can provide:

(1) a radiation-sensitive composition containing a resist compound and having high sensitivity, high resolution, high etching resistance, low outgassing amount, and good shape of the resulting resist pattern, and a method for forming a resist pattern using the radiation-sensitive composition;

(2) A radiation-sensitive composition containing a resist compound and having a good resist pattern shape, and a method for forming a resist pattern using the radiation-sensitive composition;

Detailed Description

The present invention is described in detail below.

[ Cyclic Compound ]

The present invention relates to cyclic compounds useful as resist materials.

The cyclic compound of the present invention is a cyclic compound represented by the following formula (1).

[ chemical formula 3]

(wherein L is independently selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 24 carbon atoms, -O-, -OC (═ O) O-, -N (R)⁵)-C(＝O)-、-N(R⁵)-C(＝O)O-、-S-、-SO-、-SO₂-and any combination thereof; r¹Independently a functional group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof, or a functional group selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, An acid-dissociable functional group selected from the group consisting of an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxycarbonylalkyl group, or a hydrogen atom; r' is independently alkyl with 2-20 carbon atoms or is shown in the following formula Aryl having 6 to 24 carbon atoms or a derivative thereof;

R⁴is a functional group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms (but not a tert-butyl group), a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof, or a functional group selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a substituted alkyl, An acid-dissociable functional group selected from the group consisting of a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group; r⁵Is hydrogen or alkyl with 1-10 carbon atoms; m is an integer of 1 to 4; p is an integer of 0 to 5. )

The cyclic compound represented by the above formula (1) is preferably the following compound.

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

(in each of the above formulae (1-1), (1-2) and (1-2-1), X ₂Is a hydrogen or halogen atom; m is₃Is an integer of 1 to 2; m is₄Is 1; r⁴And p is the same as above).

The cyclic compound has high heat resistance and non-crystallinity, and thus has good film-forming properties, no sublimation properties, good alkali developability, etching resistance, and the like, and is suitable for use as a resist material, particularly as a main component (base material) of a resist material. Further, surprisingly, the film has a benzene structure, has a low extinction coefficient to 193nm light, has a high refractive index, and is suitable for use as a lower layer film material.

In addition, the cyclic compound can be efficiently produced in terms of production by subjecting various aldehydes such as aromatic aldehydes, which are industrially produced, and phenols such as resorcinol and pyrogallol to a dehydration condensation reaction using a nonmetallic catalyst such as hydrochloric acid, and therefore the cyclic compound is extremely useful in practical use.

Further, when the cyclic compound is used as a solvent, it is hardly soluble in Propylene Glycol Monomethyl Ether Acetate (PGMEA) which is generally used, and is soluble in Propylene Glycol Monomethyl Ether (PGME) or cyclohexanone, and therefore, mixing can be suppressed also in forming a multilayer resist.

The cyclic compound of the present invention can be a cis-isomer or a trans-isomer, and may have any structure or a mixture thereof. When used as a resist component of a radiation-sensitive composition, a composition having only one of the cis-isomer and the trans-isomer is preferable because it is a pure compound and the uniformity of the components in the resist film is high. As a method for obtaining a cyclic compound having only one structure of cis-form and trans-form, for example: in the separation by column chromatography or preparative liquid chromatography (preparative liquid chromatography) or in the preparation, a known method such as optimization of a reaction solvent, a reaction temperature, or the like is performed.

In the present invention, among the above cyclic compounds, the following epoxy compounds are preferable.

(a) A cyclic compound represented by the following formula (2).

[ chemical formula 9]

(in the formula, R^7AIndependently a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, an alkoxy group or an ester group. )

By having the above structure, a high refractive index and a suitable extinction coefficient for light of 193nm can be obtained.

As R^7AExamples thereof include: a hydrogen atom; straight-chain alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.; a halogen atom; a cyano group; a hydroxyl group; an alkoxy group or an ester group.

Among them, hydrogen atoms, propyl groups and pentyl groups are particularly preferable for use in a composition for forming an underlayer film because a high refractive index and a suitable extinction coefficient can be obtained for 193nm light.

(b) A cyclic compound represented by the following formula (3).

[ chemical formula 10]

(in the formula, R^7BIndependently a linear alkyl group having 1 to 6 carbon atoms. )

R^7BIs a straight-chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, and the like, preferably trans.

Among these, propyl is particularly preferable because a high refractive index for 193nm light and an appropriate extinction coefficient can be obtained.

The cyclic compounds (a) and (b) can be obtained by condensation reaction of an aromatic aldehyde having 6 to 24 carbon atoms and a resorcinol-or pyrogallol-containing compound.

The cyclic compound can be produced by a known method. For example, it can be obtained by the following method: in an organic solvent (such as toluene, methanol, ethanol, etc.), in the presence of thioacetic acid or beta-mercaptopropionic acid, and an acid catalyst (hydrochloric acid, sulfuric acid, or p-toluenesulfonic acid), in a molar ratio of 1: (1 to excess) of a carbonyl compound (e.g., aromatic aldehyde) and a phenol (e.g., resorcinol, pyrogallol, etc.) at 60 to 150 ℃ for 0.5 to 20 hours, adding toluene to the reaction solution after the reaction is completed, heating to 60 to 80 ℃, stirring for 0.5 to 2 hours, cooling to room temperature, filtering and separating, and finally drying.

The molecular weight of the cyclic compound is preferably 400 to 2000, more preferably 600 to 2000, and still more preferably 800 to 1500. When the amount is within the above range, a resist material, particularly a lower layer film material, having good film forming properties, good etching resistance and a small sublimation component can be obtained.

(c) A cyclic compound selected from the compounds represented by the following formula (4-0) or (4).

[ chemical formula 11]

[ chemical formula 12]

(in each of the formulae (4-0) and (4), X₂Is a hydrogen or halogen atom; l is₁A divalent organic group selected from a single bond and a linear or branched alkyl group having 1 to 4 carbon atoms; l₁Is 0 or 1;m is an integer of 1 to 4; m is₃Is an integer of 1 to 2; m is₄Is 1. )

(d) A cyclic compound selected from the group consisting of the compounds represented by the following formula (5), or a cyclic compound selected from the group consisting of the compounds represented by the following formula (6).

[ chemical formula 13]

[ chemical formula 14]

(in the formulae (5) and (6), R¹As described above. However, at least one of R¹Is an acid dissociable functional group. )

The acid-dissociable functional group can be suitably selected from acid-dissociable functional groups proposed for hydroxystyrene resins, (meth) acrylic resins, and the like used in chemical amplification resist compositions for KrF or ArF. Preferred examples thereof include: substituted methyl, 1-substituted ethyl, 1-substituted n-propyl, 1-branched alkyl, silyl, acyl, 1-substituted alkoxymethyl, cyclic ether, alkoxycarbonyl, and the like. The acid-dissociable functional group preferably does not have a crosslinkable functional group.

The molecular weight of the cyclic compound (d) is preferably 800-. When within the above range, the resist can maintain the necessary film-forming property and the resolution can be improved.

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. Examples thereof include methoxymethyl, methylthiomethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, t-butoxymethyl, 2-methylpropoxymethyl, ethylthiomethyl, methoxyethoxymethyl, phenoxymethyl, 1-cyclopentyloxymethyl, 1-cyclohexyloxymethyl, benzylthiomethyl, phenacyl, 4-bromobenzoylmethyl, 4-methoxybenzoylmethyl, piperonyl, and a substituent represented by the following formula (7).

[ chemical formula 15]

(in the formula, R²Is alkyl with 1-4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a tert-butyl group, and an n-butyl group. )

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. Examples thereof include 1-methoxyethyl group, 1-methylthioethyl group, 1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1-diethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, t-butoxyethyl group, 2-methylpropyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1-diphenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, 1-diphenylethyl group, and a substituent represented by the following formula (8).

[ chemical formula 16]

(in the formula, R²As 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 more preferably a 1-substituted n-propyl group having 8 to 16 carbon atoms. Examples thereof include 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group.

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 1-branched alkyl group having 7 to 16 carbon atoms. Examples thereof include isopropyl group, sec-butyl group, tert-butyl group, 1-dimethylpropyl group, 1-methylbutyl group, 1-dimethylbutyl group, 2-methyladamantyl group, and 2-ethyladamantyl group.

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. Examples thereof include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, t-butyldimethylsilyl, t-butyldiethylsilyl, t-butyldiphenylsilyl, tri-t-butylsilyl and triphenylsilyl.

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 thereof include acetyl, phenoxyacetyl, propionyl, butyryl, heptanoyl, hexanoyl, pentanoyl, pivaloyl, isovaleryl, lauroyl, adamantanoyl (アダマンチルカルボニル yl), benzoyl and naphthoyl.

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 more preferably a 1-substituted alkoxymethyl group having 6 to 16 carbon atoms. Examples thereof include 1-cyclopentylmethoxymethyl, 1-cyclopentylethoxymethyl, 1-cyclohexylmethoxymethyl, 1-cyclohexylethoxymethyl, 1-cyclooctylmethoxymethyl and 1-adamantylmethoxymethyl.

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 tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxytetrahydropyranyl group, and 4-methoxytetrahydrothiopyranyl group.

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. Examples thereof include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, and an acid-dissociable functional group in the case where n is 0 represented by the following formula (9).

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. Examples thereof include methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, and n-butoxycarbonylmethyl, and an acid-dissociable functional group in the case where n is 1 to 4 as represented by the following formula (9).

[ chemical formula 17]

(in the formula, R²Is hydrogen or straight chain or branched chain alkyl with 1-4 carbon atoms; n is an integer of 0 to 4. )

Among 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, and a substituted methyl group, a 1-substituted ethyl group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group are more preferable because of their high sensitivity, and acid-dissociable functional groups having a structure selected from the group consisting of cycloalkanes having 3 to 12 carbon atoms, lactones, and aromatic rings having 6 to 12 carbon atoms are further preferable. The cycloalkane having 3 to 12 carbon atoms may be a monocyclic ring or a polycyclic ring, and is preferably a polycyclic ring. Specific examples thereof include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane, and more specifically, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane and cyclohexane, and polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclodecane. Among them, adamantane, tricycloalkane and tetracycloalkane are preferable, and adamantane and tricycloalkane are particularly preferable. The cycloalkane having 3 to 12 carbon atoms may have a substituent. Examples of the lactone include butyrolactone and a cycloalkyl group having 3 to 12 carbon atoms and having a lactone group. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and the like, 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 the groups represented by the following formula (10) is preferable because of its high resolution.

[ chemical formula 18]

(in the formula, R⁵Is hydrogen or straight chain or branched chain alkyl with 1-4 carbon atoms; r⁶Hydrogen, straight chain or branched chain alkyl with 1-4 carbon atoms, cyano, nitro, heterocyclic radical, halogen and carboxyl; n is₁Is an integer of 0 to 4; n is₂Is an integer of 1 to 5; n is₀Is an integer of 0 to 4. )

In addition, the acid-dissociable functional group R is not particularly limited as long as the effects of the present invention are not impaired¹May contain a repeating unit represented by the following formula (11) and the following formula (12) or R¹(R¹The same as described above).

[ chemical formula 19]

[ chemical formula 20]

In the formulae (11) and/or (12), R¹As described above. L is a single bond, methylene, ethylene or carbonyl. n is₅Is an integer of 0 to 4, n₆Is an integer of 1 to 3, x is an integer of 0 to 3, and satisfies 1 ≦ n₅+n₆And ≦ 5. A plurality of n₅、n₆X may be the same or different. R³Is selected from halogen atoms, alkyl, cycloalkaneAryl, aralkyl, alkoxy, aryloxy, alkenyl, acyl, alkoxycarbonyl, alkanoyloxy, aroyloxy, cyano, and nitro. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom; examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like; examples of the cycloalkyl group include cyclohexyl, norbornyl, adamantyl, and the like; examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like; examples of the aralkyl group include a benzyl group, a hydroxybenzyl group, a dihydroxybenzyl group, and the like; examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like; examples of the aryloxy group include a phenoxy group and the like; examples of the alkenyl group include alkenyl groups having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, and the like; examples of the acyl group include aliphatic acyl groups having 1 to 6 carbon atoms (e.g., formyl group, acetyl group, propionyl group, butyryl group, valeryl group, isovaleryl group, pivaloyl group, etc.) and aromatic acyl groups (e.g., benzoyl group, toluoyl group, etc.); examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 5 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, and the like; examples of the alkanoyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group and the like; examples of the arylacyloxy group include benzoyloxy group and the like. Plural R ³May be the same or different.

A method of introducing an acid-dissociable functional group into at least one phenolic hydroxyl group of the cyclic compound a is known. For example, as shown below, an acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group of the cyclic compound a. The compound for introducing an acid-dissociable functional group can be synthesized by a known method or can be easily obtained, and examples thereof include active carboxylic acid derivative compounds such as acid chlorides, acid anhydrides, and dicarbonates; an alkyl halide; vinyl alkyl ethers, dihydropyrans, alkyl halocarboxylates, and the like, but are not particularly limited.

For example, cyclic compound a can be dissolved or suspended in an aprotic solvent such as acetone, Tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, and the like. Then, a vinyl alkyl ether (e.g., ethyl vinyl ether) or dihydropyran is added thereto, and the reaction mixture is neutralized with an alkaline compound at 20 to 60 ℃ for 6 to 72 hours under normal pressure in the presence of an acid catalyst (e.g., pyridinium p-toluenesulfonate), and the resulting neutralized reaction mixture is added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain a cyclic compound d.

In addition, the cyclic compound a is dissolved or suspended in an aprotic solvent (e.g., acetone, THF, propylene glycol monomethyl ether acetate, etc.); then, adding alkyl halide (such as chloromethyl ethyl ether, etc.) or alkyl halocarboxylate (such as methyl adamantyl bromoacetate, etc.), and reacting for 6-72 hours under normal pressure and at 20-110 ℃ in the presence of an alkali catalyst (such as potassium carbonate, etc.); the reaction mixture is neutralized with an acid (e.g., hydrochloric acid), and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain cyclic compound d.

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, and the phenolic hydroxyl group and the carboxyl group are preferable, and the phenolic hydroxyl group is particularly preferable. In order to form a pattern with higher sensitivity and high resolution, the acid-dissociable functional group preferably has a property of causing a cleavage reaction in the presence of an acid in a chain manner.

The cyclic compound a can be obtained by a condensation reaction of at least one selected from the group consisting of aromatic carbonyl compounds a1 and at least one selected from the group consisting of phenolic compounds a 2.

The aromatic carbonyl compound a1 is benzaldehyde having 10 to 24 carbon atoms having a substituent containing at least one alicyclic or aromatic ring in addition to the aromatic ring of benzaldehyde, and examples thereof include: cyclopropyl benzaldehyde, cyclobutyl benzaldehyde, cyclopentyl benzaldehyde, cyclohexyl benzaldehyde, phenyl benzaldehyde, naphthalene formaldehyde, adamantane benzaldehyde, norbornyl benzaldehyde, hydroxypropionyl benzaldehyde and the like, preferably cyclohexyl benzaldehyde and phenyl benzaldehyde, and more preferably cyclohexyl benzaldehyde. The aromatic carbonyl compound a1 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 carbonyl compound a1 may be used alone or in combination of two or more.

Examples of the phenolic compound a2 include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, with resorcinol and pyrogallol being preferred, and resorcinol being 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. The phenolic compound a2 may be used singly or in combination.

The cyclic compound a can be produced by a known method. For example, it can be obtained by the following method: in an organic solvent (such as methanol, ethanol, etc.), in the presence of an acid catalyst (hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc.), using a molar ratio of 1: (0.1-10) reacting aromatic carbonyl compound A1 and phenolic compound A2 at 60-150 deg.C for about 0.5-20 hr, filtering, washing with alcohol (such as methanol), washing with water, filtering, separating, and drying. It can also be obtained by using a basic catalyst (sodium hydroxide, barium hydroxide, 1, 8-diazabicyclo [5.4.0] undec-7-ene, etc.) in place of the acid catalyst, and by carrying out the reaction in the same manner. Further, the cyclic compound a can also be produced by converting the aromatic carbonyl compound a1 into a dihalide with a hydrogen halide or a halogen gas, and reacting the isolated dihalide with the phenolic compound a 2.

In order to reduce the residual metal content of the cyclic compound a, purification may be performed as necessary. In addition, if the acid catalyst and the co-catalyst remain, in general, the storage stability of the radiation-sensitive composition is lowered; or when the basic catalyst remains, the sensitivity of the radiation-sensitive composition is generally lowered, and therefore purification for the purpose of lowering the content thereof may be performed. The purification can be carried out by a known method, and the cyclic compound a is not particularly limited as long as it is not modified, and examples thereof include: a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with an alkaline aqueous solution, a method of treatment with an ion exchange resin, a method of treatment with a silica gel column chromatograph, and the like. More preferably, two or more of these purification methods are combined. An optimum method can be appropriately selected from an acidic aqueous solution, a basic aqueous solution, an ion exchange resin and a silica gel column chromatograph according to the amount and type of the metal to be removed, the acidic compound and/or the basic compound, the type of the purified cyclic compound a, and the like. For example, the acidic aqueous solution may be an aqueous solution of hydrochloric acid, nitric acid or acetic acid having a concentration of 0.01 to 10mol/L, the basic aqueous solution may be an aqueous solution of ammonia having a concentration of 0.01 to 10mol/L, and the ion exchange resin may be a cation exchange resin such as Amberlyst 15J-HG Dry manufactured by オルガノ. Drying may also be carried out after purification. The drying may be carried out by a known method, and is not particularly limited, and examples thereof include vacuum drying and hot air drying under the condition that the cyclic compound a is not modified.

The cyclic compound d has low sublimability at 100 ℃ or lower, preferably 120 ℃ or lower, more preferably 130 ℃ or lower, still more preferably 140 ℃ or lower, and particularly preferably 150 ℃ or lower, preferably under normal pressure. The low sublimation property is preferably 10% or less, preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and particularly preferably 0.1% or less of the weight loss when the sample is held at a predetermined temperature for 10 minutes in thermogravimetric analysis. By reducing the sublimation property, contamination of the exposure apparatus due to outgassing during exposure can be prevented. In addition, a good pattern shape can be imparted with low Line Edge Roughness (LER).

The cyclic compound d satisfies: preferably, F < 3.0(F represents the total number of atoms/(total number of carbon atoms-total number of oxygen atoms)), and more preferably, F < 2.5. By satisfying the above conditions, the dry etching resistance is improved.

The cyclic compound d is selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate, and a solvent in which 1% by weight or more, more preferably 3% by weight or more, further preferably 5% by weight or more, and particularly preferably 10% by weight or more of the cyclic compound d is dissolved in a solvent exhibiting the maximum dissolving ability for the cyclic compound d at 23 ℃. By satisfying the above conditions, the use of a safe solvent in the semiconductor production process becomes possible.

The cyclic compound d can be formed into an amorphous film by spin coating. In addition, the method can be applied to a general semiconductor manufacturing process.

The amorphous film of the cyclic compound d preferably has a dissolution rate at 23 ℃ of a 2.38 mass% aqueous solution of TMAH

Hereinafter, more preferred is

Further preferably 0.0005 to 5

Is composed of

Hereinafter, the resist is insoluble in an alkaline developer and can be used as a resist. In addition, have

At a dissolution rate higher than the above, the resolution may be improved. This is presumably because the minute surface portion of the cyclic compound d is dissolved, and the LER is lowered. In addition, there is an effect of reducing defects.

The cyclic compound a0 formed by dissociation of the acid-dissociable functional group of the cyclic compound d also preferably has a property of forming an amorphous film by spin coating. Non-substitution of cyclic Compound A0The dissolution rate of the crystalline film in a 2.38 mass% aqueous TMAH solution at 23 ℃ is preferably

Above, more preferably

Further preferred is

Is composed of

In the above case, the resist can be dissolved in an alkaline developer to be a resist. In addition, have

The resolution may be improved at the following dissolution rate. This is presumably because the difference between the interface between the exposed portion dissolved in the alkaline developer and the interface between the unexposed portion not dissolved in the alkaline developer is increased by the change in solubility caused by the dissociation of the acid-dissociable functional group of the cyclic compound d. In addition, the method has the effects of reducing LER and reducing defects.

The solid component of the radiation-sensitive composition can be formed into an amorphous film by spin coating. The amorphous film formed by spin coating the solid component of the radiation-sensitive composition preferably has a dissolution rate at 23 ℃ in a 2.38 mass% aqueous solution of TMAH

The following. The amorphous film is exposed to a desired pattern by irradiation with radiation such as KrF excimer laser, ultra-violet ray, electron beam, or X-ray, and the amorphous film after heating at 20 to 250 ℃ as required has a dissolution rate of 2.38 mass% TMAH aqueous solution at 23 ℃ preferably

The above. By satisfying the above conditions, the finished product is obtainedThe rate is good, and a good pattern shape can be provided.

The glass transition temperature of the cyclic compound d is preferably 100 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 140 ℃ or higher, and particularly preferably 150 ℃ or higher. When the glass transition temperature is in the above range, the heat resistance that can maintain the pattern shape in the semiconductor photolithography process can be obtained, and the performance such as high resolution can be provided.

The calorific value of crystals determined by differential scanning calorimetry analysis of the glass transition temperature of the cyclic compound d is preferably less than 20J/g. The (crystallization temperature) - (glass transition temperature) is preferably 70 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, and particularly preferably 130 ℃ or higher. When the amount of heat generated by crystallization is less than 20J/g and (crystallization temperature) - (glass transition temperature) is within the above range, an amorphous film is easily formed by spin coating the radiation-sensitive composition, and the film-forming properties necessary for a resist can be maintained for a long period of time, whereby the resolution can be improved.

In the present invention, the calorific value of crystallization, the crystallization temperature and the glass transition temperature can be determined by the following measurement and differential scanning calorimetry using DSC/TA-50WS manufactured by Shimadzu corporation. About 10mg of the sample was placed in an aluminum non-sealed container, and the temperature was raised to a temperature higher than the melting point in a nitrogen gas flow (50ml/min) at a temperature raising rate of 20 ℃/min. After quenching, the temperature was again raised to a temperature higher than the melting point in a nitrogen gas flow (30ml/min) at a temperature raising rate of 20 ℃/min. After quenching, the temperature was again raised to 400 ℃ in a nitrogen gas flow (30ml/min) at a temperature raising rate of 20 ℃/min. The temperature at the midpoint of the region where the discontinuity appears on the base line (when the specific heat becomes half) was taken as the glass transition temperature (Tg), and the temperature at the heat generation peak which subsequently appears was taken as the crystallization temperature. The calorific value was obtained from the area of the region surrounded by the exothermic peak and the base line, and was calculated as the crystal calorific value.

(e) A cyclic compound represented by the following formula (13-0) or formula (13).

[ chemical formula 21]

[ chemical formula 22]

(in formulae (13-0) and (13), R^3AExamples thereof include a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxycarbonylalkyl group having 2 to 20 carbon atoms; x ₂、L₁、l₁And m is the same as in the above formula (4-0). )

Examples of the substituted methyl group having 2 to 20 carbon atoms, the 1-substituted ethyl group having 3 to 20 carbon atoms, the 1-substituted n-propyl group having 4 to 20 carbon atoms, the 1-branched alkyl group having 3 to 20 carbon atoms, the silyl group having 1 to 20 carbon atoms, the acyl group having 2 to 20 carbon atoms, the 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, the cyclic ether group having 2 to 20 carbon atoms, the alkoxycarbonyl group having 2 to 20 carbon atoms and the alkoxycarbonylalkyl group having 2 to 20 carbon atoms which may be similarly mentioned in the above-mentioned R¹The acid-dissociable functional group described in (1).

The cyclic compound e is more preferably a compound selected from the compounds represented by the following formula (14).

[ chemical formula 23]

(in the formula, R^3A、X₂、L₁、l₁As described above. )

The cyclic compound e is particularly preferably a compound selected from the compounds represented by the following formula (15).

[ chemical formula 24]

(in the formula, X₂、R^3AAs described above. )

R^3AMore preferably an acid-dissociable functional group having a structure selected from the group consisting of cycloalkanes having 3 to 20 carbon atoms, lactones, and aromatic rings having 6 to 12 carbon atoms. The cycloalkane having 3 to 20 carbon atoms may be monocyclic or polycyclic, and polycyclic is preferable. Specific examples thereof include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane, and more specifically, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane and cyclohexane, and polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclodecane. Among them, adamantane, tricycloalkane and tetracycloalkane are preferable, and adamantane and tricycloalkane are particularly preferable. The cycloalkane having 3 to 20 carbon atoms may have a substituent. Examples of the lactone include butyrolactone and a cycloalkyl group having 3 to 20 carbon atoms and having a lactone group. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and the like, and the benzene ring and the naphthalene ring are preferable, the naphthalene ring is particularly preferable, and the acid-dissociable functional group represented by the following formula (16) is more preferable. By having such an acid-dissociable functional group, the resolution and LER of the resulting resist pattern can be improved.

[ chemical formula 25]

(in the formula, R⁵、R⁶、n₀、n₁、n₂As described above. )

The cyclic compound e can also be obtained by a dehydration condensation reaction of the cyclic compound a0 having a carboxyl group and a compound having an alcoholic hydroxyl group.

The cyclic compound e can also be obtained by transesterification of a cyclic compound A0a and a compound having an alcoholic hydroxyl group, wherein the cyclic compound A0a is obtained by replacing a carboxyl group of a cyclic compound A0 having a carboxyl group with an ester bond represented by the following formula (17). Transesterification reactions are well known. As the compound having an alcoholic hydroxyl group, any of primary alcohols, secondary alcohols, and tertiary alcohols can be used, secondary alcohols and tertiary alcohols are more preferable, and tertiary alcohols are particularly preferable.

[ chemical formula 26]

(in the formula, R^3BIs a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. )

The linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-octyl group, and an n-dodecyl group.

The branched alkyl group having 3 to 20 carbon atoms is preferably 3 to 10 carbon atoms, and specifically includes isopropyl, tert-butyl, isopentyl, neopentyl and the like, and tert-butyl is particularly preferable.

The cycloalkyl group having 3 to 20 carbon atoms is preferably 6 to 14 carbon atoms. The alicyclic ring contained in the cycloalkyl group may be monocyclic or polycyclic, and polycyclic is more preferable. Specific examples thereof include: monocyclic alkanes, bicyclic alkanes, tricyclic alkanes, tetracycloalkanes, and the like, and more specifically, there may be mentioned: monocyclic alkanes such as cyclopropane, cyclobutane, cyclopentane and cyclohexane, and polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclodecane. Among them, adamantane, tricycloalkane and tetracycloalkane are preferable, and adamantane and tricycloalkane are particularly preferable.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.

The cyclic compound e can be obtained by reacting a cyclic compound a0 having a carboxyl group with a compound A3 having a halomethyl ether group. For example, the cyclic compound B0 can be obtained by the following method: the cyclic compound a0 having a carboxyl group is dissolved or suspended in an aprotic solvent (e.g., acetone, THF, propylene glycol monomethyl ether acetate, etc.), then, the compound A3 having a halomethyl ether group is added, and the reaction is carried out in the presence of a base catalyst (e.g., pyridine, triethylamine, diazabicycloundecene, potassium carbonate, etc.) in an amount of 0.5 to 4 equivalents, preferably 0.9 to 1.1 equivalents, more preferably 1.0 equivalent, relative to the carboxyl group of the cyclic compound a0 having a carboxyl group at normal pressure at 0 to 110 ℃ for 1 to 72 hours, after which the reaction is washed with an alcohol (e.g., methanol, etc.), washed with water, filtered and separated, and finally dried. The compound may be purified by column chromatography or the like as necessary.

The molecular weight of the cyclic compound e is 800-. In the above range, the film forming property necessary for the resist can be maintained and the resolution can be improved.

[ radiosensitive composition and Cyclic Compound for use in the composition ]

The present invention relates to a radiation-sensitive composition containing a cyclic compound of any one of the formulas (1) and (a) to (e) and a solvent.

Further, the present invention relates to the above radiation-sensitive composition, wherein the cyclic compound is a cyclic compound having a molecular weight of 700-5000 synthesized by a condensation reaction of an aldehyde compound a1 and a phenol compound a2, wherein the aldehyde compound a1 is a compound having 2 to 59 carbon atoms and 1 to 4 formyl groups, and the phenol compound a2 is a compound having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups.

(radiation-sensitive composition A)

The radiation-sensitive composition preferred in the present invention has the following characteristics: in the radiation-sensitive composition, the cyclic compound is a cyclic compound B having a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of the cyclic compound and having a molecular weight of 800-5000.

That is, the radiation-sensitive composition preferred in the present invention has the following features: the radiation-sensitive composition contains 1 to 80 wt% of a solid component and 20 to 99 wt% of a solvent, wherein the radiation-sensitive composition contains a cyclic compound B, and the cyclic compound B is 50 to 99.999 wt% of the total weight of the solid component, wherein the cyclic compound B satisfies: (a) a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of a cyclic compound A synthesized by a condensation reaction of benzaldehyde having 7 to 24 carbon atoms and having no hydroxyl group or a tert-butyl group, and a compound having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups; (b) molecular weight is 800-.

Further, a radiation-sensitive composition preferred in the present invention has the following features: the radiation-sensitive composition contains 1-80 wt% of solid components and 20-99 wt% of solvent, wherein the radiation-sensitive composition contains a cyclic compound B as a solid component, and the cyclic compound B accounts for more than 50 wt% of the total weight of the solid components, wherein the cyclic compound B satisfies the following conditions: (a) a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of a cyclic compound A synthesized by a condensation reaction of a C10-24 benzaldehyde having a substituent containing an alicyclic or aromatic ring and a C6-15 compound having 1-3 phenolic hydroxyl groups; (b) molecular weight is 800-.

In the radiation-sensitive composition of the present invention, the content of the cyclic compound B is 50% by weight or more based on the total weight of the solid content.

The cyclic compound B has a structure in which an acid-dissociable functional group is introduced into at least one phenolic hydroxyl group of the cyclic compound A, which is synthesized by a condensation reaction of benzaldehyde having 10 to 24 carbon atoms and having a substituent containing an alicyclic or aromatic ring or benzaldehyde having 7 to 24 carbon atoms and having neither a hydroxyl group nor a tert-butyl group (hereinafter, each referred to as an aromatic carbonyl compound A1) with a compound having 6 to 15 carbon atoms and having 1 to 3 phenolic hydroxyl groups (hereinafter, referred to as a phenolic compound A2), and has a molecular weight of 800-5000.

The cyclic compound a can be obtained by a condensation reaction of one or more compounds selected from the group consisting of the aromatic carbonyl compound a1 and one or more compounds selected from the group consisting of the phenolic compound a 2.

The aromatic carbonyl compound A1 is a benzaldehyde having 7 to 24 carbon atoms and having neither a hydroxyl group nor a tert-butyl group, or a benzaldehyde having 10 to 24 carbon atoms and having a substituent containing an alicyclic or aromatic ring, and examples thereof include benzaldehyde, tolualdehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde other than tert-butyl, ethylmethylbenzaldehyde, isopropylmethylbenzaldehyde, diethylbenzaldehyde, p-methoxybenzaldehyde, naphthaldehyde, anthracenealdehyde, cyclopropylbenzaldehyde, cyclobutylbenzaldehyde, cyclopentylbenzaldehyde, cyclohexylbenzaldehyde, phenylbenzaldehyde, naphthylbenzaldehyde, adamantylbenzaldehyde, norbornenylbenzaldehyde, hydroxypropylbenzaldehyde, isopropylbenzaldehyde, n-propylbenzaldehyde, bromobenzaldehyde, and dimethylaminobenzaldehyde, and preferably isopropylbenzaldehyde, n-propylbenzaldehyde, bromobenzaldehyde, and dimethylaminobenzaldehyde, N-propylbenzaldehyde, bromobenzaldehyde, dimethylaminobenzaldehyde, cyclohexylbenzaldehyde, benzaldehyde, and more preferably cyclohexylbenzaldehyde, 4-isopropylbenzaldehyde, and 4-n-propylbenzaldehyde.

The aromatic carbonyl compound a1 may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a halogen, or the like, as long as the effects of the present invention are not impaired. The aromatic carbonyl compound a1 may be used alone or in combination of two or more.

Examples of the phenolic compound a2 include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, with resorcinol and pyrogallol being preferred, and resorcinol being 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. The phenolic compound a2 may be used alone or in combination of two or more.

As regards the cyclic compound a, as described for said formulae (4), (5) and (6).

More preferably, two or more kinds of the aromatic carbonyl compound a1 and/or two or more kinds of the phenolic compound a2 are used. By using two or more aromatic carbonyl compounds a1 and/or two or more phenolic compounds a2, the solubility of the resulting cyclic compound a in a semiconductor-safe solvent can be improved.

The cyclic compound a can be formed into an amorphous film by spin coating. In addition, the method can be applied to a general semiconductor manufacturing process.

The amorphous film of the cyclic compound A preferably has a dissolution rate at 23 ℃ of a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH)

Above, more preferably

Further preferred is

Is composed of

The resolution may be improved at the following dissolution rate. In addition, the method has the effects of reducing LER and reducing defects.

The acid-dissociable functional group can be suitably selected from the acid-dissociable functional groups proposed for hydroxystyrene resins, (meth) acrylic resins, and the like used in chemical amplification resist compositions for KrF or ArF. Preference is given, for example: substituted methyl, 1-substituted ethyl, 1-substituted n-propyl, 1-branched alkyl, silyl, acyl, 1-substituted alkoxymethyl, cyclic ether, alkoxycarbonyl, and the like. The acid-dissociable functional group preferably does not have a crosslinkable functional group.

The molecular weight of the cyclic compound B is 800-5000, preferably 800-2000, more preferably 1000-2000. When within the above range, the resist can maintain the necessary film-forming property and the resolution can be improved.

The cyclic compound of the present invention can be a cis-isomer or a trans-isomer, and may have any structure or a mixture thereof. When used as a resist component of a radiation-sensitive composition, a composition having only one of the cis-isomer and the trans-isomer is preferable because it is a pure compound and the uniformity of the components in the resist film is high. As a method for obtaining a cyclic compound having only one structure of cis-form and trans-form, for example: separation by column chromatography or preparative liquid chromatography, or preparation, can be carried out by a known method such as optimization of the reaction solvent, reaction temperature, and the like.

In one embodiment of the present invention, the cyclic compound B is preferably a compound represented by the following formula (18).

[ chemical formula 27]

(in the formula, R⁴A functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (except for a t-butyl group), a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof; l, R¹、R⁵P is the same as in the above formula (1), and at least one R¹Is an acid dissociable functional group. )

The cyclic compound B is preferably a compound represented by the following formula (19) or (19-0), more preferably a compound represented by the following formula (19-1) or (10-0-1).

[ chemical formula 28]

(in the formula, L, R¹、R⁴And p is the same as above. )

[ chemical formula 29]

(in the formula, R¹、R⁴P and m are the same as above. )

[ chemical formula 30]

(in the formula, R¹、R⁴、p、m₃、m₄As described above. )

[ chemical formula 31]

(in the formula, R¹、R⁴And p is the same as above. )

The cyclic compound B is more preferably a compound selected from compounds represented by the following formula (20) or formula (21).

[ chemical formula 32]

[ chemical formula 33]

(in the formula, R¹The same as the above formula (18). )

In the formulae (20) and (21), R¹Independently selected from the group consisting of a C2-20 substituted methyl group, a C3-20 1-substituted ethyl group, a C4-20 1-substituted n-propyl group, a C3-20 1-branched alkyl group, a C1-20 silyl group, a C2-20 acyl group, a C2-20 1-substituted ethyl groupAn acid-dissociable functional group or a hydrogen atom in the group consisting of an alkoxyalkyl group, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group, R¹At least one of them is preferably an acid-dissociable functional group.

The acid-dissociable functional group selected from the group consisting of a substituted methyl group, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group is as described above.

Among 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, and a substituted methyl group, a 1-substituted ethyl group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group are more preferable because of their high sensitivity, and acid-dissociable functional groups having a structure selected from the group consisting of cycloalkanes having 3 to 12 carbon atoms, lactones, and aromatic rings having 6 to 12 carbon atoms are further preferable. The cycloalkane having 3 to 12 carbon atoms may be a monocyclic ring or a polycyclic ring, and a polycyclic ring is more preferable. Specific examples thereof include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc.; more specifically, there may be mentioned monocycloalkanes such as cyclopropane, cyclobutane, cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclodecane. Among them, adamantane, tricycloalkane and tetracycloalkane are preferable, and adamantane and tricycloalkane are particularly preferable. The cycloalkane having 3 to 12 carbon atoms may have a substituent. Examples of the lactone include butyrolactone and a cycloalkyl group having 3 to 12 carbon atoms and having a lactone group. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and the like, and a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is particularly preferable.

In particular, the acid-dissociable functional group represented by the following formula (22) is preferable because of its high resolution.

[ chemical formula 34]

The ratio of the number of halogen atoms to the total number of constituent atoms of the cyclic compound B is preferably 0.1 to 60%, more preferably 0.1 to 40%, still more preferably 0.1 to 20%, particularly preferably 0.1 to 10%, most preferably 1 to 5%. When the amount is within the above range, the sensitivity to radiation increases and the film forming property can be maintained. In addition, the solubility of the safe solvent can be improved.

The ratio of the number of nitrogen atoms to the total number of constituent atoms of the cyclic compound B is preferably 0.1 to 40%, more preferably 0.1 to 20%, still more preferably 0.1 to 10%, and particularly preferably 0.1 to 5%. When within the above range, the line edge roughness of the resulting resist pattern can be reduced, and the film formability can be maintained. The nitrogen atom is preferably a nitrogen atom contained in a secondary amine or a tertiary amine, and more preferably a nitrogen atom contained in a tertiary amine.

In the present invention, the acid-dissociable functional group is 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, and the phenolic hydroxyl group and the carboxyl group are preferable, and the phenolic hydroxyl group is particularly preferable. In order to enable formation of a pattern with higher sensitivity and high resolution, the acid-dissociable functional group preferably has a property of causing a cleavage reaction in the presence of an acid in a chain manner.

The cyclic compound B of the formula (20) or (21) is a low molecular weight compound, and has film-forming properties, heat resistance, dry etching resistance, and low outgassing properties, and therefore is preferable as a resist component of a radiation-sensitive composition. The radiation-sensitive composition containing the cyclic compound B of the formulae (20) to (21) has good resolution, sensitivity and low line edge roughness.

The cyclic compound B of the present invention may be added to a radiation-sensitive composition as an additive for improving sensitivity or etching resistance, for example, instead of being used as a main component, except that it can form a positive-type radiation-sensitive composition using itself as a main component. In this case, the cyclic compound B may be used in an amount of 1 to 49.999 wt% based on the total weight of the solid components.

The cyclic compound B can be formed into an amorphous film by spin coating. In addition, the method can be applied to a general semiconductor manufacturing process.

The cyclic compound B may have a non-acid-dissociable functional group introduced into at least one phenolic hydroxyl group thereof, within a range not impairing the effects of the present invention. The non-acid-dissociable functional group is a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. Examples thereof include: and a functional group selected from the group consisting of C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxy group, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen, carboxyl group, C1-20 alkylsilane, and derivatives thereof, which is not decomposed by the action of an acid.

The naphthoquinonediazide ester group (ナフトキノンジアジドエステル group) may be introduced into at least one phenolic hydroxyl group of the cyclic compound B of the present invention. The compound having the naphthoquinonediazide ester group introduced into at least one phenolic hydroxyl group of the cyclic compound B can be added to a radiation-sensitive composition as an acid generator or an additive, in addition to being capable of forming a positive-type radiation-sensitive composition mainly containing itself.

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 cyclic compound B. The cyclic polyphenol compound having an acid-generating functional group that generates an acid by irradiation with radiation introduced into at least one phenolic hydroxyl group of the cyclic compound B can be added to a radiation-sensitive composition as an acid generator or an additive, in addition to being capable of forming a positive-type radiation-sensitive composition with itself as a main component.

The amorphous film of the cyclic compound B preferably has a dissolution rate at 23 ℃ of a 2.38 mass% TMAH aqueous solution

Hereinafter, more preferred is

Further preferred is

Is composed of

At a dissolution rate higher than the above, the resolution may be improved. This is presumably because the minute surface portion of the cyclic compound B is dissolved, and LER is lowered. In addition, there is an effect of reducing defects.

The cyclic compound a formed by dissociation of the acid-dissociable functional group of the cyclic compound B also preferably has a property of forming an amorphous film by spin coating. The amorphous film of the cyclic polyphenol compound A preferably has a dissolution rate at 23 ℃ in a 2.38 mass% aqueous TMAH solution

Above, more preferably

Further preferred is

Is composed of

In the above case, the resist can be dissolved in an alkaline developer to be a resist. In addition, theIs provided with

The resolution may be improved at the following dissolution rate. This is presumably because the difference between the interface between the exposed portion dissolved in the alkaline developer and the interface between the unexposed portion not dissolved in the alkaline developer is increased by the change in solubility caused by the dissociation of the acid-dissociable functional group of the cyclic compound B. In addition, the method has the effects of reducing LER and reducing defects.

The following. The amorphous film is exposed to a desired pattern by irradiation with radiation such as KrF excimer laser, ultra-ultraviolet ray, electron beam, or X-ray, and the amorphous film after heating at 20 to 250 ℃ as required has a dissolution rate of 2.38 mass% TMAH aqueous solution at 23 ℃ preferably

The above. By satisfying the above conditions, the yield is improved, and a favorable pattern shape can be provided.

The radiation-sensitive composition of the present invention preferably contains 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, more preferably 1 to 50% by weight of a solid component and 50 to 99% by weight of a solvent, still more preferably 2 to 40% by weight of a solid component and 60 to 98% by weight of a solvent, and particularly preferably 2 to 10% by weight of a solid component and 90 to 98% by weight of a solvent. The amount of the cyclic compound B is 50 wt% or more, preferably 65 wt% or more, and more preferably 81 wt% or more based on the total weight of the solid content. When the blending ratio is set as described above, high resolution can be obtained and line edge roughness can be reduced.

The composition of the present invention preferably contains one or more acid generators C that directly or indirectly generate an acid by irradiation with radiation selected from any one of visible light, ultraviolet light, excimer laser, electron beam, Extreme Ultraviolet (EUV), X-ray, and ion beam. The amount of the acid generator to be used is preferably 0.001 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 3 to 30% by weight, based on the total weight of the solid components (the total of the solid components to be used, hereinafter the same, of the cyclic polyphenol compound B, the acid generator C, the low molecular weight dissolution accelerator D, the acid diffusion controller E, and the other components F). By using the acid generator in the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In the present invention, the method for producing an acid is not limited as long as the acid can be produced in the system. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing can be performed; further, if electron beams, ultra-violet rays, X-rays, or ion beams are used as the high-energy beams, further fine processing can be performed.

The acid generator C is preferably at least one compound selected from the group consisting of compounds represented by the following formulae (23-1) to (23-8).

[ chemical formula 35]

(in the formula (23-1), R¹³Each of which may be the same or different and is independently a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group or a halogen atom; x^－Is a sulfonic acid ion or a halide ion having an alkyl group, an aryl group, a halogenated alkyl group or a halogenated aryl group. )

The compound represented by the above formula (23-1) is preferably selected from the group consisting of triphenylsulfonium triflate, triphenylsulfonium nonafluoro-n-butylsulfonate, diphenyltolylsulfonium nonafluoro-n-butylsulfonate, triphenylsulfonium perfluoron-octylsulfonate, diphenyl-4-methylphenyl sulfonium triflate, bis-2, 4, 6-trimethylphenylsulfonium triflate, diphenyl-4-tert-butoxyphenylsulfonium nonafluoro-n-butylsulfonate, diphenyl-4-hydroxyphenyl sulfonium triflate, bis (4-fluorophenyl) -4-hydroxyphenyl sulfonium triflate, diphenyl-4-hydroxyphenyl sulfonium nonafluoro-n-butylsulfonate, bis (4-hydroxyphenyl) -phenyl sulfonium triflate, triphenylsulfonium nonafluoro-n-butylsulfonate, triphenylsulfonium triflate, triphenylsulfonium nonafluoron-butylsulfonate, triphenylsulfonium triflate, diphenylsulfonium, Tris (4-methoxyphenyl) sulfonium triflate, tris (4-fluorophenyl) sulfonium triflate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2, 4, 6-trimethylphenylsulfonium p-toluenesulfonate (ジフェニル -2,4,6- トリメチルフェニル -p- トルエンスルホネート), diphenyl-2, 4, 6-trimethylphenylsulfonium 2-trifluoromethylbenzenesulfonate, diphenyl-2, 4, 6-trimethylphenylsulfonium 4-trifluoromethylbenzenesulfonate, diphenyl-2, 4, 6-trimethylphenylsulfonium 2, 4-difluorophenyl-2, 4, 6-trimethylphenylsulfonium 2, diphenyl-2, 4, 6-trimethylphenylsulfonium hexafluorobenzene sulfonate, diphenyl-2, 4, 6-trimethylphenylsulfonium triflate, diphenylnaphthylsulfonium triflate, sulfonium hexaphenylsulfonium salt, At least one member selected from the group consisting of diphenyl-4-hydroxyphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenyl sulfonium 10-camphorsulfonate and 1, 3-perfluoropropane disulfonimide.

[ chemical formula 36]

(in the formula (23-2), R¹⁴May 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 hydroxyl group or a halogen atom; x^－As described above. )

The compound represented by the above formula (23-2) is preferably a compound selected from the group consisting of bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-tert-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium benzenesulfonate, bis (4-tert-butylphenyl) iodonium-2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-2, 4-difluorobenzenesulfonate, bis (4-tert-butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-tert-butylphenyl) iodonium-10-camphorsulfonate, Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium-10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2, 4-difluorobenzenesulfonate, diphenyliodonium hexafluorobenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) iodonium benzenesulfonate and bis (4-trifluoromethylphenyl) iodonium-10-camphorsulfosulfonate At least one of the group consisting of acid salts.

[ chemical formula 37]

(in the formula (23-3), Q is an alkylene group, an arylene group or an alkyleneoxy group; R¹⁵Is alkyl, aryl, haloalkyl or haloaryl. )

The compound represented by the above formula (23-3) is preferably selected from the group consisting of N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) biphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) biphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (10-camphorsulfonyloxy) naphthalimide, N- (N-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (N-octanesulfonyloxy) naphthalimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (p-toluenesulfonyloxy) naphthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthalimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (perfluorobenzenesulfonyloxy) naphthalimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthalimide, N- (nonafluoron-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (nonafluoron-butanesulfonyloxy) naphthalimide, N- (perfluoron-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide and N- (perfluoro-N-octane sulfonyloxy) naphthalimide.

[ chemical formula 38]

(in the formula (23-4), R¹⁶May be the same or different and each independently is an optionally substituted straight chain, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group. )

The compound represented by the formula (23-4) is preferably at least one selected from the group consisting of diphenyldisulfone, bis (4-methylphenyl) disulfone, dinaphthyldisulfone, bis (4-tert-butylphenyl) disulfone, bis (4-hydroxyphenyl) disulfone, bis (3-hydroxynaphthyl) disulfone, bis (4-fluorophenyl) disulfone, bis (2-fluorophenyl) disulfone, and bis (4-trifluoromethylphenyl) disulfone.

[ chemical formula 39]

(in the formula (23-5), R¹⁷May be the same or different, eachIndependently an optionally substituted linear, linear or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group or an optionally substituted aralkyl group. )

The compound represented by the above formula (23-5) is preferably at least one compound selected from the group consisting of α - (methylsulfonoxyimino) phenylacetonitrile, α - (methylsulfonoxyimino) -4-methoxyphenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) phenylacetonitrile, α - (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α - (methylsulfonoxyimino) -4-bromophenylacetonitrile.

[ chemical formula 40]

In the formula (23-6), R¹⁸The alkyl groups may be the same or different and are each independently a haloalkyl group having 1 or more chlorine atoms and 1 or more bromine atoms. The number of carbon atoms of the haloalkyl group is preferably 1 to 5.

[ chemical formula 41]

[ chemical formula 42]

In the formulae (23-7) and (23-8), R¹⁹And R²⁰Each independently an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, etc., a cycloalkyl group such as cyclopentyl, cyclohexyl, etc., an alkoxy group having 1 to 3 carbon atoms such as methoxy, ethoxy, propoxy, etc., or an aryl group such as phenyl, tolyl, naphthyl, etc., preferably an aryl group having 6 to 10 carbon atoms. L is¹⁹And L²⁰Are respectively and independently provided with 1,2-Organic groups of naphthoquinonediazide. Specific examples of the organic group having 1, 2-diazidonaphthoquinone include a 1, 2-diazidonaphthoquinone sulfonyl group, such as a 1, 2-diazidonaphthoquinone-4-sulfonyl group, a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and a 1, 2-diazidonaphthoquinone-6-sulfonyl group. Particularly preferred are 1, 2-diazidonaphthoquinone-4-sulfonyl group and 1, 2-diazidonaphthoquinone-5-sulfonyl group. p is an integer from 1 to 3, q is an integer from 0 to 4, and 1 ≦ p + q ≦ 5. J. the design is a square¹⁹A single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (23-7-1), a carbonyl group, an ester group, an amide group or an ether group; y is ¹⁹Is a hydrogen atom, an alkyl group or an aryl group; x²⁰Each independently is a group represented by the following formula (23-8-1).

[ chemical formula 43]

[ chemical formula 44]

(in the formula (23-8-1), Z²²Each independently is an alkyl, cycloalkyl or aryl group; r²²Is alkyl, cycloalkyl or alkoxy; r is an integer of 0 to 3. )

Examples of other acid generators include disulfonyl diazomethanes, such as 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 (cyclohexylsulfonyl azidomethylsulfonyl) propane, 1, 4-bis (phenylsulfonylazidomethylsulfonyl) butane, 1, 6-bis (phenylsulfonylazidomethylsulfonyl) hexane, 1, 10-bis (cyclohexylsulfonyl azidomethylsulfonyl) decane, etc.; halogen-containing triazine derivatives such as 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, tris (2, 3-dibromopropyl) isocyanurate and the like.

Among the above acid generators, those having an aromatic ring are preferable, and those represented by the formula (23-1) or (23-2) are more preferable. Further preferably X having the formula (23-1) or the formula (23-2)^－An acid generator having an aryl group-containing or halogenated aryl group-containing sulfonic acid ion is particularly preferred, and an acid generator having an aryl group-containing sulfonic acid ion is particularly preferred: diphenyl (trimethyl) phenyl sulfonium p-toluenesulfonate, triphenyl sulfonium trifluoromethanesulfonate, and triphenyl sulfonium nonafluoromethanesulfonate. By using the acid generator, LER can be reduced.

The acid generator C may be used alone or in combination of two or more.

The low-molecular-weight dissolution accelerator D is a component having an action of increasing the solubility of the cyclic compound B when the solubility thereof in a developer such as an alkali is too low, and appropriately increasing the dissolution rate of the cyclic compound B during development, 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 may be used singly or in combination of two or more. The amount of the dissolution accelerator to be blended may be suitably adjusted depending on the kind of the cyclic compound B to be used, and is an amount such that the total of the cyclic compound B and the low-molecular dissolution accelerator D is 50 to 99.999% by weight, preferably 60 to 99% by weight, more preferably 70 to 99% by weight, and still more preferably 80 to 99% by weight based on the total weight of the solid component.

The low-molecular-weight dissolution accelerator D is preferably a compound selected from the above cyclic compounds a. The cyclic compound a has a low molecular weight, high heat resistance, high amorphousness, and high affinity with the cyclic compound B, and can form a uniform resist film and impart properties such as high resolution and low LER. The cyclic compound a used as the low-molecular-weight dissolution accelerator D is more preferably the same as the cyclic compound a used for producing the cyclic compound B. The affinity between the cyclic compound B and the low-molecular-weight dissolution promoter D is further increased, and a more uniform resist film can be formed, and performance such as high resolution and low LER can be provided.

In the present invention, an acid diffusion controlling agent E having an action of suppressing diffusion of an acid generated from an acid generator by irradiation of radiation in a resist film, preventing an undesired chemical reaction in an unexposed region, or the like may also be blended in the radiation-sensitive composition. By using such an acid diffusion controller E, the resolution is improved, and the line width change of the resist pattern due to the variation in the standing time before the electron beam irradiation and the standing time after the electron beam irradiation can be suppressed, and the process stability is extremely excellent. Further, by using the acid diffusion controller E, the storage stability of the radiation-sensitive composition is improved. Examples of the acid diffusion controlling agent E include electron-ray-emitting basic compounds such as a basic compound containing a nitrogen atom, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller may be used alone or in combination of two or more.

Examples of the acid diffusion controlling agent include nitrogen-containing organic compounds, basic compounds that decompose upon exposure, and the like. Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (24) (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 II"), a polyamino compound or polymer having three or more nitrogen atoms (hereinafter, referred to as "nitrogen-containing compound III"), an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound. The acid diffusion controller may be used singly or in combination of two or more.

[ chemical formula 45]

In the above general formula (24), R⁶¹、R⁶²And R⁶³Each independently represents 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 another functional group such as a hydroxyl group. Examples of the linear, branched or cyclic alkyl group include groups having 1 to 15, preferably 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, a tert-hexyl group (テキシル group), an n-heptyl group, an n-octyl group, an n-ethylhexyl group, an n-nonyl group, an n-decyl group and the like. The aryl group includes a group having 6 to 12 carbon atoms, and specifically includes a phenyl group, a tolyl group, a xylyl group, a cumyl group, a 1-naphthyl group, and the like. Further, the aralkyl group includes a group having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specifically includes a benzyl group, an α -methylbenzyl group, a phenethyl group, a naphthylmethyl group and the like.

Specific examples of the nitrogen-containing compound I include: mono (cyclo) alkylamines such as N-hexylamine, N-heptylamine, N-octylamine, N-nonylamine, N-decylamine, N-dodecylamine, cyclohexylamine, etc., di (cyclo) alkylamines such as di-N-butylamine, di-N-pentylamine, di-N-hexylamine, di-N-octylamine, di-N-nonylamine, di-N-decylamine, methyl-N-dodecylamine, di-N-dodecylmethylamine, cyclohexylmethylamine, dicyclohexylamine, etc., tri (cyclo) alkylamines such as triethylamine, tri-N-butylamine, tri-N-pentylamine, tri-N-hexylamine, tri-N-heptylamine, tri-N-octylamine, tri-N-nonylamine, tri-N-decylamine, dimethyl-N-dodecylamine, di-N-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine, etc., alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, etc., aromatic amines such as aniline, N-methylaniline, N-dimethylaniline, 2-methylaniline, cyclohexylamine, etc, 3-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine and the like.

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 '-diaminodiphenylmethane, 4' -diaminodiphenyl ether, 4 '-diaminobenzophenone, 4' -diaminodiphenylamine, 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, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylether, 4, 1, 4-bis [1- (4-aminophenyl) -1-methylethyl ] benzene, 1, 3-bis [1- (4-aminophenyl) -1-methylethyl ] benzene, and the like.

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

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

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

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

Examples of the basic compound that is decomposed by exposure include a sulfonium compound represented by the following formula (25-1) and an iodonium compound represented by the following general formula (25-2).

[ chemical formula 46]

[ chemical formula 47]

In the above general formulae (25-1) and (25-2), R⁷¹、R⁷²、R⁷³、R⁷⁴And R⁷⁵Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a halogen atom. Z^-Is HO^-、R-COO^-(wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms or an alkylaryl group having 1 to 6 carbon atoms) or an anion represented by the following general formula (25-3).

[ chemical formula 48]

Specific examples of the basic compound that is decomposed by exposure include: triphenylsulfonium hydroxide (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 hydroxide), bis (4-tert-butylphenyl) iodonium acetate, bis (4-tert-butylphenyl) iodonium hydroxide, bis (4-tert-butylphenyl) iodonium acetate, bis (4-tert-butylphenyl) iodonium salicylate, 4-tert-butylphenyl-4-hydroxyphenyliodonium hydroxide, 4-tert-butylphenyl-4-hydroxyphenyliodonium acetate, 4-tert-butylphenyl-4-hydroxyphenyliodonium salicylate, and the like.

The amount of the acid diffusion controller E to be blended is preferably 0 to 10% by weight, more preferably 0.001 to 5% by weight, and still more preferably 0.001 to 3% by weight based on the total weight of the solid content. When the blending amount of the acid diffusion controller E is within the above range, the lowering of the resolution and the deterioration of the figure shape, the dimensional fidelity and the like can be prevented. Further, even if the standing time from the start of the electron beam irradiation to the heating after the radiation irradiation is long, the shape of the upper layer portion of the pattern is not deteriorated. When the amount of the acid diffusion controller E added is 10% by weight or less, the reduction in sensitivity, developability in the non-exposed region, and the like can be prevented. Further, by using such an acid diffusion controller, the storage stability of the resist composition is improved, the resolution is improved, and the line width change of the resist pattern due to the variation of the standing time before the electron beam irradiation and the standing time after the electron beam irradiation can be suppressed, so that the radiation-sensitive composition containing the acid diffusion controller E is extremely excellent in process stability.

One or more of various additives such as a dissolution control agent, a sensitizer, a surfactant, and an oxyacid of an organic carboxylic acid or phosphorus or a derivative thereof may be added as the other component F to the resist composition of the present invention as necessary within a range not to impair the object of the present invention.

[1] Dissolution control agent

The dissolution-controlling agent is a component having an action of controlling the solubility of the cyclic compound B to appropriately decrease the dissolution rate during development when the solubility of the cyclic compound B in a developer such as an alkali is too high. Such a dissolution control agent is preferably one that does not chemically change in the steps of baking, radiation irradiation, development, and the like of the resist coating film.

Examples of the dissolution-controlling agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, acenaphthene, etc., ketones such as acetophenone, benzophenone, phenylnaphthyl ketone, etc., sulfones such as methylphenyl sulfone, diphenyl sulfone, dinaphthyl sulfone, etc. These dissolution controlling agents may be used singly or in combination of two or more.

The amount of the dissolution-controlling agent to be blended may be suitably adjusted depending on the kind of the cyclic compound B to be used, and is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the cyclic compound.

[2] Sensitizers

The sensitizer is a component that absorbs energy of the irradiated radiation and transfers the energy to the acid generator C, thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. Examples of such sensitizers include: benzophenones, diacetyl compounds, pyrenes, phenothiazines, and fluorenes, but are not particularly limited.

These sensitizers may be used singly or in combination of two or more. The amount of the sensitizer is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, per 100 parts by weight of the cyclic compound.

[3] Surface active agent

The surfactant is a component having an action of improving coatability, texture, developability of the resist composition of the present invention, and the like. Such a surfactant may be any of anionic, cationic, nonionic, or amphoteric. Preferred surfactants are nonionic surfactants. The nonionic surfactant has good affinity with a solvent used in the preparation of the radiation-sensitive composition, and is more effective. Examples of the nonionic surfactant include, but are not particularly limited to, polyethylene oxide higher alkyl ethers, polyethylene oxide higher alkyl phenyl ethers, higher fatty acid diesters of polyethylene glycol, and the like. Examples of commercially available products include エフトップ (manufactured by ジェムコ), メガファック (manufactured by インキ chemical industries, japan), フロラード (manufactured by スリーエム sumada), アサヒガード, サーフロン (manufactured by asahi glass corporation), ペポール (manufactured by tokyo chemical industries, japan), KP (manufactured by shin-shiji chemical industries, japan), ポリフロー (manufactured by grease chemical industries, japan), and the like.

The amount of the surfactant to be blended is preferably 2 parts by weight or less as an active ingredient of the surfactant per 100 parts by weight of the cyclic compound.

[4] Oxo acids or derivatives of organic carboxylic acids or phosphorus

The resist composition of the present invention may further contain an organic carboxylic acid, an oxyacid of phosphorus, or a derivative thereof as an optional component for the purpose of preventing deterioration of sensitivity, improving the shape of a resist pattern, the stability in standing, and the like. The acid diffusion controller may be used in combination with the acid diffusion controller, or may be used alone. As the organic carboxylic acid, for example, suitable are: malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and the like. Examples of the oxygen acid of phosphorus or a derivative thereof include phosphoric acid or a derivative thereof (e.g., an ester thereof), such as phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, etc., phosphonic acid or a derivative thereof (e.g., an ester thereof), such as phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, etc., phosphinic acid or a derivative thereof (e.g., an ester thereof), such as phosphinic acid, phenylphosphinic acid, etc., and particularly preferred is phosphonic acid.

The organic carboxylic acid or the phosphorus oxyacid or the derivative thereof may be used alone or in combination of two or more. The amount of the oxygen acid or derivative thereof of the organic carboxylic acid or phosphorus is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, still more preferably 0 to 5% by weight, particularly preferably 0 to 1% by weight based on the total weight of the solid content.

[5] The dissolution control agent, sensitizer, surfactant, and other additives except for the oxyacid of organic carboxylic acid or phosphorus or its derivative

One or more additives other than the above-mentioned dissolution-controlling agent, sensitizer and surfactant may be further added to the radiation-sensitive composition of the present invention as necessary within a range not to impair the object of the present invention. Examples of such additives include dyes, pigments, and adhesion promoters. For example, when a dye or a pigment is blended, a latent image in an exposed portion can be made visible, and the influence of halation at the time of exposure can be reduced, which is preferable. Further, when the adhesion promoter is blended, adhesion to the substrate can be improved, and therefore, it is preferable. Further, as other additives, there may be mentioned antihalation agents, storage stabilizers, antifoaming agents, shape-improving agents and the like, and specific examples thereof include 4-hydroxy-4' -methylchalcone and the like.

The radiation-sensitive composition of the present invention is generally prepared by the following method: when used, each component is dissolved in a solvent to form a uniform solution, and then filtered with, for example, a filter having a pore size of about 0.2 μm, if necessary.

Examples of the solvent used for the preparation of the radiation-sensitive composition of the present invention include: ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate and the like, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like, propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate and the like, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like, lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-pentyl lactate and the like, aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate and the like, other esters, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc., aromatic hydrocarbons such as toluene, xylene, etc., ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, etc., amides such as N, N-dimethylformamide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, etc., lactones such as γ -lactone, etc., but are not particularly limited. These solvents may be used singly or in combination of two or more.

The radiation-sensitive composition of the present invention may contain a resin soluble in an alkaline aqueous solution within a range not impairing the object of the present invention. Examples of the resin soluble in an aqueous alkaline solution include: phenolic resins, polyvinyl phenol resins, polyacrylic acids, polyvinyl alcohols, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, or derivatives thereof, and the like. The blending amount of the resin soluble in the aqueous alkaline solution can be adjusted as appropriate depending on the kind of the resist compound used, and is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, and particularly preferably 0 part by weight, per 100 parts by weight of the cyclic compound B.

(radiation-sensitive composition B)

The present invention relates to a radiation-sensitive composition comprising a cyclic compound B0 and a solvent, wherein the cyclic compound B0 is synthesized by a condensation reaction of an aldehyde compound A1c having an acid dissociable functional group introduced thereto and a phenolic compound having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups, and the molecular weight of the cyclic compound B0 is 700-5000, and wherein the aldehyde compound A1 having 2 to 59 carbon atoms and 1 to 4 formyl groups is the aldehyde compound A1c having an acid dissociable functional group. The respective requirements for the method for synthesizing the cyclic compound B0 are the same as those described later with respect to the method (1) for producing the cyclic compound B0.

The cyclic compound B0 can also be obtained by the reaction of a cyclic compound a0 having a carboxyl group with a compound A3 having a halomethyl ether group. Since the carboxyl group of the cyclic compound a0 has high reactivity with the halogen of the compound A3 having a halomethyl ether group, the reaction can be carried out while suppressing side reactions (for example, the reaction of the phenolic hydroxyl group of the cyclic compound a0 with the halogen of the compound A3 having a halomethyl ether group), and the cyclic compound B0 having an acid-dissociable functional group selectively introduced into the carboxyl group can be obtained in high yield, and the productivity is high.

The cyclic compound A0 having a carboxyl group is a cyclic compound A0 having a molecular weight of 800-5000 and having 1 to 8 carboxyl groups in the molecule, which is synthesized by a condensation reaction of an aldehyde having 2 to 59 carbon atoms and having 1 to 2 carboxyl groups or ester groups and 1 to 4 formyl groups (hereinafter referred to as aldehyde compound A1d) and a compound having 6 to 15 carbon atoms and having 1 to 3 phenolic hydroxyl groups (hereinafter referred to as phenolic compound A2).

The aldehyde compound A1d is not particularly limited, and examples thereof include: aliphatic aldehyde compounds having 1 to 2 carboxyl groups or ester groups, alicyclic aldehyde compounds having 1 to 2 carboxyl groups or ester groups, aromatic aldehyde compounds having 1 to 2 carboxyl groups or ester groups, and the like.

Examples of the aliphatic aldehyde compound having 1 to 2 carboxyl groups include Ra-CHO (Ra is an alkyl group having 1 to 2 carboxyl groups or ester groups and optionally having a substituent having 1 to 20 carbon atoms), OHC-Rb-CHO (Rb is an alkylene group having 1 to 2 carboxyl groups or ester groups and optionally having a substituent having 1 to 20 carbon atoms), and Rc- (CHO)₃(Rc is a trivalent organic group having 1 to 2 carboxyl groups or ester groups which may have a substituent having 2 to 20 carbon atoms), Rd- (CHO)₄(Rd is a tetravalent organic group having 1 to 2 carboxyl groups which may have a substituent having 2 to 20 carbon atoms) and the like. The substituent is a functional group selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cyano, nitro, hydroxy, heterocyclic, halogen, carboxyl, alkylsilane, and derivatives thereof.

Examples of the alicyclic aldehyde compound include: carboxycyclohexylformaldehyde (カルボキシシクロヘキサンカルボアルデヒド), carboxycyclohexylformaldehyde which may have a substituent having 2 to 20 carbon atoms, carboxycyclooctylaldehyde, carboxynorbornanecarboxaldehyde, carboxyadamantylaldehyde, carboxyfurfural (カルボキシフルフラール), carboxydiformylcyclohexane, carboxydiformylcyclooctane (カルボキシジホルミルシクロオクタン), carboxydiformylcnorbornane, carboxydiformyladamantane, carboxytrimethylacylcyclohexane, carboxytrimethylacylcyclooctane, carboxytrimethylacylnorbornane, carboxytrimethyloyladamantane, carboxytrimethylacylcyclohexane, carboxytetramethylcyclooctane, carboxytetramethylnorbornane, carboxytetramethyladamantane and the like. The substituent is a functional group selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cyano, nitro, hydroxy, heterocyclic, halogen, alkylsilane, and derivatives thereof.

Examples of the aromatic aldehyde compound include: carboxybenzaldehyde, carboxytolualdehyde, carboxybenzaldehyde which may have a substituent having 2 to 20 carbon atoms, carboxyanisaldehyde, carboxynaphthaldehyde, carboxyanthracenal, carboxybiphenyl, carboxyformylanthracene, carboxyformylphenanthrene, carboxyformylphenothiazine (カルボキシホルミルフェノチアザン), carboxyformylpyrene, carboxyformylbenzopyrene, carboxyformylbenzindene, carboxyformylbenzonaphthalene, carboxyformylacenaphthylene, carboxyformylnaphthonaphthalene, carboxyformylpentacene, carboxyformyltriphenocene, carboxyformylpyridine, carboxyformylovalene, carboxydiformylbenzene, carboxydiformyltoluene, carboxydiformylxylene, carboxydiformylnaphthalene, carboxydiformylbiphenyl, carboxydiformylbritylbenzene, carboxydimethylbenzylxylene, carboxydimethylbenzylbiphenyl, carboxydimethylbenzylbistriphenylene, carboxybenzoylbiphenyl, carboxybenzoylphenoxide, carboxynaphthoylphenothiazine, carboxynaphthoquinone, Carboxydiformylanthracene, carboxydiformylphenanthrene, carboxydiformylpyrene, carboxydiformylbenzbiindan, carboxydiformylphenacene (カルボキシジホルミルフェナレン), carboxydiformylaacenaphthylene, carboxydiformylphenacene, carboxydiformylnaphthonaphthalene, carboxydiformylpentacene, carboxydiformylterphenylene, carboxydiformylpyridine, carboxydiformylimidazole, carboxydiformylfuran, carboxydiformylthiazole, carboxydiformylflavone, carboxydiformylisoflavone, carboxytrimethylbenzene, carboxytrimethyltoluol, carboxytrimethylxylene, carboxytrimethyloylnaphthalene, carboxytrimethyloylbiphenyl, carboxytrimethyloylterphenyl, carboxytrimethyloylanthracene, carboxytrimethyloylphenanthrene, carboxytrimethyloylpyrene, carboxytrimethyloylbenzodiindene, carboxytrimethyloylphenalene, carboxydimethyloylphenanthrylene, Carboxytrimethyloylacenaphthylene, carboxytrimethyloylphenalene, carboxytrimethyloylnaphthacene, carboxytrimethyloylpentalene, carboxytrimethyloyltriphenone, carboxytrimethyloylpyridone (カルボキシトリホルミルピリトリン), carboxytrimethyloylimidazole, carboxytrimethyloylfuran, carboxytrimethyloylthiazole, carboxytrimethyloylflavone, carboxytrimethyloylisoflavone, carboxytetramethylylbenzene, carboxytetramethylnaphthalene, carboxytetramethyloylbiphenyl, carboxytetramethyloylditritol, carboxytetramethyloylanthracene, carboxytetramethyloylphenanthrene, carboxytetramethyloylpyrene, carboxytetramethyloylbenzindene, carboxytetramethyloylphenalene, carboxytetramethylacenaphthylene, carboxytetramethyloylnonalene, carboxytetramethyloylnaphthacene, carboxytetramethyloylpentalene, carboxytetramethyloyltetrao-phenylene, carboxytetramethyloylpyridone (カルボキシテトラホルミルピリテトラン), Carboxytetracarboxylimidazole, carboxytetracarboxylfuran, carboxytetracarboxylthiazole, carboxytetracarboxylflavone, carboxytetracarboxylisoflavone, and the like. The substituent is a functional group selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cyano, nitro, hydroxy, heterocyclic, halogen, carboxyl, alkylsilane, and derivatives thereof.

Further, as the heterocycle-containing aldehyde compound, there may be mentioned: carboxyfurfural, carboxynicotinaldehyde, carboxy 2-tetrahydrofurfuraldehyde, 2-thiophenecarboxaldehyde and the like.

Examples of the aldehyde compound having 1 to 2 ester groups include: a compound having an ester bond such as the above formula (17) obtained by dehydration condensation of 1 to 2 carboxyl groups of the aldehyde compound having 1 to 2 carboxyl groups with an alcohol.

In the formula (17), the linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 12 carbon atoms, and specific examples thereof include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-dodecyl and the like.

The branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 10 carbon atoms, and specifically includes: isopropyl group, tert-butyl group, isopentyl group, neopentyl group, etc., and among them, tert-butyl group is preferable.

The aldehyde compound having 1 to 2 ester groups can be obtained by a reagent or synthesized by a known method. For example, it can be obtained by the following method: dissolving or suspending an aldehyde compound having 1-2 carboxyl groups in an organic solvent (e.g., acetone, etc.), and adding a base (e.g., potassium carbonate, etc.); then, an aldehyde compound having 1 to 2 carboxyl groups and 0.5 to 4 equivalents of a compound represented by the following formula (27) are added, reacted at 0 to 100 ℃ for 1 to 72 hours, the base (e.g., potassium carbonate) is removed by filtration or the like, and the solvent is removed. The compound may be purified (for example, by column chromatography) as required.

[ chemical formula 49]

(wherein X is a halogen atom; R)^3AAs described above. )

Examples of the halogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine, bromine and iodine, more preferably bromine and iodine, and further preferably bromine.

Among these, aromatic aldehydes having 1 to 2 carboxyl groups or ester groups and 1 to 4 formyl groups are preferable from the viewpoint of etching resistance; from the viewpoint of being advantageous for forming a fine pattern, an aromatic aldehyde having 1 to 2 carboxyl groups or ester groups and 1 to 2 formyl groups is more preferable; the aromatic aldehyde itself having 1 to 2 carboxyl groups or ester groups and 1 formyl group is more preferable because the aromatic aldehyde and the cyclic compound a can be produced in high yield and high purity.

The aromatic aldehyde compound having 1 to 2 carboxyl groups or ester groups is preferably a compound represented by the following general formula (28-0) or (28).

[ chemical formula 50]

(in the formula, X₂Is hydrogen or halogen, preferably hydrogen, fluorine, chlorine, bromine, iodine, more preferably hydrogen,Chlorine, bromine, and iodine, more preferably hydrogen, bromine, and iodine, and particularly preferably bromine; m is an integer of 1 to 4; l is₁、l₁And R^3AAs described above. )

[ chemical formula 51]

(in the formula, X₂、L₁、l₁、R^3AAs described above. )

Further, compounds represented by the following formulae (28-1) to (28-4) are preferably used.

[ chemical formula 52]

(in the formula, m, X₂、R^3AAs described above. )

[ chemical formula 53]

(wherein m and R are^3AAs described above. )

[ chemical formula 54]

(in the formula, R^3AAs described above. )

[ chemical formula 55]

(in the formula, R^3AAs described above. )

The aldehyde compound A1d may be used alone or in combination of two or more, and when used alone, the uniformity of the solid content of the resist film is high, which is preferable.

Examples of the phenolic compound a2 include: phenol, catechol, resorcinol, hydroquinone, pyrogallol, and the like, preferably resorcinol, pyrogallol, and more preferably resorcinol. The phenolic compound a2 may have a substituent selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an alkanoyloxy group (アルキロイルオキシ group), an aroyloxy group, a cyano group, a nitro group, a heterocyclic group, an alkylsilane, a substituted methyl group, a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, a 1-substituted alkoxyalkyl group, a cyclic ether group, and an alkoxycarbonylalkyl group, as long as the effects of the present invention are not impaired. The purity of the phenolic compound a2 is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more. The phenol compound a2 may be used singly or in combination, and when used singly, it is preferable because the uniformity of the solid content of the resist film is high.

The cyclic compound a0 having a carboxyl group can be obtained, for example, by the following method: in an organic solvent (such as methanol, ethanol, acetonitrile, etc.), in the presence of an acid catalyst (hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc.), using a molar ratio of 1: (0.1-10) the aldehyde compound A1d and the phenol compound A2 are reacted at 60-150 ℃ for 0.5-20 hours, filtered, washed with an alcohol such as methanol, washed with water, filtered, separated, and finally dried. If necessary, purification may be carried out by column chromatography or the like.

As the reaction solvent, alcohols such as methanol and ethanol may be used; or a case where an aliphatic aldehyde compound having an ester group is used as the aldehyde compound A1 d; in the case where a part or all of the carboxyl groups of the cyclic compound Aa having carboxyl groups after the completion of the reaction are esterified. At this time, sodium hydroxide or the like as a base is added for hydrolysis of the ester, and the mixture is stirred at 10 to 100 ℃ for about 0.5 to 20 hours. Then, the solution was transferred to a separatory funnel, and diethyl ether or the like as an organic solvent was added to separate the solution, and the aqueous layer thereof was removed, and the precipitated solid matter was neutralized with an acid such as hydrochloric acid, and recovered by filtration or the like, thereby obtaining cyclic compound a0 having an unesterified carboxyl group.

The molecular weight of the cyclic compound A0 is 700-. In the above range, the resist can maintain the necessary film-forming property, and the resolution can be improved.

The cyclic compound of the present invention can be a cis-isomer or a trans-isomer, and may have any structure or a mixture thereof. When used as a resist component of a radiation-sensitive composition, a composition having only one of the cis-isomer and the trans-isomer is preferable because it is a pure compound and the uniformity of the components in the resist film is high. A method for obtaining a cyclic compound having only one structure of cis-form and trans-form can use: separation by column chromatography or preparative liquid chromatography, or preparation, can be carried out by a known method such as optimization of the reaction solvent, reaction temperature, and the like.

The cyclic compound a0 having a carboxyl group is preferably selected from the compounds represented by the following formula (29-0) or formula (29).

[ chemical formula 56]

[ chemical formula 57]

(in each of the formulae (29-0) and (29), X₂Is a hydrogen or halogen atom; l is₁A divalent organic group selected from a single bond and a linear or branched alkylene group having 1 to 4 carbon atoms; l ₁Is 0 or 1; m is an integer of 1 to 4; m is₃Is an integer of 1 to 2; m is₄Is 1. )

The above-mentioned cyclic compound a0 having a carboxyl group is more preferably a compound selected from the group consisting of a compound represented by the following formula (30) and compounds represented by the following formula (31).

[ chemical formula 58]

[ chemical formula 59]

(in the formulae (30) and (31), X₂As described above. )

The compound a3 having a halomethyl ether group is not particularly limited, and examples thereof include an aliphatic compound having 1 to 2 halomethyl groups, an alicyclic compound having 1 to 2 halomethyl groups, and an aromatic compound having 1 to 2 halomethyl groups, and preferred examples thereof include compounds represented by the following formula (32).

[ chemical formula 60]

(in the formula, R₈Is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; x₁Is halogen; l₂Is 1 or 2. )

The linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 12 carbon atoms, and specific examples thereof include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-dodecyl and the like.

The branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 10 carbon atoms, and specifically includes: isopropyl, tert-butyl, isoamyl, neopentyl and the like.

Examples of the halogen include fluorine, chlorine, bromine, and iodine, preferably chlorine, bromine, and iodine, more preferably bromine and iodine, and further preferably bromine.

l₂Is 1 or 2, more preferably 1.

The compound a3 having a halomethyl ether group can be obtained, for example, by the following method: dissolving alcohol (such as cyclohexanol) in organic solvent such as n-hexane, adding paraformaldehyde, blowing 2.0-3.0 equivalent of hydrogen halide (such as hydrogen chloride gas) relative to alcohol, and reacting at 0-100 deg.C; after the completion of the reaction, the product was separated by distillation under reduced pressure to obtain a target compound a3 having a halomethyl ether group.

The compound A3 having a halomethyl ether group is preferably a compound represented by the following formula (32-1).

[ chemical formula 61]

(in the formula, X, R⁵、R⁶、n₀、n₁、n₂The same as in the above-mentioned formulae (22) and (27). )

The cyclic compound B0 can be obtained by the reaction of a cyclic compound a0 having a carboxyl group with a compound A3 having a halomethyl ether group. For example, it can be obtained by the following method: the cyclic compound a0 having a carboxyl group is dissolved or suspended in an aprotic solvent (e.g., acetone, THF, propylene glycol monomethyl ether acetate, etc.), then, the compound A3 having a halomethyl ether group is added, and the reaction is carried out in the presence of a base catalyst (0.5 to 4 equivalents, preferably 0.9 to 1.1 equivalents, more preferably 1.0 equivalent of pyridine, triethylamine, diazabicycloundecene, potassium carbonate, etc.) at 0 to 110 ℃ for 1 to 72 hours under normal pressure, followed by washing with an alcohol such as methanol, washing with water, separation by filtration, and drying. The compound can be purified by column chromatography or the like as necessary.

The molecular weight of the cyclic compound B0 is 800-. When within the above range, the resist can maintain the necessary film-forming property and the resolution can be improved.

The cyclic compound B0 is preferably a compound selected from compounds represented by the following formula (33-0) or (33).

[ chemical formula 62]

(in the formula, R^3A、X₂、L₁、l₁、m、m₃、m₄The same as in the above formula (13-0). )

[ chemical formula 63]

(in the formula, R^3A、X₂、L₁、l₁The same as in the above formula (13). )

The cyclic compound B0 is more preferably a compound represented by the following formula (34).

[ chemical formula 64]

(in the formula, R^3A、X₂、L₁、l₁As described above. )

The cyclic compound B0 is particularly preferably a compound represented by the following formula (35).

[ chemical formula 65]

(in the formula, R^3A、X₂As described above. )

R^3AMore preferably an acid-dissociable functional group having a structure selected from the group consisting of cycloalkanes having 3 to 20 carbon atoms, lactones, and aromatic rings having 6 to 12 carbon atoms. The cycloalkane having 3 to 20 carbon atoms may be a monocyclic ring or a polycyclic ring, and a polycyclic ring is more preferable. Specific examples thereof include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane, and more specifically, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane and cyclohexane, and polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclodecane. Among them, adamantane, tricycloalkane and tetracycloalkane are preferable, and adamantane and tricycloalkane are particularly preferable. The cycloalkane having 3 to 12 carbon atoms may have a substituent. Examples of the lactone include butyrolactone and a cycloalkyl group having 3 to 12 carbon atoms and having a lactone group. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and the like, and a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is particularly preferable.

Particularly, an acid-dissociable functional group represented by the following formula (36) is more preferable. By having such an acid-dissociable functional group, the resolution and LER of the resulting resist pattern can be improved.

[ chemical formula 66]

(in the formula, R⁵、R⁶、n₀、n₁、n₂As described above. )

The cyclic compound B0 can also be obtained by a dehydration condensation reaction of the cyclic compound a0 having a carboxyl group and a compound having an alcoholic hydroxyl group.

The cyclic compound B0 can also be obtained by transesterification of a cyclic compound A0a and a compound having an alcoholic hydroxyl group, the cyclic compound A0a being obtained by replacing a carboxyl group of the cyclic compound A0 having a carboxyl group with an ester bond represented by the above formula (17). Transesterification reactions are well known. As the compound having an alcoholic hydroxyl group, any of primary alcohols, secondary alcohols, and tertiary alcohols can be used, secondary alcohols and tertiary alcohols are more preferable, and tertiary alcohols are particularly preferable.

The compound A3 having a halomethyl ether group can be obtained by, for example, dissolving an alcohol (e.g., cyclohexanol) in an organic solvent such as n-hexane, adding paraformaldehyde, blowing 2.0 to 3.0 equivalents of a hydrogen halide (e.g., hydrogen chloride gas) with respect to the alcohol, and reacting at 0 to 100 ℃; after the completion of the reaction, the product was separated by distillation under reduced pressure to obtain a target compound a3 having a halomethyl ether group.

The cyclic compound B0 can be obtained by the reaction of a cyclic compound a0 having a carboxyl group and a compound A3 having a halomethyl ether group. For example, it can be obtained by the following method: the cyclic compound a0 having a carboxyl group is dissolved or suspended in an aprotic solvent (e.g., acetone, THF, propylene glycol monomethyl ether acetate, etc.), then, the compound A3 having a halomethyl ether group is added, and the reaction is carried out in the presence of a base catalyst (0.5 to 4 equivalents, preferably 0.9 to 1.1 equivalents, more preferably 1.0 equivalent of pyridine, triethylamine, diazabicycloundecene, potassium carbonate, etc.) at 0 to 110 ℃ for 1 to 72 hours under normal pressure, followed by washing with an alcohol such as methanol, washing with water, separation by filtration, and drying. The compound can be purified by column chromatography or the like as necessary.

In order to reduce the amount of residual metal in the cyclic compound B0, purification may be performed as necessary. In addition, if the acid catalyst and the co-catalyst remain, in general, the storage stability of the radiation-sensitive composition is lowered; or when the basic catalyst remains, the sensitivity of the radiation-sensitive composition is generally lowered, and therefore purification for the purpose of lowering the content thereof may be performed. The purification can be carried out by a known method, and the cyclic compound B0 is not particularly limited as long as it is not modified, and examples thereof include: a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with an alkaline aqueous solution, a method of treatment with an ion exchange resin, a method of treatment with a silica gel column chromatograph, and the like. More preferably, two or more of these purification methods are combined.

An optimum method can be appropriately selected from an acidic aqueous solution, a basic aqueous solution, an ion exchange resin and a silica gel column chromatograph according to the amount and type of the metal to be removed, the acidic compound and/or the basic compound, the type of the purified cyclic compound B0, and the like. For example, the acidic aqueous solution may be an aqueous solution of hydrochloric acid, nitric acid or acetic acid having a concentration of 0.01 to 10mol/L, the basic aqueous solution may be an aqueous solution of ammonia having a concentration of 0.01 to 10mol/L, and the ion exchange resin may be a cation exchange resin such as Amberlyst 15J-HG Dry manufactured by オルガノ. Drying may also be carried out after purification. The drying may be carried out by a known method, and is not particularly limited, and examples thereof include vacuum drying and hot air drying under the condition that the cyclic compound B0 is not modified.

The ratio of the number of halogen atoms to the total number of constituent atoms of the cyclic compound B0 is preferably 0.1 to 60%, more preferably 0.1 to 40%, still more preferably 0.1 to 20%, particularly preferably 0.1 to 10%, most preferably 0.1 to 5%. When the amount is within the above range, the sensitivity to radiation increases and the film forming property can be maintained. In addition, the solubility of the safe solvent can be improved.

The ratio of the number of nitrogen atoms to the total number of constituent atoms of the cyclic compound B0 is preferably 0.1 to 40%, more preferably 0.1 to 20%, still more preferably 0.1 to 10%, and particularly preferably 0.1 to 5%. When within the above range, the line edge roughness of the resulting resist pattern can be reduced, and the film formability can be maintained. The nitrogen atom is preferably a nitrogen atom contained in a secondary amine or a tertiary amine, and more preferably a nitrogen atom contained in a tertiary amine.

The solid component of the radiation-sensitive composition of the present invention and cyclic compound B0 can be formed into an amorphous film by spin coating. In addition, the method can be applied to a general semiconductor manufacturing process.

The amorphous film of the cyclic compound B0 preferably has a dissolution rate at 23 ℃ in a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution

Hereinafter, more preferred is

Further preferred is

Is composed of

At a dissolution rate higher than the above, the resolution may be improved. This is presumably because the fine surface portion of the cyclic compound B0 is dissolved, and LER is reduced. In addition, there is an effect of reducing defects.

The cyclic compound formed by dissociation of the acid-dissociable functional group of the cyclic compound B0 also preferably has a property of forming an amorphous film by spin coating. The amorphous film of cyclic compound A3 preferably has a dissolution rate at 23 ℃ in a 2.38 mass% TMAH aqueous solution

Above, more preferably

Further preferred is

Is composed of

When the above-mentioned compound is used, it can be dissolved in alkaliThe developing solution becomes a resist. In addition, have

The resolution may be improved at the following dissolution rate. This is presumably because the difference between the interface between the exposed portion dissolved in the alkaline developer and the interface between the unexposed portion not dissolved in the alkaline developer is increased by the change in solubility caused by the dissociation of the acid-dissociable functional group of the cyclic compound B0. In addition, the method has the effects of reducing LER and reducing defects.

The amorphous film formed by spin coating the solid component of the radiation-sensitive composition preferably has a dissolution rate at 23 ℃ in a 2.38 mass% aqueous solution of TMAH

The following. The amorphous film after exposure to a desired pattern by irradiation with radiation such as KrF excimer laser, ultraviolets, electron beam, or X-ray, and heating at 20 to 250 ℃ as necessary, preferably has a dissolution rate at 23 ℃ relative to a 2.38 mass% aqueous TMAH solution

The glass transition temperature of the cyclic compound B0 is preferably 100 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 140 ℃ or higher, and particularly preferably 150 ℃ or higher. When the glass transition temperature is in the above range, the heat resistance that can maintain the pattern shape in the semiconductor photolithography process can be obtained, and the performance such as high resolution can be provided.

The calorific value of crystallization determined by differential scanning calorimetry analysis of the glass transition temperature of the cyclic compound B0 is preferably less than 20J/g. The (crystallization temperature) - (glass transition temperature) is preferably 70 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, and particularly preferably 130 ℃ or higher. When the amount of heat generated by crystallization is less than 20J/g and (crystallization temperature) - (glass transition temperature) is within the above range, an amorphous film is easily formed by spin coating the radiation-sensitive composition, and the film-forming properties necessary for a resist can be maintained for a long period of time, whereby the resolution can be improved.

The cyclic compound B0 of the present invention may be added to a radiation-sensitive composition as an additive for improving sensitivity or etching resistance, for example, without being a main component, except that it can form a positive-type radiation-sensitive composition with itself as a main component. In this case, the cyclic compound B0 may be used in an amount of 1 to 50% by weight based on the total weight of the solid components.

In the radiation-sensitive resist composition of the present invention, it preferably contains 1 to 80% by weight of the solid component and 20 to 99% by weight of the solvent, more preferably 1 to 50% by weight of the solid component and 50 to 99% by weight of the solvent, still more preferably 2 to 40% by weight of the solid component and 60 to 98% by weight of the solvent, and particularly preferably 2 to 10% by weight of the solid component and 90 to 98% by weight of the solvent. The amount of the cyclic compound B0 is preferably 50% by weight or more, more preferably 60 to 95% by weight, still more preferably 65 to 90% by weight, and particularly preferably 70 to 85% by weight based on the total weight of the solid content. When the blending ratio is set as described above, high resolution can be obtained and line edge roughness can be reduced. As the solvent, the same solvents as in the above-described radiation-sensitive composition a can be similarly used.

A non-acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group of the cyclic compound B0 within a range not to impair the effects of the present invention. The non-acid-dissociable functional group is a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. Examples thereof include: and a functional group selected from the group consisting of C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxy group, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen, carboxyl group, C1-20 alkylsilane, and derivatives thereof, which is not decomposed by the action of an acid.

A naphthoquinonediazide ester group may be introduced into at least one phenolic hydroxyl group of the cyclic compound B0 of the present invention. The compound having the naphthoquinonediazide ester group introduced into at least one phenolic hydroxyl group of the cyclic compound B0 can be added to a radiation-sensitive composition as an acid generator or an additive, in addition to being capable of forming a positive-type radiation-sensitive composition mainly containing itself.

An acid-generating functional group that generates an acid upon irradiation with radiation may be introduced to at least one phenolic hydroxyl group of the cyclic compound B0. The cyclic polyphenol compound having an acid-generating functional group that generates an acid by irradiation with radiation introduced into at least one phenolic hydroxyl group of the cyclic compound B0 can be added to a radiation-sensitive composition as an acid generator or an additive, in addition to being capable of forming a positive-type radiation-sensitive composition mainly containing itself.

The composition of the present invention preferably contains one or more acid generators C that directly or indirectly generate an acid by irradiation with radiation selected from any one of visible light, ultraviolet light, excimer laser, electron beam, Extreme Ultraviolet (EUV), X-ray, and ion beam. The amount of the acid generator C used is preferably 0.001 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 3 to 30% by weight, based on the total weight of the solid components (the total of the solid components such as the cyclic polyphenol compound B0, the acid generator C, the low molecular weight dissolution promoter D, the acid diffusion controller E, and other optional components F, the same applies hereinafter). By using the acid generator in the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In the present invention, the method for producing an acid is not limited as long as the acid can be produced in the system. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing can be performed; further, if electron beams, ultra-violet rays, X-rays, or ion beams are used as the high-energy beams, further fine processing can be performed.

The amount of the acid generator C is preferably 15 to 25% by weight based on the total weight of the solid content. By using the acid generator C in the above range, high sensitivity can be obtained.

The radiation-sensitive composition of the present invention may contain a resin soluble in an alkaline aqueous solution within a range not impairing the object of the present invention. Examples of the resin soluble in an aqueous alkaline solution include: phenolic resins, polyvinyl phenol resins, polyacrylic acids, polyvinyl alcohols, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, or derivatives thereof, and the like. The blending amount of the resin soluble in the aqueous alkaline solution can be adjusted as appropriate depending on the kind of the resist compound used, and is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, and particularly preferably 0 part by weight, per 100 parts by weight of the cyclic compound B0.

(radiation-sensitive composition C)

The present invention relates to a radiation-sensitive composition containing a solvent and any one of the cyclic compounds of the formulae (1) and (a) to (e).

The present invention also relates to the radiation-sensitive composition, wherein the cyclic compound is a cyclic compound A having a molecular weight of 700-5000, which is synthesized by a condensation reaction of a compound having 2 to 59 carbon atoms and 1 to 4 formyl groups (aldehyde compound A1) and a compound having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups (phenolic compound A2).

That is, the radiation-sensitive composition preferred in the present invention has the following features: the radiation-sensitive composition contains 1-80 wt% of a solid component and 20-99 wt% of a solvent, wherein the radiation-sensitive composition contains a cyclic compound A synthesized by a condensation reaction of benzaldehyde having 7-24 carbon atoms and no hydroxyl group or tert-butyl group and a compound having 6-15 carbon atoms and 1-3 phenolic hydroxyl groups, and the molecular weight of the cyclic compound A is 700-5000-.

Further, a radiation-sensitive composition preferred in the present invention has the following features: the radiation-sensitive composition comprises 1-80 wt% of a solid component and 20-99 wt% of a solvent, wherein the radiation-sensitive composition comprises a cyclic compound A, an acid generator C, an acid crosslinking agent G and an acid diffusion control agent E, wherein the cyclic compound A is synthesized by a condensation reaction of benzaldehyde having 10-24 carbon atoms and substituents containing alicyclic or aromatic rings and a compound having 6-15 carbon atoms and 1-3 phenolic hydroxyl groups, and has a molecular weight of 700-5000; the acid generator C directly or indirectly generates an acid by irradiation with radiation selected from any one of the group consisting of visible rays, ultraviolet rays, excimer laser, electron rays, extreme ultraviolet rays (EUV), X-rays, and ion beams.

The radiation-sensitive composition of the present invention contains a cyclic polyphenol compound. The content of the cyclic compound A is 50% by weight or more based on the total weight of the solid content.

The cyclic compound A is a cyclic compound having a molecular weight of 700-5000, which is synthesized by a condensation reaction of benzaldehyde having 10-24 carbon atoms and having a substituent containing an alicyclic ring or an aromatic ring or benzaldehyde having 7-24 carbon atoms and not having any one of a hydroxyl group and a tert-butyl group (hereinafter, referred to as an aromatic carbonyl compound A1) and a compound having 6-15 carbon atoms and having 1-3 phenolic hydroxyl groups (hereinafter, referred to as a phenolic compound A2).

The cyclic compound A has the advantages of good film forming property, heat resistance, alkali developability, etching resistance and the like.

The cyclic compound a can be obtained by a condensation reaction of one or more compounds selected from the group consisting of aromatic carbonyl compounds a1 and one or more compounds selected from the group consisting of phenolic compounds a 2.

The aromatic carbonyl compound a1 is benzaldehyde having 10 to 24 carbon atoms having a substituent containing an alicyclic ring or an aromatic ring, or benzaldehyde having 7 to 24 carbon atoms not having any of a hydroxyl group and a tert-butyl group, and examples thereof include: benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde other than t-butyl, ethylmethylbenzaldehyde, isopropylmethylbenzaldehyde, diethylbenzaldehyde, p-methoxybenzaldehyde, cyclopropylbenzaldehyde, cyclobutylbenzaldehyde, cyclopentylbenzaldehyde, cyclohexylbenzaldehyde, benzaldehyde, naphthaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde, hydroxypropionbenzaldehyde, isopropylbenzaldehyde, n-propylbenzaldehyde, bromobenzaldehyde, and dimethylaminobenzaldehyde, and the like, preferably isopropylbenzaldehyde, n-propylbenzaldehyde, bromobenzaldehyde, and dimethylaminobenzaldehyde, cyclohexylbenzaldehyde, benzaldehyde, and more preferably 4-isopropylbenzaldehyde, cyclohexylbenzaldehyde, and 4-n-propylbenzaldehyde.

The aromatic carbonyl compound a1 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 carbonyl compound a1 may be used alone or in combination of two or more.

In the cyclic compound a in the present invention, a crosslinking reactive group that causes a crosslinking reaction by irradiation of visible rays, ultraviolet rays, excimer laser, electron rays, extreme ultraviolet rays (EUV), X-rays, and ion beams or a chemical reaction caused thereby may also be introduced. The introduction is carried out, for example, by reacting the cyclic compound a and the crosslinking reactive group-introducing agent under a base catalyst. Examples of the crosslinking reactive group include a carbon-carbon unsaturated bond, an epoxy group, an azido group, a halophenyl group and a chloromethyl group. Examples of the crosslinking reactive group-introducing reagent include carboxylic acid derivatives (e.g., acids, acid chlorides, acid anhydrides, and dicarbonates) having such crosslinking reactive groups, and alkyl halides. The resist composition containing the cyclic compound a having a crosslinking reactive group can also be used as a non-polymer radiation-sensitive composition having high resolution, high heat resistance and solvent solubility.

The cyclic compound a of the present invention may be added to a radiation-sensitive composition as an additive for improving sensitivity or etching resistance, for example, instead of being used as a main component, except that it can form a positive-type radiation-sensitive composition using itself as a main component. In this case, the cyclic compound A may be used in an amount of 1 to 49.999 wt% based on the total weight of the solid components.

The cyclic compound a can be used as a material for a positive resist, which is a compound hardly soluble in an alkaline developer, by irradiation with KrF excimer laser, ultra-ultraviolet rays, electron beams, or X-rays. This is considered to be because the cyclic compound a is hardly soluble in an alkaline developer by causing a condensation reaction between the compounds by irradiation with KrF excimer laser, ultra-violet ray, electron beam, or X-ray. The LER of the resist pattern thus obtained is very small.

The cyclic compound a may have a non-acid-dissociable functional group introduced into at least one phenolic hydroxyl group thereof, within a range not impairing the effects of the present invention. The non-acid-dissociable functional group is a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. Examples thereof include: and a functional group selected from the group consisting of C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxy group, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen, carboxyl group, C1-20 alkylsilane, and derivatives thereof, which is not decomposed by the action of an acid.

The naphthoquinonediazide ester group may be introduced into at least one phenolic hydroxyl group of the cyclic compound a of the present invention. The compound having the naphthoquinonediazide ester group introduced into at least one phenolic hydroxyl group of the cyclic compound a may be added to the radiation-sensitive composition as a positive-type radiation-sensitive composition, an acid generator, or an additive, which is mainly composed of itself, in addition to the negative-type positive-type radiation-sensitive composition formed mainly of itself.

An acid-generating functional group that generates an acid upon irradiation with radiation may be introduced to at least one phenolic hydroxyl group of the cyclic compound a. The cyclic polyphenol compound having an acid-generating functional group that generates an acid by irradiation with radiation introduced into at least one phenolic hydroxyl group of the cyclic compound a can form a negative-type positive-type radiation-sensitive composition with itself as a main component, and can be added to a radiation-sensitive composition as a positive-type radiation-sensitive composition with itself as a main component, an acid generator, or an additive.

The cyclic compound a can be produced by a known method. For example, it can be obtained by the following method: in an organic solvent (such as methanol, ethanol, etc.), in the presence of an acid catalyst (hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc.), using a molar ratio of 1: (0.1-10) reacting the aromatic carbonyl compound A1 with the phenolic compound A2 at 60-150 ℃ for about 0.5-20 hours, filtering, washing with an alcohol such as methanol, washing with water, filtering, separating, and drying. It can also be obtained by using a basic catalyst (sodium hydroxide, barium hydroxide, 1, 8-diazabicyclo [5.4.0] undec-7-ene, etc.) in place of the acid catalyst, and by carrying out the reaction in the same manner. Further, the cyclic polyphenol compound a can also be produced by converting the aromatic carbonyl compound a1 into a dihalide with a hydrogen halide or a halogen gas, and reacting the isolated dihalide with the phenolic compound a 2.

The cyclic compound is more preferably produced using two or more aromatic carbonyl compounds a1 and/or two or more phenolic compounds a 2. By using two or more aromatic carbonyl compounds a1 and/or two or more phenolic compounds a2, the solubility of the resulting cyclic compound a in a semiconductor-safe solvent can be improved.

In order to reduce the amount of residual metal in the cyclic compound a, purification may be performed as necessary. In addition, if the acid catalyst and the co-catalyst remain, in general, the storage stability of the radiation-sensitive composition is lowered; or when the basic catalyst remains, the sensitivity of the radiation-sensitive composition is generally lowered, and therefore purification for the purpose of lowering the content thereof is possible. The purification can be carried out by a known method, and the cyclic compound a is not particularly limited as long as it is not modified, and examples thereof include: a method of washing with water, a method of washing with an acidic aqueous solution, a method of washing with an alkaline aqueous solution, a method of treatment with an ion exchange resin, a method of treatment with a silica gel column chromatograph, and the like. More preferably, two or more of these purification methods are combined. An optimum method can be appropriately selected from an acidic aqueous solution, a basic aqueous solution, an ion exchange resin and a silica gel column chromatograph according to the amount and type of the metal to be removed, the acidic compound and/or the basic compound, the type of the purified cyclic compound a, and the like. Examples of the acidic aqueous solution include aqueous solutions of hydrochloric acid, nitric acid and acetic acid having a concentration of 0.01 to 10 mol/L; examples of the alkaline aqueous solution include an aqueous ammonia solution having a concentration of 0.01 to 10 mol/L; examples of the ion exchange resin include cation exchange resins such as Amberlyst 15J-HG Dry manufactured by オルガノ. Drying may also be carried out after purification. The drying may be carried out by a known method, and is not particularly limited, and examples thereof include vacuum drying and hot air drying under the condition that the cyclic compound a is not modified.

The cyclic compound a has low sublimability at 100 ℃ or lower, preferably 120 ℃ or lower, more preferably 130 ℃ or lower, still more preferably 140 ℃ or lower, and particularly preferably 150 ℃ or lower, preferably under normal pressure. The low sublimation property is preferably 10% or less, preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and particularly preferably 0.1% or less of the weight loss when the sample is held at a predetermined temperature for 10 minutes in thermogravimetric analysis. By reducing the sublimation property, contamination of the exposure apparatus due to outgassing during exposure can be prevented. In addition, good pattern shapes can be imparted with low LER.

The cyclic compound A satisfies: preferably, F < 3.0(F represents the total number of atoms/(total number of carbon atoms-total number of oxygen atoms)), and more preferably, F < 2.5. By satisfying the above conditions, the dry etching resistance is improved.

The cyclic compound a is selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate, and is dissolved in a solvent exhibiting the maximum dissolving capacity with respect to the cyclic polyphenol compound a at 23 ℃, preferably at least 1 wt%, more preferably at least 3 wt%, further preferably at least 5 wt%, particularly preferably at least 10 wt%. By satisfying the above conditions, the use of a safe solvent in the semiconductor production process becomes possible.

The glass transition temperature of the cyclic compound a is preferably 100 ℃ or higher, more preferably 120 ℃ or higher, still more preferably 140 ℃ or higher, and particularly preferably 150 ℃ or higher. When the glass transition temperature is in the above range, the heat resistance that can maintain the pattern shape in the semiconductor photolithography process can be obtained, and the performance such as high resolution can be provided.

The calorific value of crystals determined by differential scanning calorimetry analysis of the glass transition temperature of the cyclic compound A is preferably less than 20J/g. The (crystallization temperature) - (glass transition temperature) is preferably 70 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, and particularly preferably 130 ℃ or higher. When the amount of heat generated by crystallization is less than 20J/g and (crystallization temperature) - (glass transition temperature) is within the above range, an amorphous film is easily formed by spin coating the radiation-sensitive composition, and the film-forming properties necessary for a resist can be maintained for a long period of time, whereby the resolution can be improved.

In the present invention, the calorific value of crystallization, the crystallization temperature and the glass transition temperature can be determined by the following measurement and differential scanning calorimetry analysis using DSC/TA-50WS manufactured by Shimadzu corporation. About 10mg of the sample was placed in an aluminum non-sealed container, and the temperature was raised to a temperature higher than the melting point in a nitrogen gas flow (50ml/min) at a temperature raising rate of 20 ℃/min. After quenching, the temperature was again raised to a temperature higher than the melting point in a nitrogen gas flow (30ml/min) at a temperature raising rate of 20 ℃/min. After quenching, the temperature was again raised to 400 ℃ in a nitrogen gas flow (30ml/min) at a temperature raising rate of 20 ℃/min. The temperature at the midpoint of the region where the discontinuity appears on the base line (when the specific heat becomes half) was taken as the glass transition temperature (Tg), and the temperature at the heat generation peak which subsequently appears was taken as the crystallization temperature. The calorific value was obtained from the area of the region surrounded by the exothermic peak and the base line, and was calculated as the crystal calorific value.

The molecular weight of the cyclic compound A is 700-5000, preferably 800-2000, and more preferably 900-1500. When within the above range, the resist can maintain the necessary film-forming property and the resolution can be improved.

In one embodiment of the present invention, the cyclic compound A is preferably a compound represented by the following formula (37), (37-1) or (37-2).

[ chemical formula 67]

(in the formula, R⁴A functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (except for a t-butyl group), a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof; l is the same as above; p is an integer of 0 to 5. )

[ chemical formula 68]

[ chemical formula 69]

(in the above formulae (37-1) and (37-2), X₂Is a hydrogen or halogen atom; m is an integer of 1 to 4; m is₃Is an integer of 1 to 2; m is₄Is 1; r⁴And p is the same as above. )

The cyclic compound a is more preferably a compound represented by the following formula (38).

[ chemical formula 70]

(in the formula, R⁴And p is the same as above. )

The cyclic compound a is more preferably a compound represented by the following formula (39).

[ chemical formula 71]

The cyclic compound a is more preferably a compound represented by the following formula (40), and still more preferably a compound represented by the following formula (41).

[ chemical formula 72]

(in the formula, R⁷Independently a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a halogen atom, a cyano group, a hydroxyl group, an alkoxy group or an ester group. )

[ chemical formula 73]

The hydrogen atom of the hydroxyl group in the above formula may be substituted with an organic group containing a repeating unit represented by the following formula (42-1), a hydrogen atom or a terminal group represented by the following formula (42-2) as long as the effect of the present invention is not impaired.

[ chemical formula 74]

[ chemical formula 75]

In the formulae (42-1) and/or (42-2), L is a single bond, methylene, ethylene or carbonyl. The plurality of L's may be the same or different. n is₅Is an integer of 0 to 4, n₆Is an integer of 1 to 3, x is an integer of 0 to 3, and satisfies 1 ≦ n ₅+n₆And ≦ 5. A plurality of n₅、n₆X may be the same or different. R³Is a substituent selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkanoyloxy group, an aroyloxy group, a cyano group, and a nitro group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like; examples of the cycloalkyl group include cyclohexyl, norbornyl, adamantyl, and the like; examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like; examples of the aralkyl group include a benzyl group, a hydroxybenzyl group, a dihydroxybenzyl group, and the like; examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like; examples of the aryloxy group include a phenoxy group and the like; examples of the alkenyl group include alkenyl groups having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, and the like; examples of the acyl group include aliphatic acyl groups having 1 to 6 carbon atoms (e.g., formyl group, acetyl group, and propyl group) Acyl, butyryl, valeryl, isovaleryl, pivaloyl, etc.) and aromatic acyl (e.g., benzoyl, toluoyl, etc.); examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 5 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, and the like; examples of the alkanoyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group and the like; examples of the arylacyloxy group include benzoyloxy group and the like. Plural R³May be the same or different.

The ratio of the number of halogen atoms to the total number of constituent atoms of the cyclic compound a is preferably 0.1 to 60%, more preferably 0.1 to 40%, still more preferably 0.1 to 20%, particularly preferably 0.1 to 10%, most preferably 1 to 5%. When the amount is within the above range, the sensitivity to radiation increases and the film forming property can be maintained. In addition, the solubility of the safe solvent can be improved.

The ratio of the number of nitrogen atoms to the total number of constituent atoms of the cyclic compound a is preferably 0.1 to 40%, more preferably 0.1 to 20%, still more preferably 0.1 to 10%, and particularly preferably 0.1 to 5%. When within the above range, the line edge roughness of the resulting resist pattern can be reduced. The nitrogen atom is preferably a nitrogen atom contained in a secondary amine or a tertiary amine, and more preferably a nitrogen atom contained in a tertiary amine.

Above, more preferably

Further preferred is

Is composed of

The resolution may be improved at the following dissolution rate. This is presumably because the difference in the interface between the unexposed portion dissolved in the alkaline developer and the exposed portion not dissolved in the alkaline developer is increased by the change in the solubility of the cyclic compound a before and after exposure. In addition, the method has the effects of reducing LER and reducing defects.

The solid component of the radiation-sensitive composition of the present invention can be formed into an amorphous film by spin coating. The amorphous film formed by spin coating the solid component of the radiation-sensitive composition of the present invention preferably has a dissolution rate at 23 ℃ in a 2.38 mass% aqueous solution of TMAH

Above, more preferably

Further preferred is

Is composed of

The resolution may be improved at the following dissolution rate. This is presumably because the difference in the interface between the unexposed portion dissolved in the alkaline developer and the exposed portion not dissolved in the alkaline developer is increased by the change in the solubility of the cyclic compound a before and after exposure.In addition, the method has the effects of reducing LER and reducing defects.

The amorphous film formed by spin-coating the solid component of the radiation-sensitive composition of the present invention is preferably dissolved in a 2.38 mass% aqueous solution of TMAH at 23 ℃ at a portion exposed to radiation such as KrF excimer laser, extreme ultraviolet ray, electron beam, or X-ray

Hereinafter, more preferred is

Further preferred is

Is composed of

At a dissolution rate higher than the above, the resolution may be improved. This is presumably because the minute surface portion of the cyclic compound a is dissolved, and LER is lowered. In addition, there is an effect of reducing defects.

The radiation-sensitive composition of the present invention preferably contains 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, more preferably 1 to 50% by weight of a solid component and 50 to 99% by weight of a solvent, still more preferably 2 to 40% by weight of a solid component and 60 to 98% by weight of a solvent, and particularly preferably 2 to 10% by weight of a solid component and 90 to 98% by weight of a solvent. The amount of the cyclic polyphenol compound a is 50 wt% or more, preferably 65 wt% or more, and more preferably 81 wt% or more based on the total weight of the solid content. When the blending ratio is set as described above, high resolution can be obtained and line edge roughness can be reduced.

The composition of the present invention preferably contains one or more acid generators C that directly or indirectly generate an acid by irradiation with radiation selected from any one of visible light, ultraviolet light, excimer laser, electron beam, Extreme Ultraviolet (EUV), X-ray, and ion beam. The amount of the acid generator used is preferably 0.001 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 3 to 30% by weight, based on the total weight of the solid components (the total of the solid components used in any of the cyclic polyphenol compound a, the acid generator C, the acid crosslinking agent G, the acid diffusion-controlling agent E, and the other components F, and the like, hereinafter the same). By using the acid generator in the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In the present invention, the method for producing an acid is not limited as long as the acid can be produced in the system. If excimer laser is used instead of ultraviolet rays such as g-line and i-line, finer processing can be performed; further, if electron beams, ultra-violet rays, X-rays, or ion beams are used as the high-energy beams, further fine processing can be performed.

The acid generator C is the same as that described for the radiation-sensitive composition a.

The radiation-sensitive composition of the present invention preferably contains one or more acid crosslinking agents G. The acid crosslinking agent G is a compound capable of crosslinking the cyclic compound a intramolecularly or intermolecularly in the presence of an acid generated from the acid generator C. Examples of such a crosslinking agent G include: a compound having one or more crosslinking-reactive substituents (hereinafter, referred to as crosslinkable substituents) with the cyclic compound a.

Examples of such crosslinkable substituents include: (i) hydroxyalkyl groups or substituents derived therefrom, such as hydroxy (C1-C6 alkyl), C1-C6 alkoxy (C1-C6 alkyl), acetoxy (C1-C6 alkyl), and the like; (ii) carbonyl or a substituent derived therefrom, such as formyl, carboxyl (C1-C6 alkyl), etc.; (iii) a substituent containing a nitrogen-containing group such as dimethylaminomethyl group, diethylaminomethyl group, dimethylol aminomethyl group, diethylol aminomethyl group, morpholinomethyl group, etc.; (iv) a substituent containing a glycidyl group such as a glycidyl ether group, a glycidyl ester group, a glycidyl amino group, or the like; (v) substituents derived from aromatic groups, such as aryloxy groups of C1-C6 (alkyl groups of C1-C6), aralkyloxy groups of C1-C6 (alkyl groups of C1-C6), etc. (benzyloxymethyl, benzoyloxymethyl, etc.); (vi) and substituents having a polymerizable unsaturated bond such as vinyl group and isopropenyl group. The crosslinkable substituent of the acid crosslinking agent G of the present invention is preferably a hydroxyalkyl group, an alkoxyalkyl group, or the like, and particularly preferably an alkoxymethyl group.

Examples of the acid crosslinking agent G having the crosslinkable substituent include: (i) methylol group-containing compounds such as methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing glycoluril compounds, methylol group-containing phenol compounds, and the like; (ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds, and the like; (iii) carboxymethyl group-containing compounds such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycoluril compounds, carboxymethyl group-containing phenol compounds, and the like; (iv) epoxy compounds such as bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, phenol resin epoxy compounds, resol phenol resin epoxy compounds, polyhydroxystyrene epoxy compounds, and the like.

Further, as the acid crosslinking agent G, a compound and a resin which impart crosslinkability by introducing the crosslinkable substituent into an acidic functional group in a compound having a phenolic hydroxyl group and an alkali-soluble resin can be used. The introduction rate of the crosslinkable substituent in this case is adjusted to be usually 5 to 100 mol%, preferably 10 to 60 mol%, and more preferably 15 to 40 mol% based on the total acidic functional groups in the compound having a phenolic hydroxyl group and the alkali-soluble resin. When the amount is within the above range, the crosslinking reaction proceeds sufficiently, the residual film rate decreases, and swelling, bending, and the like of the pattern can be avoided, which is preferable.

In the radiation-sensitive composition of the present invention, the acid crosslinking agent G is preferably an oxyalkylated urea compound or a resin thereof, or an oxyalkylated glycoluril compound or a resin thereof. Particularly preferred examples of the acid crosslinking agent G include a compound represented by the following formula (43) and an alkoxymethylated melamine compound (acid crosslinking agent G1).

[ chemical formula 76]

(in the above formula, each R⁷Independently represents a hydrogen atom, an alkyl group or an acyl group; r⁸-R¹¹Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group; x²Represents a single bond, a methylene group or an oxygen atom. )

R in the formula (43)⁷Preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms. An alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include: methyl, ethyl, propyl. An acyl group having 2 to 6 carbon atoms, more preferably an acyl group having 2 to 4 carbon atoms, and examples thereof include: acetyl and propionyl. R in the formula (21)⁸-R¹¹More preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. An alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include: methyl, ethyl, propyl. An alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and examples thereof include: methoxy, ethoxy, propoxy. X ²Represents a single bond, a methylene group or an oxygen atom, and is preferably a single bond or a methylene group. In addition, R⁷-R¹¹、X²The above-exemplified groups may further have a substituent, such as an alkyl group (e.g., methyl group or ethyl group), an alkoxy group (e.g., methoxy group or ethoxy group), a hydroxyl group, or a halogen atom. A plurality of R⁷、R⁸-R¹¹Each of which may be the same or different.

Specific examples of the compound represented by the formula (43-1) include the following compounds.

[ chemical formula 77]

Specific examples of the compound represented by the formula (43-2) include: n, N, N, N-tetrakis (methoxymethyl) glycoluril, N, N-tetrakis (ethoxymethyl) glycoluril, N, N, N-tetrakis (N-propoxymethyl) glycoluril, N, N, N-tetrakis (isopropoxymethyl) glycoluril, N, N-tetrakis (N-butoxymethyl) glycoluril, N, N, N-tetrakis (tert-butoxymethyl) glycoluril, and the like. Among these, N-tetrakis (methoxymethyl) glycoluril is particularly preferable.

Specific examples of the compound represented by the formula (43-3) include the following compounds.

[ chemical formula 78]

Specific examples of the alkoxymethylated melamine compound include N, N-hexa (methoxymethyl) melamine, N-hexa (ethoxymethyl) melamine, N-hexa (N-propoxymethyl) melamine, N-hexa (isopropoxymethyl) melamine, N-hexa (N-butoxymethyl) melamine, and N, N-hexa (tert-butoxymethyl) melamine. Among them, N-hexa (methoxymethyl) melamine is particularly preferable.

The acid crosslinking agent G1 can be obtained, for example, by the following method: a urea compound or a glycoluril compound is condensed with formalin to introduce a methylol group, and then etherified with a lower alcohol such as methanol, ethanol, propanol, or butanol, and a compound precipitated by cooling the reaction solution or a resin thereof is recovered. The acid crosslinking agent G1 is also commercially available, for example, CYMEL (trade name, manufactured by Mitsui サイアナミッド) and ニカラック (manufactured by Mitsui ケミカル Co., Ltd.).

Further, as another particularly preferred acid crosslinking agent G, there may be mentioned a phenol derivative having 1 to 6 benzene rings in the molecule, two or more hydroxyalkyl groups and/or alkoxyalkyl groups in the whole molecule, and the hydroxyalkyl groups and/or alkoxyalkyl groups are bonded to any one of the benzene rings (acid crosslinking agent G2). Preferred are phenol derivatives having a molecular weight of 1500 or less, having 1 to 6 benzene rings in the molecule, having a total of two or more hydroxyalkyl groups and/or alkoxyalkyl groups, and having the hydroxyalkyl groups and/or alkoxyalkyl groups bonded to any one or more of the benzene rings.

As the hydroxyalkyl group bonded to the benzene ring, preferred is a hydroxyalkyl group having 1 to 6 carbon atoms, such as a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxy-1-propyl group and the like. The alkoxyalkyl group bonded to the benzene ring is preferably an alkoxyalkyl group having 2 to 6 carbon atoms, and specifically preferably: methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl, 2-methoxyethyl and 2-methoxy-1-propyl.

Particularly preferred examples of these phenol derivatives are as follows.

[ chemical formula 79]

[ chemical formula 80]

[ chemical formula 81]

[ chemical formula 82]

[ chemical formula 83]

[ chemical formula 84]

In the above formula, L¹-L⁸Which may be identical or different, independently of one another represent hydroxymethyl, methoxymethyl or ethoxymethyl. The phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound having no corresponding hydroxymethyl group (in the above formula, L)¹-L⁸A compound which is a hydrogen atom) with formaldehyde in the presence of a base catalyst. In this case, the reaction is preferably carried out at a reaction temperature of 60 ℃ or lower in order to prevent resinification or gelation. Specifically, it can be synthesized by the methods described in JP-A-6-282067 and JP-A-7-64285.

The phenol derivative having an alkoxymethyl group can be obtained by reacting a phenol derivative having a corresponding hydroxymethyl group with an alcohol in the presence of an acid catalyst. In this case, the reaction is preferably carried out at a reaction temperature of 100 ℃ or lower in order to prevent resinification or gelation. Specifically, the compound can be synthesized by the method described in EP 632003A1 or the like.

The phenol derivative having a hydroxymethyl group and/or an alkoxymethyl group thus synthesized is preferred in view of stability during storage; the phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage. The acid crosslinking agent G2 may be used alone or in combination of two or more.

In addition, as another particularly preferred acid crosslinking agent G, a compound having at least one α -hydroxyisopropyl group (acid crosslinking agent G3) can be exemplified. The structure of the compound is not particularly limited as long as it has an α -hydroxyisopropyl group. Furthermore, the hydrogen atom of the hydroxyl group in the above-mentioned α -hydroxyisopropyl group may be dissociated by at least one acid-dissociable group (R-COO-group, R-SO)₂A group or the like, R represents a group selected from a linear hydrocarbon group having 1 to 12 carbon atoms,A cyclic 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). Examples of the compound having an α -hydroxyisopropyl group include: one or more of substituted or unsubstituted aromatic compounds containing at least one α -hydroxyisopropyl group, biphenyl compounds, naphthalene compounds, furan compounds, and the like. Specific examples thereof include: a compound represented by the following general formula (44-1) (hereinafter, referred to as benzene-based compound 1), a compound represented by the following general formula (44-2) (hereinafter, referred to as diphenyl-based compound 2), a compound represented by the following general formula (44-3) (hereinafter, referred to as naphthalene-based compound 3), a compound represented by the following general formula (44-4) (hereinafter, referred to as furan-based compound 4), and the like.

[ chemical formula 85]

In the above general formulae (44-1) to (44-4), each A²Independently represents an alpha-hydroxyisopropyl group or a hydrogen atom, and at least one A²Is alpha-hydroxyisopropyl. In addition, in the general formula (44-1), R⁵¹Represents a hydrogen atom, a hydroxyl group, a linear or branched alkylcarbonyl group having 2 to 6 carbon atoms, or a linear or branched alkoxycarbonyl group having 2 to 6 carbon atoms. Further, in the general formula (44-2), R⁵²Represents a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, -O-, -CO-, or-COO-. In the general formula (44-4), R⁵³And R⁵⁴Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

Specific examples of the benzene compound 1 include: alpha-hydroxyisopropylbenzenes such as alpha-hydroxyisopropylbenzene, 1, 3-bis (. alpha. -hydroxyisopropyl) benzene, 1, 4-bis (. alpha. -hydroxyisopropyl) benzene, 1,2, 4-tris (. alpha. -hydroxyisopropyl) benzene, 1,3, 5-tris (. alpha. -hydroxyisopropyl) benzene, etc., alpha-hydroxyisopropylphenols such as 3-. alpha. -hydroxyisopropylphenol, 4-. alpha. -hydroxyisopropylphenol, 3, 5-bis (. alpha. -hydroxyisopropyl) phenol, 2,4, 6-tris (. alpha. -hydroxyisopropyl) phenol, etc., alpha-hydroxyisopropylphenyl alkylketones such as 3-. alpha. -hydroxyisopropylphenyl methylketone, 4-. alpha. -hydroxyisopropylphenyl methylketone, 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 tert-butyl ketone, 4- α -hydroxyisopropylphenyl n-amyl ketone, 3, 5-bis (. alpha. -hydroxyisopropyl) phenyl methyl ketone, 3, 5-bis (. alpha. -hydroxyisopropyl) phenyl ethyl ketone, 2,4, 6-tris (. alpha. -hydroxyisopropyl) phenyl methyl ketone and the like, 4- α -hydroxyisopropylphenyl alkyl carboxylates such as methyl 3- α -hydroxyisopropylbenzoate, methyl 4-hydroxyisopropylbenzoate and the like, Ethyl 4- α -hydroxyisopropylbenzoate, n-propyl 4- α -hydroxyisopropylbenzoate, isopropyl 4- α -hydroxyisopropylbenzoate, n-butyl 4- α -hydroxyisopropylbenzoate, tert-butyl 4- α -hydroxyisopropylbenzoate, n-pentyl 4- α -hydroxyisopropylbenzoate, methyl 3, 5-bis (. alpha. -hydroxyisopropyl) benzoate, ethyl 3, 5-bis (. alpha. -hydroxyisopropyl) benzoate, methyl 2,4, 6-tris (. alpha. -hydroxyisopropyl) benzoate, and the like.

Further, specific examples of the diphenyl compound 2 include: α -hydroxyisopropylbiphenyls such as 3- α -hydroxyisopropylbiphenyl, 4- α -hydroxyisopropylbiphenyl, 3, 5-bis (. alpha. -hydroxyisopropyl) biphenyl, 3' -bis (. alpha. -hydroxyisopropyl) biphenyl, 3,4' -bis (. alpha. -hydroxyisopropyl) biphenyl, 4,4' -bis (. alpha. -hydroxyisopropyl) biphenyl, 2,4, 6-tris (. alpha. -hydroxyisopropyl) biphenyl, 3', 5-tris (. alpha. -hydroxyisopropyl) biphenyl, 3,4', 5-tris (. alpha. -hydroxyisopropyl) biphenyl, 2,3',4, 6-tetrakis (. alpha. -hydroxyisopropyl) biphenyl, 2,4,4', 6-tetrakis (. alpha. -hydroxyisopropyl) biphenyl, 3,3',5,5' -tetrakis (. alpha. -hydroxyisopropyl) biphenyl, 2,3',4,5', 6-pentakis (. alpha. -hydroxyisopropyl) biphenyl, 2',4,4',6,6' -hexakis (. alpha. -hydroxyisopropyl) biphenyl, etc., and a-hydroxyisopropyl-diphenylalkanes such as 3-. alpha. -hydroxyisopropyl-diphenylmethane, 4-. alpha. -hydroxyisopropyl-diphenylmethane, 1- (4-. alpha. -hydroxyisopropyl-phenyl) -2-phenylethane, 1- (4-. alpha. -hydroxyisopropyl-phenyl) -2-phenylpropane, 2- (4-. alpha. -hydroxyisopropyl-phenyl) -2-phenylpropane, 1- (4-. alpha. -hydroxyisopropyl-phenyl) -3-phenylpropane, etc, 1- (4-. alpha. -hydroxyisopropylphenyl) -4-phenylbutane, 1- (4-. alpha. -hydroxyisopropylphenyl) -5-phenylpentane, 3, 5-bis (. alpha. -hydroxyisopropyldiphenylmethane, 3' -bis (. alpha. -hydroxyisopropyl) diphenylmethane, 3,4' -bis (. alpha. -hydroxyisopropyl) diphenylmethane, 4' -bis (. alpha. -hydroxyisopropyl) diphenylmethane, 1, 2-bis (. alpha. -hydroxyisopropylphenyl) ethane, 1, 2-bis (. alpha. -hydroxypropylphenyl) propane, 2-bis (. alpha. -hydroxypropylphenyl) propane, 1, 3-bis (. alpha. -hydroxypropylphenyl) propane, 1-hydroxy-isopropylphenyl) propane, 1- (4-. alpha. -hydroxypropylphenyl) propane, 1- (4-. alpha. -hydroxy-isopropylphenyl) propane, 5-phenylpentane, 3-bis (. alpha. -hydroxyisopropylphenyl) propane, 3-bis (4-. alpha. -hydroxy-propylphenyl) propane, 3-, 2,4, 6-tris (. alpha. -hydroxyisopropyl) diphenylmethane, 3', 5-tris (. alpha. -hydroxyisopropyl) diphenylmethane, 3,4', 5-tris (. alpha. -hydroxyisopropyl) diphenylmethane, 2,3',4, 6-tetrakis (. alpha. -hydroxyisopropyl) diphenylmethane, 2,4,4', 6-tetrakis (. alpha. -hydroxyisopropyl) diphenylmethane, 3',5,5' -tetrakis (. alpha. -hydroxyisopropyl) diphenylmethane, 2,3',4,5', 6-pentakis (. alpha. -hydroxyisopropyl) diphenylmethane, 2',4,4',6,6 '-hexakis (. alpha. -hydroxyisopropyl) diphenylmethane, etc., and alpha-hydroxyisopropyl diphenyl ethers such as 3-. alpha. -hydroxyisopropyl diphenyl ether, 3', 5',6, 6' -hexakis (. alpha. -hydroxyisopropyl) diphenylmethane, 4- α -hydroxyisopropyl diphenyl ether, 3, 5-bis (. alpha. -hydroxyisopropyl) diphenyl ether, 3' -bis (. alpha. -hydroxyisopropyl) diphenyl ether, 3,4' -bis (. alpha. -hydroxyisopropyl) diphenyl ether, 4,4' -bis (. alpha. -hydroxyisopropyl) diphenyl ether, 2,4, 6-tris (. alpha. -hydroxyisopropyl) diphenyl ether, 3', 5-tris (. alpha. -hydroxyisopropyl) diphenyl ether, 3,4', 5-tris (. alpha. -hydroxyisopropyl) diphenyl ether, 2,3',4, 6-tetrakis (. alpha. -hydroxyisopropyl) diphenyl ether, 2,4,4', 6-tetrakis (. alpha. -hydroxyisopropyl) diphenyl ether, 3',5,5' -tetrakis (. alpha. -hydroxyisopropyl) diphenyl ether, 2,3',4,5', 6-pentakis (. alpha. -hydroxyisopropyl) diphenyl ether, 2',4,4',6,6' -hexakis (. alpha. -hydroxyisopropyl) diphenyl ether and the like, and alpha-hydroxyisopropyl diphenyl ketones such as 3-. alpha. -hydroxyisopropyl diphenyl ketone, 4-. alpha. -hydroxyisopropyl diphenyl ketone, 3, 5-bis (. alpha. -hydroxyisopropyl) diphenyl ketone, 3' -bis (. alpha. -hydroxyisopropyl) diphenyl ketone, 3,4' -bis (. alpha. -hydroxyisopropyl) diphenyl ketone, 4,4' -bis (. alpha. -hydroxyisopropyl) diphenyl ketone, 2,4, 6-tris (. alpha. -hydroxyisopropyl) diphenyl ketone, 3', 5-tris (. alpha. -hydroxyisopropyl) diphenyl ketone, 3,4', 5-tris (. alpha. -hydroxyisopropyl) diphenylketone, 2,3',4, 6-tetrakis (. alpha. -hydroxyisopropyl) diphenylketone, 2,4,4', 6-tetrakis (. alpha. -hydroxyisopropyl) diphenylketone, 3',5,5 '-tetrakis (. alpha. -hydroxyisopropyl) diphenylketone, 2,3',4,5', 6-pentakis (. alpha. -hydroxyisopropyl) diphenylketone, 2',4,4',6,6' -hexakis (. alpha. -hydroxyisopropyl) diphenylketone, etc., and a-hydroxyisopropyl benzoate, such as phenyl 3-. alpha. -hydroxyisopropyl benzoate, phenyl 4-. alpha. -hydroxyisopropyl benzoate, 3-. alpha. -hydroxyisopropyl benzoate, 4-. alpha. -hydroxyisopropyl benzoate, etc, 3, 5-bis (α -hydroxyisopropyl) benzoate, 3- α -hydroxyisopropyl benzoate, 4- α -hydroxyisopropyl benzoate, 3- α -hydroxyisopropyl benzoate, 4- α -hydroxyisopropyl benzoate, 3, 5-bis (α -hydroxyisopropyl) phenyl benzoate, 2,4, 6-tris (α -hydroxyisopropyl) benzoate, 3, 5-bis (α -hydroxyisopropyl) phenyl benzoate, 4- α -hydroxyisopropyl benzoate, 3, 5-bis (α -hydroxyisopropyl) benzoate, 3, 5-bis (α -hydroxyisopropyl) phenyl 3- α -hydroxyisopropyl benzoate, 3, 5-bis (α -hydroxyisopropyl) phenyl 4- α -hydroxyisopropyl benzoate, 2,4, 6-tris (α -hydroxyisopropyl) phenyl benzoate, 3- α -hydroxyisopropyl 2,4, 6-tris (α -hydroxyisopropyl) benzoate, 4- α -hydroxyisopropyl 2,4, 6-tris (α -hydroxyisopropyl) benzoate, 3, 5-bis (α -hydroxyisopropyl) phenyl 3, 5-bis (α -hydroxyisopropyl) benzoate, 2,4, 6-tris (α -hydroxyisopropyl) phenyl 3- α -hydroxyisopropyl benzoate, 3- α -hydroxyisopropyl) phenyl 3,4, 6-tris (α -hydroxyisopropyl) phenyl 3- α -hydroxyisopropyl benzoate, 2,4, 6-tris (. alpha. -hydroxyisopropyl) phenyl 4-. alpha. -hydroxyisopropyl) benzoate, 3, 5-bis (. alpha. -hydroxyisopropyl) phenyl 2,4, 6-tris (. alpha. -hydroxyisopropyl) benzoate, 2,4, 6-tris (. alpha. -hydroxyisopropyl) phenyl 3, 5-bis (. alpha. -hydroxyisopropyl) benzoate, 2,4, 6-tris (. alpha. -hydroxyisopropyl) phenyl 2,4, 6-tris (. alpha. -hydroxyisopropyl) benzoate, and the like.

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

In addition, specific examples of the furan-based compound 4 include: 3- (. alpha. -hydroxyisopropyl) furan, 2-methyl-4- (. alpha. -hydroxyisopropyl) furan, 2-ethyl-4- (. alpha. -hydroxyisopropyl) furan, 2-n-propyl-4- (. alpha. -hydroxyisopropyl) furan, 2-isopropyl-4- (. alpha. -hydroxyisopropyl) furan, 2-n-butyl-4- (. alpha. -hydroxyisopropyl) furan, 2-tert-butyl-4- (. alpha. -hydroxyisopropyl) furan, 2-n-pentyl-4- (. alpha. -hydroxyisopropyl) furan, 2, 5-dimethyl-3- (. alpha. -hydroxyisopropyl) furan, 2-methyl-4, 2, 5-diethyl-3- (. alpha. -hydroxyisopropyl) furan, 3, 4-bis (. alpha. -hydroxyisopropyl) furan, 2, 5-dimethyl-3, 4-bis (. alpha. -hydroxyisopropyl) furan, 2, 5-diethyl-3, 4-bis (. alpha. -hydroxyisopropyl) furan, and the like.

The acid crosslinking agent G3 is preferably a compound having two or more free α -hydroxyisopropyl groups, more preferably the benzene compound 1 having two or more α -hydroxyisopropyl groups, the diphenyl compound 2 having two or more α -hydroxyisopropyl groups, and the naphthalene compound 3 having two or more α -hydroxyisopropyl groups, and particularly preferably α -hydroxyisopropylbiphenyl having two or more α -hydroxyisopropyl groups, and naphthalene compound 3 having two or more α -hydroxyisopropyl groups.

The acid crosslinking agent G3 can be obtained by the following method: reacting acetyl group-containing compound (such as 1, 3-diacetylbenzene) with Grignard reagent (such as CH)₃MgBr, etc.), and then carrying out methylation and hydrolysis; or a method in which an isopropyl group-containing compound (e.g., 1, 3-diisopropylbenzene) is oxidized with oxygen or the like to produce a peroxide, and then reduced.

In the present invention, the blending ratio of the acid crosslinking agent G is 0.5 to 70 parts by weight, preferably 0.5 to 40 parts by weight, and more preferably 1 to 30 parts by weight per 100 parts by weight of the above cyclic compound A. When the blending ratio of the acid crosslinking agent G is 0.5 parts by weight or more, the effect of suppressing the solubility of the resist film in an alkaline developer is improved, the residual film rate is reduced, and the swelling and warpage of the pattern can be suppressed, and therefore, it is preferable; on the other hand, 70 parts by weight or less is preferable because a decrease in heat resistance as a resist can be suppressed.

The blending ratio of at least one compound selected from the group consisting of the acid crosslinking agents G1, G2 and G3 in the acid crosslinking agent G is not particularly limited, and may be set in various ranges depending on the kind of the substrate used for forming the resist pattern.

Preferably, the alkoxymethylated melamine compound and/or the compounds represented by (43-1) to (43-3) are present in an amount of 50 to 99% by weight, preferably 60 to 99% by weight, more preferably 70 to 98% by weight, and still more preferably 80 to 97% by weight, of the total acid crosslinking agent component. It is preferable that the alkoxymethylated melamine compound and/or the compounds represented by (43-1) to (43-3) are contained in an amount of 50 wt% or more based on the total acid crosslinking agent component because the resolution can be improved; when the amount is 99 wt% or less, the cross-sectional shape of the figure is preferably a rectangular cross-sectional shape.

In the present invention, an acid diffusion controller E having an action of controlling diffusion of an acid generated from an acid generator by irradiation of radiation in a resist film, preventing an undesired chemical reaction not in an exposed region, or the like may be blended in the radiation-sensitive composition. By using such an acid diffusion controller E, the storage stability of the resist composition is improved; further, the resolution is improved, and the line width change of the resist pattern due to the variation of the standing time before the electron beam irradiation and the standing time after the electron beam irradiation is suppressed, so that the radiation-sensitive composition containing the acid diffusion controller E is extremely excellent in process stability. Examples of such an acid diffusion controller E include: an electron-ray-radiolucent basic compound, such as a nitrogen atom-containing basic compound, a basic sulfonium compound, a basic iodonium compound, or the like. The acid diffusion controlling agent may be used alone or in combination of two or more. Specifically, the same substances as those described with respect to the above-mentioned radiation-sensitive composition a can be used.

The amount of the acid diffusion controller E to be blended is preferably 0.001 to 10% by weight, more preferably 0.001 to 5% by weight, and still more preferably 0.001 to 3% by weight based on the total weight of the solid content. Within the above range, a decrease in resolution, a deterioration in the shape of the pattern, the fidelity of the size, and the like can be prevented. Further, even if the standing time from the start of the electron beam irradiation to the heating after the radiation irradiation is long, the shape of the upper layer portion of the pattern is not deteriorated. When the amount of the acid diffusion controller E added is 10% by weight or less, the reduction in sensitivity, developability of unexposed portions, and the like can be prevented. Further, by using such an acid diffusion controller, the storage stability of the resist composition is improved, the resolution is improved, and the line width change of the resist pattern due to the variation of the standing time before the electron beam irradiation and the standing time after the electron beam irradiation can be suppressed, so that the radiation-sensitive composition containing the acid diffusion controller E is extremely excellent in process stability.

One or more of various additives such as a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, and an oxoacid of an organic carboxylic acid or phosphorus or a derivative thereof may be added to the resist composition of the present invention as needed within a range not to impair the object of the present invention.

Low molecular weight dissolution promoter

The low-molecular-weight dissolution accelerator is a component having an action of increasing the solubility of the cyclic compound a when the solubility thereof in a developer such as an alkali is too low, and appropriately increasing the dissolution rate of the cyclic compound a during development, and can be used within a range not impairing the effects of the present invention. Examples of the dissolution accelerating agent include low molecular weight phenolic compounds, for example: bisphenols, tris (hydroxyphenyl) methane, and the like. These dissolution promoters may be used singly or in combination of two or more. The amount of the dissolution accelerator to be blended may be adjusted as appropriate depending on the kind of the cyclic compound a to be used, and the sum of the cyclic compound a and the low-molecular-weight dissolution accelerator is an amount of 50 to 99.999% by weight, preferably 60 to 99% by weight, more preferably 70 to 99% by weight, and still more preferably 80 to 99% by weight based on the total weight of the solid component.

As the dissolution-controlling agent, the sensitizer, the surfactant, and various additives such as an organic carboxylic acid or an oxyacid of phosphorus or a derivative thereof, the same ones as those described for the above-mentioned radiation-sensitive composition a can be used.

The blending ratio of the radiation-sensitive resist composition of the present invention (cyclic compound A/acid generator C/acid crosslinking agent G/acid diffusion controller E/optional component F) is, in% by weight based on solid matter, preferably 3-96.9/0.1-30/3-65/0.01-30/0-93.9, more preferably 65-96.9/0.1-30/0.3-34.9/0.01-30/0-30, still more preferably 65-96.9/0.1-30/0.3-34.9/0.01-30/0-10, still more preferably 65-96.9/0.1-30/0.6-34.9/0.01-30/0-5, most preferably 65-96.9/0.1-30/0.6-30/0.01-30/0. When the above blending ratio is used, the properties such as sensitivity, resolution and alkali developability are excellent.

When the arbitrary component F is not contained, the composition of the total solid matter in the radiation-sensitive resist composition of the present invention is preferably: 3-96.9% of A, 0.1-30% of C, 0.3-96.9% of G, 0.01-30% of E and (A + C + G + E is 100% by weight); more preferably, a is 65 to 96.9 wt%, C is 0.1 to 32 wt%, G is 0.3 to 34.9 wt%, E is 0.01 to 30 wt%, and (a + C + G + E) ═ 100 wt%); further preferably 70 to 96.9% by weight of a, 0.1 to 27% by weight of C, 0.3 to 29.9% by weight of G, 0.01 to 30% by weight of E, and (a + C + G + E) ═ 100% by weight); particularly preferably, a is 80 to 96.9 wt%, C is 0.1 to 17 wt%, G is 0.3 to 19.9 wt%, E is 0.01 to 30 wt%, and (a + C + G + E) ═ 100 wt%); most preferably, a is 90 to 96.9 wt%, C is 0.1 to 7 wt%, G is 0.3 to 9.9 wt%, E is 0.01 to 30 wt%, and (a + C + G + E) ═ 100 wt%); when the amount is within the above range, the properties such as sensitivity, resolution and alkali developability are excellent.

As the solvent used in the preparation of the radiation-sensitive composition of the present invention, the same solvents as those described for the above-mentioned radiation-sensitive composition a can be used.

The radiation-sensitive composition of the present invention may contain a resin soluble in an alkaline aqueous solution within a range not impairing the object of the present invention. Examples of the resin soluble in an aqueous alkaline solution include: phenolic resins, polyvinyl phenol resins, polyacrylic acids, polyvinyl alcohols, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol or vinyl phenol as monomer units, or derivatives thereof, and the like. The blending amount of the resin soluble in the aqueous alkaline solution may be adjusted as appropriate depending on the kind of the resist compound used, and is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, and particularly preferably 0 part by weight, per 100 parts by weight of the cyclic compound a.

(composition D for Forming an underlayer film and underlayer film)

The present invention relates to an underlayer coating forming composition containing any one of the radiation-sensitive compositions C described above.

The present invention also relates to an underlayer coating forming composition containing a cyclic compound represented by formula (45).

[ chemical formula 86]

(in the formula, R¹Independently represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 24 carbon atoms, an allyl group, a hydroxyalkyl group, a cyanoalkyl group, a haloalkyl group, a hydroxyaryl group, a cyanoaryl group or a haloaryl group. )

The cyclic compound has a glass transition temperature of 200 ℃ or higher, high heat resistance, and is amorphous, and therefore has good film-forming properties and no sublimation properties. Further, surprisingly, the benzene-based optical fiber has a benzene structure, and also has advantages of a relatively low extinction coefficient to 193nm light and a high refractive index.

R in the formula (45) according to the present invention¹Specific examples of (3) include: a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexylethyl, cyclohexylpropyl, and the like; a linear, branched or cyclic hydroxyalkyl group having 1 to 20 carbon atoms such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, a hydroxynonyl group, a hydroxydecyl group, a hydroxycyclohexylethyl group, a hydroxycyclohexylpropyl group, and the like; a linear, branched or cyclic cyanoalkyl group having 1 to 20 carbon atoms such as cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, cyanohexyl, cyanoheptyl, cyanooctyl, cyanononyl, cyanodecyl, cyanocyclohexylethyl, cyanocyclohexylpropyl, and the like; a linear, branched or cyclic haloalkyl group having 1 to 20 carbon atoms, such as a halomethyl group, a haloethyl group, a halopropyl group, a halobutyl group, a halopentyl group, a halohexyl group, a haloheptyl group, a halooctyl group, a halononyl group, a halodecyl group, a halocyclohexylethyl group, a halocyclohexylpropyl group, and the like; aryl having 6 to 20 carbon atoms, e.g. phenyl, naphthyl, indanyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl A phenyl group, a pyrenyl group, a biphenyl group, a biphenylyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a n-propylphenyl group, an isobutylphenyl group, a tert-butylphenyl group, a biphenyl group, a 4-cyclohexylphenyl group, a 4-propyl-4-cyclohexylphenyl group, a 4-butyl-4-cyclohexylphenyl group, a 4-pentyl-4-cyclohexylphenyl group, a 4-salicylylphenyl group (4- サリチルフェニル group), a 4-norbornylphenyl group, a 4-adamantylphenyl group, a 4-dicyclopentadienylphenyl group, a 4-tricyclopentylphenyl group, etc.; cyanoaryl groups such as 4-cyanophenyl group, 4-cyanobiphenyl group and the like; halogenated aryl groups such as 4-halogenated phenyl, 4-halogenated biphenyl and the like; hydroxyaryl groups such as 4-hydroxyphenyl and the like.

Among them, particularly preferred are aryl groups, hydroxyaryl groups, cyanoaryl groups, and halogenated aryl groups having 6 to 24 carbon atoms.

The cyclic compound of the present invention can be a cis-isomer or a trans-isomer, and may have any structure or a mixture thereof. As a method for obtaining a cyclic compound having only one structure of cis-form and trans-form, for example: separation by column chromatography or preparative liquid chromatography, or preparation, can be carried out by a known method such as optimization of the reaction solvent, reaction temperature, and the like.

Further, the cyclic compound contained in the composition for forming an underlayer film of the present invention is preferably a cyclic compound represented by the following formula (46).

[ chemical formula 87]

(in the formula, R²Independently hydrogen atom, linear, branched or cyclic hydrocarbon group with 1-12 carbon atoms, halogen atom, cyano, hydroxyl, alkoxy and ester group. )

By having the structure represented by the formula (46), it is possible to impart further etching resistance by converting an aldehyde (e.g., formaldehyde, acetaldehyde, or the like) and an acid catalyst into a phenol resin, and it is possible to suppress mixing without using a relatively expensive crosslinking agent and photoacid generator.

The invention is of the formula (46)R in (1)²Examples thereof include: linear, branched or cyclic hydrocarbon groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, 4-n-pentylcyclohexyl, 4-n-hexylcyclohexyl, dicyclohexyl, norbornyl, norbornenyl, cyclopentenyl, tricyclopentenyl, adamantyl and the like; halo, fluoro, chloro, bromo, iodo, and the like; a cyano group; a hydroxyl group; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, and the like; ester groups such as carbomethoxy, carbethoxy, propisocarbonyl, isopropanoyl, butyloxycarbonyl, isobutyloxycarbonyl and the like.

Among them, a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms (e.g., cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-n-propylcyclohexyl group, 4-n-butylcyclohexyl group, 4-n-pentylcyclohexyl group, 4-n-hexylcyclohexyl group, norbornyl group, etc.) is preferable because it imparts a high refractive index and an appropriate extinction coefficient to light of 193 nm.

Further, the cyclic compound contained in the composition for forming an underlayer film of the present invention is preferably a compound represented by the formula (2) or the formula (3).

The cyclic compound represented by the formula (45) can be obtained by a condensation reaction of a resorcinol-containing compound and at least one selected from the group consisting of aliphatic aldehydes having 1 to 20 carbon atoms and aromatic aldehydes having 6 to 24 carbon atoms.

Examples of the aliphatic aldehyde having 1 to 20 carbon atoms or the aromatic aldehyde having 6 to 24 carbon atoms include: straight-chain or branched-chain aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isopropanal, 1-butyraldehyde, isobutyraldehyde, 1-valeraldehyde, isovaleraldehyde, pivalaldehyde, 1-hexanal, isohexanal, 1-decanal, and 1-dodecanal; aromatic aldehydes such as benzaldehyde, tolualdehyde, ethylbenzaldehyde, cuminaldehyde, n-propylbenzaldehyde, isobutylaldehyde, tert-butylaldehyde, benzaldehyde, 4-cyclohexylbenzaldehyde, 4-propyl-4-cyclohexylbenzaldehyde, 4-butyl-4-cyclohexylbenzaldehyde, 4-pentyl-4-cyclohexylbenzaldehyde, 4-cyanobenzaldehyde, 4-halogenobenzaldehyde, 4-hydroxybenzaldehyde, 4-salicylaldehyde, 4-norbornylbenzaldehyde, 4-adamantanylbenzaldehyde, 4-dicyclopentadiene benzaldehyde, 4-tricyclopentylbenzaldehyde, naphthaldehyde, phenanthreneformaldehyde, anthraceneformaldehyde, pyreneformaldehyde and the like.

Among these compounds containing an aliphatic aldehyde having 1 to 20 carbon atoms or an aromatic aldehyde having 6 to 24 carbon atoms, 4-propyl-4-cyclohexylbenzaldehyde and 4-pentyl-4-cyclohexylbenzaldehyde are preferable, and 4- (trans-4-n-propylcyclohexyl) benzaldehyde and 4- (trans-4-n-pentylcyclohexyl) benzaldehyde are particularly preferable.

The cyclic compound represented by formula (45) can be produced by a known method. For example, it can be obtained by the following method: in an organic solvent (toluene, methanol, ethanol, etc.), in the presence of thioacetic acid or β -mercaptopropionic acid, and an acid catalyst (hydrochloric acid, sulfuric acid, or p-toluenesulfonic acid), in a molar ratio of 1: (1 to excess) carbonyl compound (e.g., aromatic aldehyde) and phenol (e.g., phenol, o-cresol, resorcinol) at 60-150 deg.C for 0.5-20 hr, adding toluene to the reaction solution, heating to 60-80 deg.C, stirring for 0.5-2 hr, cooling to room temperature, filtering, separating, and drying.

The molecular weight of the cyclic compound is preferably 400 to 2000, more preferably 600 to 2000, and still more preferably 800 to 1500. When the amount is within the above range, a lower layer film material having good film forming properties, good etching resistance and a small sublimation component can be obtained.

The cyclic compound may be in the cis-form or the trans-form, and may have any structure or mixture.

In the lower layer film composition of the present invention, a resin having a repeating unit represented by the following formula, which is obtained by a dehydration condensation reaction of the above cyclic compound and aldehyde, may be used.

[ chemical formula 88]

Examples of the aldehydes used herein include: formaldehyde, trioxane, paraformaldehyde, acetaldehyde, and the like. Among them, formaldehyde is particularly preferable.

Here, the repeating unit is not limited. Since polyphenols themselves do not have sublimability, unreacted polyphenol compounds may remain, but when Mw exceeds 50000, spin coating may not be performed due to excessive viscosity.

The present invention may contain a crosslinking agent G and an acid generator C for suppressing mixing.

Specific examples of the crosslinking agent that can be used in the present invention include: a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, an epoxy compound, a thioepoxy compound, an isocyanate compound, an azide compound, a compound having a double bond such as an alkenyl ether group, which is substituted with at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group. They may also be used as additives, or these crosslinkable groups may be introduced as pendant groups into the polymer side chains. In addition, compounds containing hydroxyl groups may also be used as crosslinking agents.

Among the above compounds, if an epoxy compound is exemplified, the following can be exemplified: tris (2, 3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether and the like. Specifically, the melamine compound is exemplified by: hexamethylolmelamine, hexamethoxymethylmelamine, a compound of hexamethylolmelamine wherein 1 to 6 of the methylol groups of the hexamethylolmelamine are methylolated or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound of hexamethylolmelamine wherein 1 to 6 of the methylol groups of the hexamethylolmelamine are acyloxymethylated or a mixture thereof. Examples of the guanamine compound include: tetramethylol guanamine, tetramethoxymethyl guanamine, a compound in which 1 to 4 methylol groups of the tetramethylol guanamine are methylated by methoxy group or a mixture thereof, tetramethoxyethyl guanamine, tetraalkoxyguanamine, a compound in which 1 to 4 methylol groups of the tetramethylol guanamine are methylated by acyloxy group or a mixture thereof. Examples of the glycoluril compound include: tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are methylolated or a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylols of tetramethylol urea are methoxymethylated, a mixture thereof, and tetramethoxyethyl urea.

Examples of the alkenyl ether group-containing compound include: ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1, 2-propylene glycol divinyl ether, 1, 4-butanediol divinyl ether, tetramethylglycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1, 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

The blending amount of the crosslinking agent G is preferably 5 to 50 parts, particularly preferably 10 to 40 parts, per 100 parts (by mass, the same applies hereinafter) of the cyclic compound. When the amount is less than 5 parts, the mixture may be mixed with the resist; when the amount exceeds 50 parts, the antireflection effect may be reduced, and cracks may appear in the crosslinked film.

An acid generator C for further promoting the crosslinking reaction by heat may be added. The acid generator C includes an acid generator that generates an acid by thermal decomposition and an acid generator that generates an acid by light irradiation, and any one of the acid generators may be added.

Examples of the acid generator C used in the present invention include:

1) An onium salt of the general formula (P1a-1), (P1a-2), (P1a-3) or (P1b),

2) a diazomethane derivative of the following general formula (P2),

3) glyoxime derivatives of the following general formula (P3),

4) a disulfone derivative of the general formula (P4),

5) a sulfonic acid ester of an N-hydroxyimide compound of the following general formula (P5),

6) a beta-ketosulfonic acid derivative, a process for preparing the same,

7) a derivative of a disulfone, which is,

8) a nitrobenzyl sulfonate derivative, a process for preparing the same,

9) sulfonate derivatives, and the like.

[ chemical formula 89]

(in the formula, R^101a、R^101b、R^101cEach represents a linear, branched or cyclic alkyl group, alkenyl group, oxoalkyl group or oxoalkenyl group having 1 to 12 carbon atoms, aryl group having 6 to 20 carbon atoms, or aralkyl group or aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. In addition, R^101bAnd R^101cOr may form a ring, and when forming a ring, R^101b、R^101cEach represents an alkylene group having 1 to 6 carbon atoms. K^-Denotes a non-nucleophilic counterion. Is shown at R^101d、R^101e、R^101f、R^101gRepresents R^101a、R^101b、R^101cTo which a hydrogen atom is added. R^101dAnd R^101e、R^101dAnd R^101eAnd R^101fOr may form a ring, and when forming a ring, R^101dAnd R^101eAnd R^101dAnd R^101eAnd R^101fRepresents an alkylene group having 3 to 10 carbon atoms. Also disclosed is an aromatic heterocyclic ring having a nitrogen atom in the ring. )

R is as defined above^101a、R^101b、R^101c、R^101d、R^101e、R^101f、R^101gThe alkyl groups may be the same or different from each other, and specifically, as the alkyl group, there may be mentioned: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptylCyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl and the like. Examples of the alkenyl group include: vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl, and the like. Examples of the oxoalkyl group include: 2-oxocyclopentyl group, 2-oxocyclohexyl group and the like, and further include: 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, 2- (4-methylcyclohexyl) -2-oxoethyl and the like. Examples of the aryl group include: a phenyl group; naphthyl and the like; or an alkoxyphenyl group such as p-methoxyphenyl, bonded methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, m-tert-butoxyphenyl, etc.; alkylphenyl such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl and the like; alkylnaphthyl groups such as methylnaphthyl, ethylnaphthyl, and the like; alkoxynaphthyl groups such as methoxynaphthyl group, ethoxynaphthyl group and the like; dialkylnaphthyls such as dimethylnaphthyls, diethylnaphthyls, and the like; dialkoxynaphthyl groups such as dimethoxynaphthyl group, diethoxynaphthyl group and the like. Examples of the aralkyl group include: benzyl, phenethyl, and the like. Examples of the aryloxyalkyl group include: 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like. As K ^-Examples of the non-nucleophilic counter ion include: halide ions such as chloride ions, bromide ions, etc.; fluoroalkyl sulfonates such as trifluoromethylsulfonate, 1,1, 1-trifluoroethylsulfonate, nonafluorobutylsulfonate and the like; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4, 5-pentafluorobenzenesulfonate and the like; alkyl sulfonates such as methanesulfonate (メシレート), butylsulfonate, and the like.

In addition, R^101d、R^101e、R^101f、R^101gAn aromatic heterocyclic ring having a nitrogen atom in the ring of the formula (I): imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyritinoid, etc.), and the likePyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine), lutidine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-t-butylpyridine, biphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, N-methylpyrrolidone, etc.), pyrrolidine derivatives, and pyridine derivatives, Pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-cyanoquinoline, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthroline derivatives, acridine derivatives, phenazine derivatives, 1, 10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, and the like.

The general formulae (P1a-1) and (P1a-2) have both effects of a photoacid generator and a thermal acid generator, but the general formula (P1a-3) functions as a thermal acid generator.

[ chemical formula 90]

(in the formula, R^102a、R^102bEach represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. R¹⁰³Represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. R^104a、R^104bEach represents a 2-oxoalkyl group having 3 to 7 carbon atoms. K^-Denotes a non-nucleophilic counterion. )

As R^102a、R^102bSpecific examples thereof include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl and the like. As R¹⁰³Examples thereof include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, 1, 4-cyclohexylene, 1, 2-cyclohexylene, 1, 3-cyclopentylene, 1, 4-cyclooctylene, 1, 4-cyclohexanedimethylene and the like. As R^104a、R^104bExamples thereof include: 2-propionyl group, 2-cyclopentyl group, 2-cyclohexyl group, 2-cycloheptyl group and the like. K^-Examples thereof include: the same groups as those described in the formulae (P1a-1), (P1a-2) and (P1 a-3).

[ chemical formula 91]

(in the formula, R¹⁰⁵、R¹⁰⁶Represents a linear, branched or cyclic alkyl group or a haloalkyl group having 1 to 12 carbon atoms; aryl or halogenated aryl with 6-20 carbon atoms; or an aralkyl group having 7 to 12 carbon atoms. )

As R¹⁰⁵、R¹⁰⁶Examples thereof include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, pentyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl and the like. Examples of the haloalkyl group include: trifluoromethyl, 1,1, 1-trifluoroethyl, 1,1, 1-trichloroethyl, nonafluorobutyl, and the like. Examples of the aryl group include: a phenyl group; alkoxyphenyl such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, m-tert-butoxyphenyl and the like; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl and the like. Examples of the halogenated aryl group include: fluorophenyl, chlorophenyl, 1,2,3,4, 5-pentafluorophenyl and the like. Examples of the aralkyl group include: benzyl, phenethylAnd the like.

[ chemical formula 92]

(in the formula, R¹⁰⁷、R¹⁰⁸、R¹⁰⁹Represents a linear, branched or cyclic alkyl group or a haloalkyl group having 1 to 12 carbon atoms; aryl or halogenated aryl with 6-20 carbon atoms; or an aralkyl group having 7 to 12 carbon atoms. R ¹⁰⁸、R¹⁰⁹Or may be bonded to each other to form a cyclic structure, and when the cyclic structure is formed, R is¹⁰⁸、R¹⁰⁹Each represents a linear or branched alkylene group having 1 to 6 carbon atoms. )

As R¹⁰⁷、R¹⁰⁸、R¹⁰⁹Examples of the alkyl group, haloalkyl group, aryl group, haloaryl group and aralkyl group in (1) include those mentioned in R¹⁰⁵、R¹⁰⁶The same groups as those described in (1) above. Further, as R¹⁰⁸、R¹⁰⁹Examples thereof include: methylene, ethylene, propylene, butylene, hexylene, and the like.

[ chemical formula 93]

(in the formula, R^101a、R^101bAs described above. )

[ chemical formula 94]

(in the formula, R¹¹⁰Represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and some or all of the hydrogen atoms of these groups may be further substituted with a linear or branched alkyl group or alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetyl group or a phenyl group. R¹¹¹Representing a carbon number of 1 to 8A linear, branched or substituted alkyl, alkenyl or alkoxyalkyl, phenyl or naphthyl group, wherein some or all of the hydrogen atoms of these groups may be further substituted by: an alkyl group or an alkoxy group having 1 to 4 carbon atoms; phenyl which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom. )

Herein as R¹¹⁰Examples of the arylene group of (a) include a 1, 2-phenylene group, a 1, 8-naphthylene group and the like; examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a phenylethylene group, a norbornane-2, 3-diyl group and the like; examples of the alkenylene group include a 1, 2-vinylene group, a 1-phenyl-1, 2-vinylene group, and a 5-norbornene-2, 3-diyl group. As R¹¹¹Alkyl of (a) is with R^101a～R^101cThe same groups; examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 3-butenyl group, an isobutenyl group, a 1-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a dimethylallyl group, a 1-hexenyl group, a 3-hexenyl group, a 5-hexenyl group, a 1-heptenyl group, a 3-heptenyl group, a 6-heptenyl group, and a 7-octenyl group; examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentyloxymethyl group, a hexyloxymethyl group, a heptyloxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a butoxyethyl group, a pentyloxyethyl group, a hexyloxyethyl group, a methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, a butoxypropyl group, a methoxybutyl group, an ethoxybutyl group, a propoxybutyl group, a methoxypentyl group, an ethoxypentyl group, a methoxyhexyl group, and a methoxy.

Examples of the alkyl group having 1 to 4 carbon atoms which may be further substituted include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like; examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group; examples of the phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group include a phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group and the like; examples of the heteroaromatic group having 3 to 5 carbon atoms include a pyridyl group, a furyl group and the like.

Specific examples thereof include: onium salts such as tetramethylammonium triflate, tetramethylammonium nonafluorobutylsulfonate, triethylammonium nonafluorobutylsulfonate, pyridinium nonafluorobutylsulfonate, triethylammonium camphylsulfonate, pyridinium camphylsulfonate, tetra-n-butylammonium nonafluorobutylsulfonate, tetraphenylammonium nonafluorobutylsulfonate, tetramethylammonium p-toluenesulfonate, diphenyliodonium triflate, (p-tert-butoxyphenyl) phenyliodonium triflate, diphenyliodonium p-toluenesulfonate, p-tert-butoxyphenyl) phenyliodonium p-toluenesulfonate, triphenylsulfonium triflate, bis (p-tert-butylphenyl) diphenylsulfonium triflate, tris (p-tert-butoxyphenyl) sulfonium triflate, triphenylsulfonium p-toluenesulfonate, p-tert-butoxyphenyl) diphenylsulfonium p-toluenesulfonate, triphenylsulfonium triflate, triethylammonium nonafluorobutylsulfonate, pyridinium triflate, diphenyliodonium triflate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutylsulfonate, triphenylsulfonium butylsulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonate dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, ethylenebis [ methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate ] (a salt of a compound, 1, 2' -naphthylcarbonylmethyltetrahydrothiophenium trifluoromethanesulfonate and the like;

Diazomethane derivatives, such as bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (ditolylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-pentylsulfonyl) diazomethane, bis (isopentylsulfonyl) diazomethane, bis (sec-pentylsulfonyl) diazomethane, bis (tert-pentylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-pentylsulfonyl) diazomethane, bis (di-butylsulfonyl) diazomethane, bis (sec-pentylsulfonyl) diazomethane, bis (tert-pentyl, 1-tert-pentylsulfonyl-1- (tert-butylsulfonyl) diazomethane, and the like.

Glyoxime derivatives such as bis- (p-tolylsulfonyl) - α -dimethylglyoxime, bis- (p-tolylsulfonyl) - α -diphenylglyoxime, bis- (p-tolylsulfonyl) - α -dicyclohexylglyoxime, bis- (p-tolylsulfonyl) -2, 3-pentanedione glyoxime, bis- (p-tolylsulfonyl) -2-methyl-3, 4-pentanedione glyoxime, bis- (n-butylsulfonyl) - α -dimethylglyoxime, bis- (n-butylsulfonyl) - α -diphenylglyoxime, bis- (n-butylsulfonyl) - α -dicyclohexylglyoxime, bis- (n-butylsulfonyl) -2, 3-pentanedione glyoxime, bis- (n-butylsulfonyl) - α -phenylglyoxime, bis- (n-butylsulfonyl) - α -dicyclohexylglyoxime, bis- (n-butylsulfonyl) -2, 3-pentanedione glyoxime, bis (p-, Bis- (n-butylsulfonyl) -2-methyl-3, 4-pentanedionato-glyoxime, bis- (methylsulfonyl) - α -dimethylglyoxime, bis- (trifluoromethylsulfonyl) - α -dimethylglyoxime, bis- (1,1, 1-trifluoroethylsulfonyl) - α -dimethylglyoxime, bis- (tert-butylsulfonyl) - α -dimethylglyoxime, bis- (perfluorooctylsulfonyl) - α -dimethylglyoxime, bis- (cyclohexylsulfonyl) - α -dimethylglyoxime, bis- (phenylsulfonyl) - α -dimethylglyoxime, bis- (p-fluorophenylsulfonyl) - α -dimethylglyoxime, bis- (p-tert-butylphenyl-sulfonyl) - α -dimethylglyoxime, bis- (p-tert-butylphenyl-sulfonylato) - α -dimethylglyoxime, bis- (p-toluenesulfonyl) - α -dimethylglyoxime, bis- (p-tert-butylphenyl-butylbenzenesulfonyl) - α -dimethylglyoxime, bis- (, Bis- (xylylsulfonyl) - α -dimethylglyoxime, bis- (camphenylsulfonyl) - α -dimethylglyoxime, and the like;

Disulfone derivatives such as bis-naphthylsulfonylmethane, bis-trifluoromethylsulfonylmethane, bis-methylsulfonylmethane, bis-ethylsulfonylmethane, bis-propylsulfonylmethane, bis-isopropylsulfonylmethane, bis-p-toluenesulfonylmethane, bis-phenylsulfonylmethane and the like.

β -ketosulfone derivatives such as 2-cyclohexylcarbonyl-2- (p-tolylsulfonyl) propane, 2-isopropylcarbonyl-2- (p-tolylsulfonyl) propane and the like;

disulfone derivatives such as diphenyl disulfone derivatives, dicyclohexyl disulfone derivatives, and the like;

nitrobenzyl sulfonate derivatives such as 2, 6-dinitrobenzyl p-toluenesulfonate, 2, 4-dinitrobenzyl p-toluenesulfonate, and the like.

Sulfonate derivatives such as 1,2, 3-tris (methylsulfonyloxy) benzene, 1,2, 3-tris (trifluoromethylsulfonyloxy) benzene, 1,2, 3-tris (p-tolylsulfonyloxy) benzene, etc.;

sulfonate derivatives of N-hydroxysuccinimide compounds, e.g., N-hydroxysuccinimide methylsulfonate, N-hydroxysuccinimide trifluoromethylsulfonate, N-hydroxysuccinimide ethylsulfonate, N-hydroxysuccinimide 1-propylsulfonate, N-hydroxysuccinimide 2-propylsulfonate, N-hydroxysuccinimide 1-pentylsulfonate, N-hydroxysuccinimide 1-octylsulfonate, N-hydroxysuccinimide p-tolylsulfonate, N-hydroxysuccinimide p-methoxyphenylsulfonate, N-hydroxysuccinimide 2-chloroethylsulfonate, N-hydroxysuccinimide phenylsulfonate, N-hydroxysuccinimide-2, 4, 6-trimethylphenylsulfonate, N-hydroxysuccinimide methylsulfonate, N-hydroxysuccinimide 1-naphthyl sulfonate, N-hydroxysuccinimide 2-naphthyl sulfonate, N-hydroxy-2-phenylsuccinimide methylsulfonate, N-hydroxymaleimide ethylsulfonate, N-hydroxy-2-phenylmaleimide methylsulfonate, N-hydroxyglutarimide phenylsulfonate, N-hydroxyphthalimide methylsulfonate, N-hydroxyphthalimide phenylsulfonate, N-hydroxyphthalimide trifluoromethylsulfonate, N-hydroxyphthalimide p-tolylsulfonate, N-hydroxynaphthalimide methylsulfonate, N-hydroxynaphthalimide phenylsulfonate, N-hydroxynaphthalimide, N-hydroxy-5-norbornyl-2, 3-dicarboxyimide methylsulfonate, N-hydroxy-5-norbornyl-2, 3-dicarboxyimide trifluoromethylsulfonate, N-hydroxy-5-norbornyl-2, 3-dicarboxyimide p-tolylsulfonate, etc.;

Particularly preferably used are: onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 1, 2' -naphthylcarbonylmethyltetrahydrothiophenium trifluoromethanesulfonate and the like; diazomethane derivatives such as bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, and the like; glyoxime derivatives such as bis- (p-tolylsulfonyl) - α -dimethylglyoxime, bis- (n-butylsulfonyl) - α -dimethylglyoxime, and the like; disulfone derivatives such as bis-naphthylsulfonylmethane, and the like; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methylsulfonate, N-hydroxysuccinimide trifluoromethylsulfonate, N-hydroxysuccinimide 1-propylsulfonate, N-hydroxysuccinimide 2-propylsulfonate, N-hydroxysuccinimide 1-pentylsulfonate, N-hydroxysuccinimide p-tolylsulfonate, N-hydroxynaphthalene diimide methylsulfonate, N-hydroxynaphthalene diimide phenylsulfonate, and the like.

The acid generator C may be used alone or in combination of two or more. The amount of the acid generator C added is preferably 0.1 to 50 parts, more preferably 0.5 to 40 parts, per 100 parts of the polyphenol compound. When the amount is less than 0.1 part, the amount of the acid produced may be small and the crosslinking reaction may be insufficient; when the amount exceeds 50 parts, a mixing phenomenon may occur due to migration of acid to the upper layer resist.

Further, in the material for forming an underlayer film of the present invention, an alkaline compound for improving storage stability may be blended.

The basic compound serves to prevent a crosslinking reaction from proceeding by a small amount of acid generated from the acid generator C, and to quench the acid. Examples of such basic compounds include primary, secondary and tertiary aliphatic amines; mixing amines; aromatic amines; heterocyclic amines; a nitrogen-containing compound having a carboxyl group; a nitrogen-containing compound having a sulfonyl group; a nitrogen-containing compound having a hydroxyl group; a nitrogen-containing compound having a hydroxyphenyl group; an alcoholic nitrogen-containing compound; an amide derivative; imide derivatives, and the like.

Specifically, examples of the aliphatic primary amines include ammonia, methylamine, ethylamine, N-propylamine, isopropylamine, N-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexane, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine, examples of the aliphatic secondary amines include dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dihexadecylamine, N-dimethylmethylenediamine, N-dimethylethylenediamine, N-dimethyltetraethylenepentamine, and examples of the aliphatic tertiary amines include trimethylamine, and the like, Triethylamine, tri-N-propylamine, triisopropylamine, tri-N-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonyl amine, tridecylamine, tridodecyl amine, trihexadecyl amine, N ' -tetramethylmethylenediamine, N ' -tetramethylethylenediamine, N ' -tetramethyltetraethylenepentamine, and the like.

Examples of the mixed amines include: dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, etc. Specific examples of the aromatic amine and heterocyclic amine include: aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2, 4-dinitroaniline, 2, 6-dinitroaniline, 3, 5-dinitroaniline, N-dimethyltoluidine, etc.), (p-tolyl) diphenylamine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, naphthyldiamine, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2, 4-dimethylpyrrole, 2, 5-dimethylpyrrole, N-methylpyrrole, etc.), (e.g., aniline, N-methylaniline, N, Oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, lutidine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, etc, 4-t-butylpyridine, biphenylylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinylpyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-cyanoisoquinoline, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pyridone derivatives, quinoxaline derivatives, pyridone derivatives, pteridine derivatives, carbazole derivatives, phenanthroline derivatives, acridine derivatives, phenazine derivatives, 1, 10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, and the like.

Further, examples of the nitrogen-containing compound having a carboxyl group include: aminobenzoic acid, indole carboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glutamyl leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like; examples of the nitrogen-containing compound having a sulfonyl group include: pyridinium 3-pyridinesulfonic acid and p-toluenesulfonate; examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the nitrogen-containing compound of an alcoholic type include: 2-hydroxypyridine, aminocresol, 2, 4-quinolinediol, 3-indolylmethanol hydrosol (3- インドールメタノールヒドレート), monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N-diethylethanolamine, triisopropanolamine, 2' -iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl ] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidone, 3-piperidyl-1, 2-propanediol, 8-hydroxy julolidine, 3-quinuclidinone, 3-tropine, 1-methyl-2-pyrrolidinoethanol, 1-acridinoethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, and the like. Examples of the amide derivative include: formamide, N-methylformamide, N-dimethylformamide, acetamide, N-methylacetamide, N-dimethylacetamide, propionamide, benzamide, and the like. Examples of the imide derivative include: phthalimide, succinimide, maleimide, and the like.

The amount of the basic compound to be blended is 0.001 to 2 parts, particularly preferably 0.01 to 1 part, per 100 parts of the cyclic compound. When the mixing amount is less than 0.001 part, no mixing effect is generated; when the amount exceeds 2 parts, all of the acid generated by heat may be trapped and crosslinking may not be performed.

In addition, other polymers for the purpose of controlling absorbance may be added to the composition for forming an underlayer film of the present invention. It is also possible to add: a naphthol resin having high transparency at 193 nm; naphthol modified resins of xylene resins; phenol-modified resins of naphthalene resins; a dicyclopentadiene resin; (meth) acrylic acid esters; resins containing a naphthalene ring (vinylnaphthalene, polyacenaphthylene, etc.), a biphenyl ring (phenanthrenequinone, fluorene, etc.), a heterocyclic ring having a hetero atom (thiophene, indene, etc.), or resins containing no aromatic ring.

Further, by introducing a substituent which condenses an aromatic group or an alicyclic group, the glass transition point can be lowered as compared with a usual phenol resin. At this time, the glass transition point can be lowered by 10 to 50 ℃ although it depends on the kind of the substituent to be introduced or the proportion thereof.

As another method for lowering the glass transition point, there is a method in which a hydrogen atom of a hydroxyl group of hydroxystyrene is substituted with an acid labile group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a tert-butyl group, a tert-pentyl group or an acetal, an acetyl group or a pivaloyl group, or the like.

The substitution rate in this case is in the range of 10 to 80 mol%, preferably 15 to 70 mol%, based on the hydroxyl group.

The organic solvent that can be used in the lower layer film-forming material of the present invention is not particularly limited as long as it is a solvent in which the above cyclic compound, acid generator C, crosslinking agent G, other additive F, and the like can be dissolved.

Examples thereof include: ketone solvents such as acetone, butanone, methyl isobutyl ketone, cyclohexanone, and the like; cellulose solvents such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.; alcohol solvents such as methanol, ethanol, isopropanol, 1-ethoxy-2-propanol, etc.; aromatic hydrocarbons such as toluene, xylene, etc.

Among the above solvents, cyclohexanone, propylene glycol monomethyl ether, ethyl lactate, and methyl hydroxyisobutyrate are particularly preferable.

The blending amount of the solvent is preferably 200-10000 parts, particularly preferably 300-5000 parts, relative to 100 parts of the cyclic compound.

In the method for forming an underlayer film of the present invention, after spin coating, the solvent is evaporated, and baking is preferably performed in order to prevent mixing with the upper layer resist and to promote a crosslinking reaction. The baking temperature is in the range of 80 to 300 deg.C, preferably in the range of 10 to 300 seconds. The thickness of the underlayer film may be suitably selected, and is preferably 30 to 20000nm, particularly preferably 50 to 15000 nm. After the lower layer film is prepared, a silicon-containing resist layer or a single-layer resist layer containing common hydrocarbon is prepared on the lower layer film under the condition of two-layer process; in the case of a three-layer process, an intermediate layer containing silicon is formed thereon, and a single-layer resist layer containing no silicon is formed thereon.

In this case, a known resist composition can be used for forming the resist layer.

As a silicon-containing resist composition used in a two-layer process, a positive photoresist composition is used in which a silicon atom-containing polymer (polysilsesquioxane derivative, vinylsilane derivative, or the like) is used as a base polymer, and an organic solvent, an acid generator, and a basic compound and the like are contained as necessary, from the viewpoint of oxygen etching resistance. As the silicon atom-containing polymer, a known polymer that can be used in such a resist composition can be used. As the silicon-containing intermediate layer used in the three-layer process, an intermediate layer using polysilsesquioxane as a raw material is preferably used. By providing the intermediate layer with an effect as an antireflection film, reflection can be suppressed.

When a material containing a large amount of aromatic groups and having high substrate etching resistance is used as an underlayer film for 193nm exposure, the substrate reflection increases due to an increase in k value, but by suppressing reflection in the intermediate layer, the substrate reflection can be made 0.5% or less. As the intermediate layer having the effect of preventing reflection, polysilsesquioxane, which has introduced a light absorbing group having a phenyl group or a silicon-silicon bond for exposure at 193nm and is crosslinked by acid or heat, is preferably used. In addition, an intermediate layer formed by a Chemical Vapor Deposition (CVD) method may also be used. As an intermediate layer which is formed by a CVD method and has a good effect as an antireflection film, a SiON film is known. The method of forming the intermediate layer by the spin coating method is simple and has an advantage in cost as compared with the CVD method. The upper layer resist in the three-layer process may be either a positive or negative type, and the same resist as a commonly used single layer resist may be used.

The underlayer film of the present invention can also be used as an antireflection film for a general single-layer resist. The lower layer film of the present invention has excellent etching resistance for substrate processing, and therefore can be expected to function as a hard film for substrate processing.

The present invention relates to a method for forming a multilayer resist pattern, wherein the method comprises: the method for producing a resist pattern includes the steps of forming the underlayer film on a substrate, forming at least one photoresist layer on the underlayer film, irradiating the photoresist layer with radiation in a range to which the photoresist layer is applied, performing alkali development to form a resist pattern, etching the underlayer film using plasma containing at least oxygen gas with the resist pattern as a mask, and transferring the resist pattern to the underlayer film.

When a resist layer is formed using the resist composition, a spin coating method can be preferably used as in the case of forming the underlayer film. After spin-coating the resist composition, a pre-bake is performed, preferably at 80-180 deg.C for 10-300 seconds. Thereafter, exposure, post-exposure baking (PEB), and alkali development were carried out according to a conventional method to obtain a resist pattern. The thickness of the resist film is not particularly limited, but is preferably 30 to 500nm, and more preferably 50 to 400 nm.

The light used for exposure is a high-energy beam having a wavelength of 300nm or less, and specifically includes excimer laser beams of 248nm, 193nm, and 157 nm; soft X-ray of 3-20nm, electron beam, X-ray, etc.

Next, the resulting resist pattern is masked and etched. The lower film in the two-layer process is etched by using oxygen. In addition to oxygen, inert gases (He, Ar, etc.) or CO, CO may be added₂、NH₃、SO₂、N₂、NO₂、H₂A gas; or only CO or CO can be used without oxygen₂、NH₃、N₂、NO₂、H₂Etching is performed under gas. The latter gas can be used in particular in side wall protection with the aim of preventing undercuts of the side walls of the pattern. Etching of the intermediate layer in a trilayer process, usingThe intermediate layer is processed by masking the resist pattern with fluorocarbon (フロン -series metal oxide layer ガス). Next, the oxygen etching is performed to mask the intermediate layer pattern, thereby processing the lower layer film.

The following etching of the substrate to be processed may be carried out by a conventional method, for example, etching of a substrate of SiO₂And in the case of SiN, etching with fluorocarbon as a main body is carried out; when the substrate is p-Si, Al or W, etching is performed mainly with a chlorine-based gas or a bromine-based gas. When a substrate to be processed is etched with fluorocarbon, a silicon-containing resist in a two-layer resist process and a silicon-containing intermediate layer in a three-layer process are peeled off simultaneously with the substrate to be processed. When a substrate is etched with a chlorine-based gas or a bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer needs to be peeled off separately from the substrate processing by dry etching using a fluorocarbon.

The lower layer film of the present invention is characterized in that the substrates to be processed have good etching resistance.

The substrate to be processed is formed on a substrate. The substrate is not particularly limited, and Si, α -Si, p-Si, SiO and the like can be used₂SiN, SiON, W, TiN, Al, etc., and a material property different from that of the film to be processed (substrate to be processed). As the film to be processed, various low-k films (Si, SiO) can be used₂SiON, SiN, p-Si, α -Si, W-Si, Al, Cu, Al-Si, etc.) and their stopper films (stopper film), can be formed in a thickness of usually 50 to 10000nm, particularly 100-5000 nm.

(Process (1) for production of Cyclic Compound B0)

The invention relates to a preparation method of a cyclic compound B0. As a first-stage reaction, an acid-dissociable functional group-introducing reagent is reacted with an aldehyde compound A1b having 2 to 59 carbon atoms and having a reactive functional group and 1 to 4 formyl groups to synthesize an aldehyde compound A1c into which an acid-dissociable functional group is introduced; as the second-stage reaction, a condensation reaction of the aldehyde compound A1c and the phenol compound a2 is carried out.

The cyclic compound B0 is a cyclic compound B0 having a molecular weight of 800-5000, which is synthesized by a condensation reaction of an aldehyde compound A1c and a phenol compound A2.

The cyclic compound B0 can be obtained by the following method: as a first-stage reaction, an acid-dissociable functional group is introduced into an aldehyde compound A1b having 2 to 59 carbon atoms and 1 to 4 formyl groups to synthesize an aldehyde compound A1 c; as the second-stage reaction, a condensation reaction of the aldehyde compound A1c and the phenol compound a2 is carried out.

A general cyclic low-molecular weight compound having an acid-dissociable functional group is produced by synthesizing a cyclic low-molecular weight polyphenol compound and reacting the cyclic low-molecular weight compound with a compound for introducing an acid-dissociable functional group, which will be described later.

However, such a method has the following cases: the cyclic low-molecular compound is hardly soluble in an organic solvent (e.g., tetrahydrofuran) used in the reaction, and is difficult to react with a compound for introducing an acid-dissociable functional group. Further, even if the cyclic low-molecular compound is soluble in an organic solvent, the reaction of the cyclic low-molecular compound with the compound for introducing the acid-dissociable functional group cannot be selectively performed, and a mixture of a combination of a plurality of substituted and unsubstituted compounds is obtained. It is generally difficult to selectively isolate the cyclic low-molecular compound having an acid-dissociable functional group from the mixture, and moreover, the yield is low and it is not practical.

In contrast, in the production method of the present invention, an acid dissociable functional group is introduced into the aldehyde compound A1b having 2 to 59 carbon atoms and 1 to 4 formyl groups by the first-stage reaction to synthesize the aldehyde compound A1 c. In this case, the compound A1b having 2 to 59 carbon atoms and 1 to 4 formyl groups and the compound for introducing an acid-dissociable functional group, which are the raw materials of the aldehyde compound A1c, are soluble in the organic solvent used for the reaction of THF or the like, and the reaction proceeds smoothly.

Then, as the second-stage reaction, the condensation reaction of the aldehyde compound A1c into which an acid dissociable functional group has been introduced and the phenol compound a2 is carried out to obtain the cyclic compound B0 into which an acid dissociable functional group has been introduced, and therefore, the solubility in the organic solvent used in the reaction is good and the reaction is not adversely affected, and further, the cyclic compound B0 into which an acid dissociable functional group has been selectively introduced can be obtained in high yield and productivity because the site derived from the aldehyde compound A1c has an acid dissociable functional group and the site derived from the phenol compound a2 has no acid dissociable functional group.

The aldehyde compound A1c is an aldehyde having 3 to 60 carbon atoms and 1 to 4 formyl groups, which has an acid-dissociable functional group.

The aldehyde compound A1c can be produced by introducing an acid-dissociable functional group into the compound A1b having 2 to 59 carbon atoms and 1 to 4 formyl groups.

The aldehyde compound having 2 to 59 carbon atoms and 1 to 4 formyl groups is not particularly limited, and examples thereof include: aliphatic aldehyde compounds, alicyclic aldehyde compounds, aromatic aldehyde compounds, and the like.

Examples of the aliphatic aldehyde compound include acetaldehyde, Ra-CHO (Ra is an optionally substituted alkyl group having 2 to 20 carbon atoms), OHC-Rb-CHO (Rb is an optionally substituted alkylene group having 1 to 20 carbon atoms), and Rc- (CHO)₃(Rc represents a trivalent organic group having 2 to 20 carbon atoms which may have a substituent),Rd-(CHO)₄(Rd is a tetravalent organic group which may have a substituent having 2 to 20 carbon atoms), and the like. The substituent is a functional group selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cyano, nitro, hydroxy, heterocyclic, halogen, carboxyl, alkylsilane, and derivatives thereof.

Examples of the alicyclic aldehyde compound include: cyclohexyl formaldehyde (シクロヘキサンカルボアルデヒド), cyclohexyl formaldehyde which may have a substituent having 2 to 20 carbon atoms, cyclooctyl formaldehyde, norbornyl formaldehyde, adamantyl formaldehyde, furfural, diformylcyclohexane, diformylcyclooctane, diformylcornane, diformyladamantane, trimethylacylcyclohexane, trimethylacylcyclooctane, trimethylacylnorbornane, trimethyloyladamantane, trimethyloylcyclohexane, tetramethylacylcyclooctane, tetramethyloylnorbornane, tetramethyloyladamantane, and the like. The substituent is a functional group selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cyano, nitro, hydroxy, heterocyclic, halogen, carbonyl, alkylsilane, and derivatives thereof.

Examples of the aromatic aldehyde compound include: benzaldehyde, tolualdehyde, benzaldehyde which may have a substituent having 2 to 20 carbon atoms, anisaldehyde, naphthaldehyde, anthracenal, diphenylaldehyde, formylfluorene, formylbiphenyl, formylanthracene, formylphenanthrene, formylphenothiazine, formylpyrene, formylbenzopyrene, formylbenzindene, formylbenzonaphthalene, formylacenaphthylene, formylnaphthonaphthalene, formylvalerene, formyltriphenocene, formylpyridine, formylovalene, diformylbenzene, diformyltoluene, diformylxylene, diformylnaphthalene, diformylbiphenyl, diformylditritylene, diformylanthracene, diformylphenanthrene, diformylpyrene, diformylbenzenediindene, diformylphenalene, diformylnaphthonaphthalene, diformylpentacene, diformylpyridine, diformylphenanthrene, diformylpyrene, diformylbenzene, diformylphenalene, diformylphenacene, diform, Diformylimidazole, diformylfuran, diformylthiazole, diformylflavone, diformylisoflavonoid, trimethylacetophenone, trimethyltoluol, trimethylxylene, trimethylnaphthalene, trimethylbiphenyl, trimethylterphenyl, trimethylanthracene, trimethylphenanthrene, trimethylpyrene, trimethylbenzindene, trimethylphenalene, trimethylacenaphthylene, trimethylphenalene, trimethylnaphthonaphthalene, trimethylvalerene, trimethylterphenyl, trimethylpyridone, trimethylimidazole, trimethylfuran, trimethylthiazole, trimethylflavone, trimethylisoflavone, tetramethylbenzene, tetramethylnaphthalene, tetramethylbiphenyl, tetramethylterphenyl, tetramethylanthracene, tetramethylphenanthrene, tetramethylpyrene, tetramethylbenzindene, tetramethylphenalene, Tetraformylacenaphthylene, tetraacylphenalene, tetraacylnaphthonaphthalene, tetraacylpentalene, tetraacyltetrao-phenylene, tetraacylpyridone, tetraacylimidazole, tetraacylfuran, tetraacylthiazole, tetraacylflavone, tetraacylisoflavone, etc. The substituent is a functional group selected from the group consisting of alkyl, cycloalkyl, aryl, alkoxy, cyano, nitro, hydroxy, heterocyclic, halogen, carboxyl, alkylsilane, and derivatives thereof.

Further, as the heterocycle-containing aldehyde compound, there may be mentioned: furfural, nicotinaldehyde, 2-tetrahydrofuraldehyde, 2-thiophenecarboxaldehyde, and the like.

These compounds are preferably substituted with a hydroxyl group, a borate group, a halogen atom, a carboxyl group, or the like, and an acid-dissociable functional group is easily introduced.

Among them, aromatic aldehydes having 1 to 4 formyl groups are preferable from the viewpoint of etching resistance; from the viewpoint of facilitating the formation of a fine pattern, an aromatic aldehyde having 1 to 2 formyl groups is more preferable; the aromatic aldehyde having 1 formyl group is more preferable from the viewpoint of enabling the aromatic aldehyde itself and the cyclic compound B0 to be produced in high yield and high purity.

The compound for introducing an acid-dissociable functional group can be synthesized by a known method or can be easily obtained, and examples thereof include active carboxylic acid derivative compounds such as acid chlorides, acid anhydrides, and dicarbonates; an alkyl halide; vinyl alkyl ethers, dihydropyrans, alkyl halocarboxylates, and the like, but are not particularly limited. The purity of the compound having 2 to 59 carbon atoms and 1 to 4 formyl groups and the compound for introducing an acid-dissociable functional group is not particularly limited, but is usually 95% by mass or more, preferably 99% by mass or more. The compound having 2 to 59 carbon atoms and 1 to 4 formyl groups and the compound for introducing an acid-dissociable functional group may be used alone or in combination of two or more, but are preferably used alone because the uniformity of the solid content of the resist film is high.

The aldehyde compound A1c can be prepared, for example, as follows. For example, it is possible to prepare a phenol compound by dissolving or suspending a benzaldehyde having a phenolic hydroxyl group (e.g., 4-hydroxybenzaldehyde, etc.) in an organic solvent (e.g., acetone, tetrahydrofuran, etc.). Then, adding alkyl halide (such as cyclohexyl chloromethyl ether, etc.) or alkyl halocarboxylate (such as methyl adamantyl bromoacetate, etc.), and reacting for 0.1-72 hours under normal pressure and at 20-110 ℃ in the presence of alkali catalyst (such as potassium carbonate, etc.); the reaction solution was neutralized with an acid, and added to distilled water to precipitate a white solid, and then the separated white solid was washed with distilled water and finally dried.

The aldehyde compound A1c can be obtained by the following method: dissolving or suspending benzaldehyde having a phenolic hydroxyl group (e.g., 4-hydroxybenzaldehyde, etc.) in an aprotic solvent (e.g., acetone, tetrahydrofuran, propylene glycol monomethyl ether acetate, etc.); then, adding vinyl alkyl ether (such as cyclohexyl vinyl ether, etc.), and reacting for 0.1-72 hours at 20-60 ℃ under normal pressure in the presence of acid catalyst (such as pyridinium p-toluenesulfonate, etc.); then, the reaction solution was neutralized with an alkali compound, added to distilled water to precipitate a white solid, and then the separated white solid was washed with distilled water and finally dried.

The aldehyde compound a1 can be obtained by the following process: carboxybenzaldehyde (e.g., 3-carboxybenzaldehyde, etc.) and an alcohol having an acid-dissociable functional group (e.g., methyladamantyl methanol, etc.) are reacted in an organic solvent (e.g., tetrahydrofuran, etc.) using an esterification catalyst (e.g., an acid, a base, etc.).

The aldehyde compound A1c can be obtained by the following process: a halogenated benzaldehyde (e.g., 4-chlorobenzaldehyde, 4-bromobenzaldehyde, etc.) or 4-chloromethylbenzaldehyde or 4-bromomethylbenzaldehyde is reacted with a Grignard reagent by a Grignard reaction using a copper catalyst.

The aldehyde compound A1c can be obtained by the following process: in an organic solvent (e.g., tetrahydrofuran, etc.), a halogenated benzaldehyde (e.g., 4-chlorobenzaldehyde, 4-bromobenzaldehyde, etc.) or 4-chloromethylbenzaldehyde or 4-bromomethylbenzaldehyde is reacted with a Grignard reagent by a Grignard reaction using a copper catalyst.

The aldehyde compound A1c can be obtained by the following process: formylated phenylboronic acids (e.g., 4-formylphenylboronic acid, etc.) are reacted with alkyl halides (e.g., cyclohexyl chloromethyl ether, etc.) or alkyl halocarboxylates (e.g., methyl adamantyl bromoacetate, etc.) in an organic solvent (e.g., tetrahydrofuran, etc.) by suzuki coupling using palladium and a base catalyst.

The aldehyde compound A1c is not particularly limited, and examples thereof include: examples of the compound having 1 to 4 formyl groups and having 2 to 59 carbon atoms include compounds having an acid-dissociable functional group introduced thereto.

The aldehyde compound A1c is preferably an aromatic aldehyde compound from the viewpoint of etching resistance; from the viewpoint of facilitating the formation of a fine pattern, an aromatic aldehyde compound having 1 to 2 formyl groups is more preferable; further preferred is an aromatic aldehyde compound having 1 formyl group.

The aldehyde compound A1c is preferably a compound represented by the following formula (47).

[ chemical formula 95]

(wherein L is selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, -O-, -OC (. gtoreq.O) -, -OC (. gtoreq.O) O-, -N (R)₅)-C(＝O)-、-N(R₅)-C(＝O)O-、-S-、-SO-、-SO₂-and any combination thereof; r¹An acid-dissociable functional group or a hydrogen atom selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group; r ²A functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof; r⁵Is hydrogen atom or alkyl with 1-10 carbon atoms; m is₁Is an integer of 1 to 5; m is₂Is an integer of 0 to 4; m is₁+m₂＝5。)

The compound represented by the above formula (47) can be produced by the method described above.

The aldehyde compound A1c is more preferably a compound represented by the following formula (48).

[ chemical formula 96]

(in the formula, L, R¹、m₁As described above. )

The compound represented by the above formula (48) can be produced by the method described above.

The aldehyde compound A1c is more preferably a compound represented by the following formula (49).

[ chemical formula 97]

(in the formula, L, R¹As described above. )

The compound represented by the above formula (1-3) can be produced by the method described above.

The aldehyde compound A1c is particularly preferably a compound represented by the following formula (50).

[ chemical formula 98]

(in the formula, R¹As described above. )

The compound represented by the above formula (50) can be produced by the method described above.

In the formulae (47) to (50), R¹An acid-dissociable functional group selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group having 2 to 20 carbon atoms. These may use the same groups as those described for the above cyclic compounds. R¹The same or different, and the same is preferable because the uniformity of the solid content of the resist film is high.

R¹More preferably an acid-dissociable functional group having a structure selected from the group consisting of cycloalkanes having 3 to 20 carbon atoms, lactones, and aromatic rings having 6 to 12 carbon atoms. The cycloalkane having 3 to 12 carbon atoms may be a monocyclic ring or a polycyclic ring, and a polycyclic ring is more preferable. Specific examples thereof include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc.; more specifically, there may be mentioned monocycloalkanes such as cyclopropane, cyclobutane, cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclodecane. Among them, adamantane, tricycloalkane and tetracycloalkane are preferable, and adamantane and tricycloalkane are particularly preferable. Cycloalkane having 3 to 12 carbon atoms May have a substituent. Examples of the lactone include butyrolactone and a cycloalkyl group having 3 to 12 carbon atoms and having a lactone group. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and the like, and a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is particularly preferable.

Particularly preferred is an acid-dissociable functional group represented by the following formula (50-1). By having the acid-dissociable functional group, the resolution and LER of the resulting resist pattern are improved.

[ chemical formula 99]

(in the formula, R⁵、R⁶、n₀、n₁、n₂As described above. )

Examples of the phenolic compound a2 include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, with resorcinol and pyrogallol being preferred, and resorcinol being more preferred. The phenolic compound a2 may have a substituent selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an alkanoyloxy group, an aroyloxy group, a cyano group, a nitro group, a heterocyclic group, an alkylsilane, a substituted methyl group, a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, a 1-substituted alkoxyalkyl group, a cyclic ether group, and an alkoxycarbonylalkyl group, as long as the effects of the present invention are not impaired. The purity of the phenolic compound a2 is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more. The phenol compound a2 may be used singly or in combination, and is preferable because the uniformity of the solid content of the resist film is high when used singly.

In one embodiment of the present invention, the cyclic compound B0 is preferably a compound represented by the following formula (51).

[ chemical formula 100]

In the formula, R³Independently a functional group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane having 1 to 20 carbon atoms, and derivatives thereof, or a functional group selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a substituted alkoxy, An acid-dissociable functional group selected from the group consisting of a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group; l, R ¹、R²、m₁And m₂The same as in the above formula (47).

In the formula, R³The same or different, and the same is more preferable because the uniformity of the radiation-sensitive composition increases and the roughness of the resulting resist pattern decreases.

The cyclic compound B0 represented by the above formula (51) can be produced, for example, as follows.

For example, it can be prepared by the following method: in an organic solvent (such as methanol, ethanol, etc.), in the presence of an acid catalyst (hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, etc.), using a molar ratio of 1: (0.1-10) aldehyde compound A1c and phenol compound A2, reacting at 0-100 deg.C for about 0.5-72 hr, filtering, washing with alcohol (such as methanol), washing with water, filtering, separating, and drying. It can also be obtained by using a basic catalyst (sodium hydroxide, barium hydroxide, 1, 8-diazabicyclo [5.4.0] undec-7-ene, etc.) in place of the acid catalyst, and by carrying out the reaction in the same manner. Further, the cyclic compound B0 can be produced by converting the aldehyde compound A1c into a dihalide with a hydrogen halide or a halogen gas, and reacting the isolated dihalide with the phenol compound a 2.

The cyclic compound B0 is more preferably a compound represented by the following formula (52).

[ chemical formula 101]

(in the formula, L, R¹、R²、m₁And m₂The same as in the above formula (51). )

The cyclic compound B0 represented by the above formula (52) can be produced by the method described above.

The cyclic compound B0 is more preferably a compound represented by the following formula (53).

[ chemical formula 102]

(in the formula, L, R¹、m₁The same as in the above formula (51). )

The cyclic compound B0 represented by the above formula (53) can be produced by the method described above.

The cyclic compound B0 is particularly preferably a compound represented by the following formula (54).

[ chemical formula 103]

(in the formula, R¹The same as in the above formula (51). )

The cyclic compound B0 represented by the above formula (54) can be produced by the method described above.

In the formula (51), R³Is a functional group selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cyano group, a nitro group, a hydroxyl group, a heterocyclic group, a halogen, a carboxyl group, an alkylsilane, and derivatives thereof, or an acid-dissociable functional group selected from the group consisting of a substituted methyl group of C2-20, a 1-substituted ethyl group of C3-20, a 1-substituted n-propyl group of C4-20, a 1-branched alkyl group of C3-20, a silyl group of C1-20, an acyl group of C2-20, a 1-substituted alkoxyalkyl group of C2-20, a cyclic ether group of C2-20, and an alkoxycarbonyl group of C2-20.

Examples of the acid-dissociable functional group selected from the group consisting of a C2-20 substituted methyl group, a C3-20 1-substituted ethyl group, a C4-20 1-substituted n-propyl group, a C3-20 1-branched alkyl group, a C1-20 silyl group, a C2-20 acyl group, a C2-20 1-substituted alkoxyalkyl group, a C2-20 cyclic ether group and a C2-20 alkoxycarbonyl group include a group dissociating with an acid and a group dissociating with the above-mentioned R¹The same acid-dissociable functional group, and the like.

An acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group of the cyclic compound B0 within a range not to impair the effects of the present invention. A method of introducing an acid-dissociable functional group into at least one phenolic hydroxyl group of the cyclic compound B0 is known. For example, the method can be performed in the same manner as the above-described method of introducing an acid-dissociable functional group into a compound having from 1 to 4 formyl groups and from 2 to 59 carbon atoms.

For example, the target compound can be obtained by the following method: dissolving or suspending the cyclic compound B0 in an aprotic solvent (e.g., acetone, Tetrahydrofuran (THF), propylene glycol monomethyl ether acetate, etc.); then, adding vinyl alkyl ether (such as ethyl vinyl ether) or dihydropyran, and reacting for 1-72 hours at 20-60 ℃ under normal pressure in the presence of acid catalyst (such as pyridinium p-toluenesulfonate); then, the reaction solution was neutralized with an alkali compound, added to distilled water to precipitate a white solid, and then the separated white solid was washed with distilled water and finally dried.

The target compound can be obtained by the following method: dissolving or suspending the cyclic compound B0 in an aprotic solvent (e.g., acetone, THF, propylene glycol monomethyl ether acetate, etc.); then, adding alkyl halide (such as ethyl chloromethyl ether, etc.) or alkyl halocarboxylate (such as methyl adamantyl bromoacetate, etc.), and reacting for 1-72 hours under normal pressure and at 20-110 ℃ in the presence of alkali catalyst (such as potassium carbonate, etc.); the reaction solution is neutralized with an acid such as hydrochloric acid, and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and finally dried.

The cyclic compound B0 is a low molecular weight compound, has film-forming properties, heat resistance, dry etching resistance, and low outgassing properties, and is a pure compound, and therefore has high uniformity of components in a resist film, and is therefore preferable as a resist component of a radiation-sensitive composition. The radiation-sensitive composition containing the cyclic compound B0 has good resolution, sensitivity and low line edge roughness.

(Process (2) for production of Cyclic Compound B0)

The present invention relates to a process for producing a cyclic compound B0, wherein, as a first-stage reaction, a condensation reaction of an aldehyde compound A1d having 2 to 59 carbon atoms and having 1 to 2 carboxyl groups or ester groups and 1 to 4 formyl groups with a phenol compound A2 is carried out to synthesize a cyclic compound A0 having 1 to 8 carboxyl groups in the molecule and having a molecular weight of 700-5000; as the second reaction, a reaction of the cyclic compound A0 having a carboxyl group and the compound A3 having a halomethyl ether group was carried out.

Instead of the halomethylether-based compound A3, an alkyl halocarboxylate a4 may also be used to give the cyclic compound B0.

The alkyl halocarboxylate a4 is not particularly limited, and examples thereof include: aliphatic compounds having 1 to 2 haloalkylcarboxy groups, alicyclic compounds having 1 to 2 haloalkylcarboxy groups, aromatic compounds having 1 to 2 haloalkylcarboxy groups, and the like, and compounds represented by the following formula (55) are preferable.

[ chemical formula 104]

(in the formula, R⁷Is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; x is a halogen atom; l is ₁Is a divalent organic group selected from a single bond and a linear or branched alkyl group having 1 to 4 carbon atoms. )

The branched alkyl group having 3 to 20 carbon atoms is preferably 3 to 10 carbon atoms, and specific examples thereof include an isopropyl group, a tert-butyl group, an isopentyl group, and a neopentyl group.

The cycloalkyl group having 3 to 20 carbon atoms is preferably 6 to 14 carbon atoms. The alicyclic ring contained in the cycloalkyl group may be monocyclic or polycyclic, and polycyclic is more preferable. Specific examples thereof include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc.; more specifically, there may be mentioned monocycloalkanes such as cyclopropane, cyclobutane, cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclodecane. Among them, adamantane, tricycloalkane and tetracycloalkane are preferable, and adamantane and tricycloalkane are particularly preferable.

Alkyl halocarboxylate a4 can be obtained by the following process: for example, an alcohol (e.g., 2-methyl-2-adamantanol, etc.) is dissolved in an organic solvent (e.g., tetrahydrofuran, etc.), a base such as pyridine, etc. is added in an amount of 0.8 to 2.4 equivalents relative to the alcohol, and a halocarboxylic acid halide (e.g., bromoacetyl bromide, etc.) is added in an amount of 0.8 to 2.4 equivalents relative to the alcohol, and the reaction is carried out at 0 to 100 ℃; after the reaction is completed, the product is isolated by column chromatography or the like to obtain the desired alkyl halocarboxylate a 4.

The cyclic compound B0 can be obtained by the reaction of a cyclic compound a0 having a carboxyl group and an alkyl halocarboxylate a 4. For example, cyclic compound B0 can be obtained by the following method: for example, the cyclic compound a0 having a carboxyl group is dissolved or suspended in an aprotic solvent (e.g., acetone, THF, propylene glycol monomethyl ether acetate, etc.), followed by addition of an alkyl halocarboxylate a4, reaction at 0.5 to 4 equivalents, preferably 0.9 to 1.1 equivalents, more preferably 1.0 equivalent, relative to the carboxyl group of the cyclic compound a0 having a carboxyl group, in the presence of a base catalyst (e.g., pyridine, triethylamine, diazabicycloundecene, potassium carbonate, etc.) at normal pressure at 0 to 110 ℃ for 1 to 168 hours, followed by washing with an alcohol (e.g., methanol, etc.), followed by washing with water, followed by filtration and isolation, and finally, drying. The compound may be purified by column chromatography or the like as necessary.

The respective requirements other than those described above are the same as those described for the above-mentioned radiation-sensitive composition B.

(method of Forming resist Pattern)

The present invention relates to a method of forming a resist pattern, the method comprising: a step of forming a resist film on a substrate using any one of the above-described radiation-sensitive compositions a to C of the present invention; exposing the resist film; and a step of developing the resist film to form a resist pattern.

To form a resist pattern, first, the radiation-sensitive composition of the present invention is applied to a substrate (e.g., a silicon wafer, a wafer covered with aluminum, etc.) by an application method such as spin coating, cast coating, roll coating, etc., to form a resist film. If necessary, a surface treatment agent (e.g., hexamethylenedisilazane) may be applied to the substrate in advance.

Next, the coated substrate is heated as necessary. The heating temperature varies depending on the blending composition of the radiation-sensitive composition, etc., but is preferably 20 to 250 ℃ and more preferably 20 to 150 ℃. Heating is preferable because adhesiveness of the resist to the substrate may be improved. Next, the resist film is exposed to a desired pattern by any one of radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, Extreme Ultraviolet (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected depending on the blend composition of the radiation-sensitive resist composition and the like. In the present invention, in order to stably form a high-fidelity fine pattern in exposure, it is preferable to heat the pattern after irradiation with radiation. The heating conditions vary depending on the blending composition of the radiation-sensitive resist composition, etc., but are preferably 20 to 250 ℃ and more preferably 20 to 150 ℃.

Next, the exposed resist film is developed with an alkali developer to form a predetermined resist pattern. As the alkali developing solution, for example, an alkali aqueous solution in which at least one of monoalkylamines, dialkylamines, or trialkylamines, monoalkylamines, dialkanolamines, or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline, and the like is dissolved at a concentration of preferably 1 to 10% by weight, more preferably 1 to 5% by weight can be used. When the concentration of the alkaline aqueous solution is 10% by mass or less, the dissolution of the exposed portion in the developer can be suppressed, and therefore, the concentration is preferable.

In addition, an appropriate amount of an alcohol or the above-mentioned surfactant (e.g., methanol, ethanol, isopropanol, etc.) may be added to the alkali developing solution. Of these, isopropanol is particularly preferably added in an amount of 10 to 30% by weight. This is preferable because the wettability of the resist with the developer can be improved. When such a developer composed of an alkaline aqueous solution is used, it is generally washed with water after development.

After the resist pattern was formed, a patterned wiring board was obtained by etching. The etching method can be performed by a known method, such as dry etching using plasma gas, wet etching using an alkali solution, a copper chloride solution, an iron chloride solution, or the like.

After the resist pattern is formed, plating may be performed. Examples of the plating method include copper plating, tin plating, nickel plating, and gold plating.

The residual resist pattern after etching can be stripped with an organic solvent or an alkaline aqueous solution having a stronger alkalinity than that of the alkaline aqueous solution used for development. 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 aqueous strong alkali solution include: 1-20 wt% aqueous sodium hydroxide solution and 1-20 wt% aqueous potassium hydroxide solution. Examples of the above-mentioned peeling method include: dipping method, spraying method, etc. The wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a through hole with a small diameter.

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

Examples

The embodiments of the present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In the following synthesis examples and examples, the structures of the compounds are shown by ¹H-NMR measurement.

Synthesis of Cyclic Compound A in Synthesis example 1

Synthesis of CR-1

In a four-necked flask (1000L) equipped with a dropping funnel, a Diety condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, resorcinol (22g, 0.2mol) manufactured by Kanto chemical Co., Ltd., 4-isopropylbenzaldehyde (29.6g, 0.2mol) and absolute ethanol (200ml) were charged under a nitrogen gas flow to prepare an ethanol solution. The solution was heated to 85 ℃ with a mantle resistance heater while stirring. Then, 75ml of concentrated hydrochloric acid (35%) was added dropwise over 30 minutes through a dropping funnel, and the stirring was continued at 85 ℃ for 3 hours. After the reaction, the reaction mixture was cooled to room temperature and then cooled in an ice bath. After standing for 1 hour, a pale yellow crude crystal of interest was produced, which was isolated by filtration. The crude crystals were washed 2 times with 500ml of methanol, separated by filtration, and dried under vacuum to give the desired product (hereinafter referred to as CR-1) (45.6g, yield 95%). The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the target substance was 960. In addition, in deuterated dimethyl sulfoxide (heavy ジメチルスルホキシド) solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.2(m, 24H), 2.6 to 2.7(m, 4H), 5.5(s, 24H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 8H).

[ chemical formula 105]

Synthesis of CR-2

Synthesis was carried out in the same manner as in CR-1 except that 4-isopropylbenzaldehyde in the synthesis example of CR-1 was replaced with 4-n-propylbenzaldehyde. As a result, CR-2(45.6g, yield 95%)). The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the target substance was 960. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.4 to 1.6(m, 8H), 2.3 to 2.5(m, 8H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 8H).

[ chemical formula 106]

Synthesis of CR-3

Synthesis was carried out in the same manner as in CR-1 except that half the molar amount of 4-isopropylbenzaldehyde in the synthesis example of CR-1 was replaced with 4-n-propylbenzaldehyde. As a result, CR-3(45.6g) was obtained. The compound was analyzed by LC-MS, and the molecular weight of the target substance was 960. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.2(m, 36H), 1.4 to 1.6(m, 8H), 2.3 to 2.7(m, 12H), 5.5(d, 8H), 6.0 to 6.8(m, 48H), 8.4,8.5(m, 16H).

[ chemical formula 107]

R^1AIso-propyl/n-propyl (1/1)

Synthesis of CR-4

Synthesis was carried out in the same manner as for CR-1 except that 1/4 mol in 4-isopropylbenzaldehyde in the example of CR-1 synthesis was replaced by bromobenzaldehyde. As a result, 45.5g of CR-4 was obtained. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.2(m, 18H), 2.6 to 2.7(m, 3H), 5.5(m, 4H), 6.0 to 6.8(m, 24H), 8.4 to 8.5(m, 8H).

By¹The chemical shift values of H-NMR are suggestive of the overall structure of the number of bromine atoms relative to CR-4The ratio of the number of the constituent atoms was 0.8%.

[ chemical formula 108]

R^1BIsopropyl/bromo (3/1)

Synthesis of CR-5

Synthesis was carried out in the same manner as in CR-1 except that 1/4 mol in 4-isopropylbenzaldehyde in the synthesis example of CR-1 was replaced by bromobenzaldehyde and 1/8 mol was replaced by dimethylaminobenzaldehyde. As a result, 45.5g of CR-5 was obtained.

In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.2(m, 30H), 2.6 to 2.7(m, 5H), 2.9(m, 6H), 5.5(m, 8H), 6.0 to 6.8(m, 48H), 8.4,8.5(m, 16H).

By¹The chemical shift value in H-NMR was found to be 0.8% for the number of bromine atoms and 0.4% for the number of nitrogen atoms, respectively, based on the total number of constituent atoms of CR-5.

[ chemical formula 109]

R^1CIs isopropyl/bromo/N (CH)₃)₂(5/2/1)

Synthesis of CR-6

Synthesis was carried out in the same manner as in CR-1 except that 4-isopropylbenzaldehyde was replaced with 2, 4-dimethylbenzaldehyde in the synthesis example of CR-1. As a result, CR-6(44.3g, yield 98%) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 904. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(d, 12H), 1.4 to 1.6(d, 12H), 5.6(t, 4H), 6.1 to 6.5(m, 20H), 8.3 to 8.5(m, 8H).

[ chemical formula 110]

Synthesis of CR-7

Synthesis was carried out in the same manner as in CR-1 except that 4-isopropylbenzaldehyde in the synthesis example of CR-1 was replaced with isobutylbenzaldehyde. As a result, CR-7(49.0g, yield 96%) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the target substance was 1017. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.7(m, 4H), 2.3 to 2.4(m, 8H), 5.5(d, 4H), 5.8 to 6.8(m, 24H), 8.4 to 8.6(t, 8H).

[ chemical formula 111]

Synthesis of CR-8

Synthesis was carried out in the same manner as for CR-1 except that 4-isopropylbenzaldehyde (ビフェニルアルデヒド) was used instead of biphenylformaldehyde in the synthesis example of CR-1. As a result, CR-8(53.5g, yield 98%) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the objective substance was 1096. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 24H), 8.6 to 8.7(t, 8H).

[ chemical formula 112]

Synthesis of CR-9

Synthesis was carried out in the same manner as in CR-1 except that 4-isopropylbenzaldehyde in the synthesis example of CR-1 was replaced with 3-bromo-4-methylbenzaldehyde. As a result, CR-9(56.3g, 97% yield) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 1160. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.2(d, 12H), 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 20H), 8.6 to 8.7(t, 8H).

[ chemical formula 113]

Synthesis of CR-10

Synthesis was carried out in the same manner as in CR-1 except that 4-isopropylbenzaldehyde in the synthesis example of CR-1 was replaced with 5-bromo-2, 4-dimethylbenzaldehyde. As a result, CR-10(57.8g, yield 95%) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the objective substance was found to be 1216. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(d, 12H), 1.4 to 1.6(d, 12H), 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 16H), 8.6 to 8.7(t, 8H).

[ chemical formula 114]

Synthesis of CP-1

Synthesis was carried out in the same manner as for CR-1 except that resorcinol in the synthesis example of CR-1 was replaced with pyrogallol. As a result, CP-1(49.9g, yield 97%) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the target substance was 1024. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.4 to 1.6(m, 8H), 2.3 to 2.5(m, 8H), 5.5(s, 4H), 6.0 to 6.8(m, 20H), 8.4 to 8.5(m, 12H).

[ chemical formula 115]

Synthesis of CP-2

Synthesis was carried out in the same manner as in CR-1 except that 4-isopropylbenzaldehyde was replaced by 4-biphenylformaldehyde and resorcinol was replaced by pyrogallol in the synthesis example of CR-1. As a result, CP-2(55.8g, yield 96%) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 1160. In addition, the obtained product is in deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 20H), 8.6 to 8.7(m, 12H).

[ chemical formula 116]

Synthesis of Cyclic Compound B in Synthesis example 2

Synthesis of BOC50CR-1

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 8.7g (40mmol) of di-tert-butyl dicarbonate was added dropwise under a nitrogen gas flow to a solution composed of 9.6g (10mmol) of CR-1 synthesized in Synthesis example 1, 0.1g (1mmol) of 4, 4' -dimethylaminopyridine and 500ml of acetone. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. 13.0g in total of BOC50CR-1 in which 50 mol% of the phenolic hydroxyl group was replaced with tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.3(m, 60H), 2.6 to 2.7(m, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of tBu50CR-1

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, a THF solution (100 ml) of t-butyl bromoacetate (7.7 g, 40mmol) was added dropwise to a solution composed of CR-1 synthesized in Synthesis example 1 (9.6 g, 10mmol), potassium carbonate (13.8 g) and THF (400 ml) under a nitrogen gas flow. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. 12.9g in total of tBu50CR-1 in which 50 mol% of the phenolic hydroxyl group was replaced by a tert-butoxycarbonylmethyl group was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.2(m, 24H), 1.5(d, 36H), 2.6 to 2.7(m, 4H), 4.4 to 4.5(d, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of MAD50CR-1

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, a solution of 9.6g (10mmol) of CR-1 synthesized in Synthesis example 1, 13.8g of potassium carbonate and 400ml of THF was added dropwise with a solution of 11.4g (40mmol) of methyladamantyl bromoacetate in 100ml of THF under a stream of nitrogen gas. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 14.0g in total of MAD50CR-1 in which 50 mol% of the phenolic hydroxyl groups were replaced with methyl adamantyloxycarbonylmethyl groups was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.2(m, 24H), 1.4 to 2.2(m, 68H), 2.6 to 2.7(m, 4H), 4.4 to 4.5(d, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of EE50CR-1

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 2.9g (40mmol) of ethyl vinyl ether was dropped into a solution composed of 9.6g (10mmol) of CR-1 synthesized in Synthesis example 1, 2.5g of pyridinium p-toluenesulfonate and 400ml of acetone under a nitrogen gas flow. The reaction solution was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 11.2g in total of EE50CR-1 in which 50 mol% of the phenolic hydroxyl groups were replaced with ethoxyethyl groups was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.1 to 1.2(m, 24H), 1.3 to 1.4(m, 12H), 2.6 to 2.7(m, 4H), 3.3 to 3.4(m, 8H), 5.1(m, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of CE50CR-1

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 5.0g (40mmol) of cyclohexyl vinyl ether was dropped under a nitrogen gas flow into a solution composed of 9.6g (10mmol) of CR-1 synthesized in Synthesis example 1, 2.5g of pyridinium p-toluenesulfonate and 400ml of 1, 3-dioxolane. The reaction solution was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 12.2g in total of CE50CR-1 in which 50 mol% of the phenolic hydroxyl groups were replaced with cyclohexyloxyethyl groups was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.2(m, 24H), 1.3 to 1.4(m, 12H), 2.6 to 2.7(m, 4H), 5.1(m, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of BOC50CR-2

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-2 was replaced with CR-1 in the synthesis example of BOC50 CR-1. As a result, 30.0g in total of BOC50CR-2 in which 50 mol% of the phenolic hydroxyl group was replaced by tert-butoxycarbonyl was obtained.

Dissolving the obtained product in deuterated dimethyl sulfoxideIn the preparation¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.4 to 1.6(m, 8H), 2.3 to 2.5(m, 8H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of tBu50CR-2

Synthesis was carried out in the same manner as for tBu50CR-1 except that CR-2 was replaced with CR-1 in the synthesis example of tBu50 CR-1. As a result, 30.0g in total of tBu50CR-2 in which 50 mol% of the phenolic hydroxyl group was replaced by a tert-butoxycarbonylmethyl group was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.4 to 1.6(m, 44H), 2.3 to 2.5(m, 8H), 4.4 to 4.5(d, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of MAD50CR-2

Synthesis was carried out in the same manner as for MAD50CR-1, except that CR-2 was replaced with CR-1 in the example of the synthesis of MAD50 CR-1. As a result, 30.0g in total of MAD50CR-2 in which 50 mol% of the phenolic hydroxyl groups were replaced with methyl adamantyloxycarbonylmethyl groups was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.4 to 2.2(m, 76H), 2.3 to 2.5(m, 8H), 4.4 to 4.5(d, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of EE50CR-2

Synthesis was carried out in the same manner as EE50CR-1 except that CR-2 was replaced with CR-1 in the synthesis example of EE50 CR-1. As a result, 30.0g in total of EE50CR-2 in which 50 mol% of the phenolic hydroxyl groups were replaced with ethoxyethyl groups was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.3 to 1.4(m, 12H), 3.3 to 3.4(m, 8H), 5.1(m, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of CE50CR-2

Synthesis was carried out in the same manner as in CE50CR-1 except that CR-2 was used instead of CR-1 in the synthesis example of CE50 CR-1. As a result, 30.0g in total of CE50CR-2 in which 50 mol% of the phenolic hydroxyl groups were replaced with cyclohexyloxyethyl groups was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.3 to 1.4(m, 12H), 1.4 to 1.6(m, 8H), 2.3 to 2.5(m, 8H), 5.1(m, 4H), 5.5(s, 4H), 6.0 to 6.8(m, 24H), 8.4,8.5(d, 4H).

Synthesis of BOC50CR-3

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-3 was used instead of CR-1 in the synthesis example of BOC50 CR-1. As a result, 30.0g in total of BOC50CR-3 in which 50 mol% of the phenolic hydroxyl group was replaced by tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.2(m, 36H), 1.2 to 1.3(m, 72H), 1.4 to 1.6(m, 8H), 2.3 to 2.7(m, 12H), 5.5(d, 8H), 6.0 to 6.8(m, 48H), 8.4,8.5(m, 8H).

Synthesis of BOC50CR-4

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-4 was replaced with CR-1 in the synthesis example of BOC50 CR-1. As a result, 30.0g in total of BOC50CR-4 in which 50 mol% of the phenolic hydroxyl group was replaced by tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.2(m, 18H), 1.2 to 1.3(m, 36H), 2.6 to 2.7(m, 3H), 5.5(m, 4H), 6.0 to 6.8(m, 24H), 8.4 to 8.5(m, 4H).

Synthesis of BOC50CR-5

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-5 was replaced with CR-1 in the synthesis example of BOC50 CR-1. As a result, 30.0g in total of BOC50CR-5 in which 50 mol% of the phenolic hydroxyl group was replaced by tert-butoxycarbonyl was obtained.

¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1-1.2(m, 30H), 1.2-1.3(m, 72H), 2.6-2.7(m, 5H), 2.9(m，6H)、5.5(m，8H)、6.0-6.8(m，48H)、8.4,8.5(m，8H)。

Synthesis of BOC50CR-6

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-6 was replaced with CR-1 in the synthesis example of BOC50 CR-1. As a result, 31.0g of BOC50CR-6 in which 50 mol% of the phenolic hydroxyl group was replaced with tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(d, 12H), 1.4 to 1.6(d, 12H), 5.6(t, 4H), 6.1 to 6.5(m, 20H), 8.3 to 8.5(m, 4H).

Synthesis of BOC50CR-7

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-1 in the synthesis example of BOC50CR-1 was replaced with CR-7. As a result, 30.8g of BOC50CR-7 in which 50 mol% of the phenolic hydroxyl group was replaced with tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 0.9(d, 24H), 1.1 to 1.3(s, 36H), 1.7(m, 4H), 2.3 to 2.4(m, 8H), 5.5(d, 4H), 5.8 to 6.8(m, 24H), 8.4 to 8.6(t, 4H).

Synthesis of BOC50CR-8

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-8 was used instead of CR-1 in the synthesis example of BOC50 CR-1. As a result, 30.5g in total of BOC50CR-8 in which 50 mol% of the phenolic hydroxyl group was replaced by tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.3(s, 36H), 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 24H), 8.6 to 8.7(t, 4H).

Synthesis of BOC50CR-9

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-9 was replaced with CR-1 in the synthesis example of BOC50 CR-1. As a result, 29.5g of BOC50CR-9 in which 50 mol% of the phenolic hydroxyl group was replaced with tert-butoxycarbonyl group was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.2(d, 12H), 1.1 to 1.3(s, 36H), 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 20H), 8.6 to 8.7(t, 4H).

Synthesis of BOC50CR-10

Synthesis was carried out in the same manner as for BOC50CR-1 except that CR-10 was replaced with CR-1 in the synthesis example of BOC50 CR-1. As a result, 29.4g of BOC50CR-10 in which 50 mol% of the phenolic hydroxyl group was substituted with tert-butoxycarbonyl group was obtained.

In deuterated dimethyl sulfoxide solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(d, 12H), 1.1 to 1.3(s, 36H), 1.4 to 1.6(d, 12H), 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 16H), 8.6 to 8.7(t, 4H).

Synthesis of BOC67CP-1

Synthesis was carried out in the same manner as BOC50CR-1 except that CR-1 in the synthesis example of BOC50CR-1 was replaced with CP-1. As a result, 37.2g of BOC67CP-1 in which 67 mol% of the phenolic hydroxyl group was replaced with tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.0(m, 12H), 1.1 to 1.3(s, 72H), 1.4 to 1.6(m, 8H), 2.3 to 2.5(m, 8H), 5.5(s, 4H), 6.0 to 6.8(m, 20H), 8.4 to 8.5(m, 4H).

Synthesis of BOC67CP-2

Synthesis was carried out in the same manner as BOC50CR-1 except that CR-1 in the synthesis example of BOC50CR-1 was replaced with CP-2. As a result, 38.6g of BOC67CP-2 in which 67 mol% of the phenolic hydroxyl group was replaced with tert-butoxycarbonyl was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.1 to 1.3(s, 72H), 6.0 to 7.4(d, 4H), 6.1 to 6.5(m, 20H), 8.6 to 8.7(m, 4H).

Examples 1 to 57 and comparative examples 1 to 3

The components shown in Table 1 were prepared to prepare a homogeneous solution, which was then filtered through a Teflon membrane filter having a pore size of 0.2 μm to prepare a resist composition, and the following evaluations were carried out for each composition. The results are shown in Table 2.

(1) Evaluation of film Forming Property of resist film

A resist film of 10X 10mm square formed by spin-coating the resist composition on a silicon wafer with a spin coater was visually observed, and all the surface properties were confirmed to be good.

(2) Pattern formation test

(2-1) evaluation of resolving power

After spin coating the resist onto a clean silicon wafer, a pre-exposure bake (PB) was performed in an oven to form a resist film with a thickness of 0.1 μm. The resist film was irradiated with a radiation beam from an electron beam lithography apparatus (ELS-7500, manufactured by エリオニクス Co., Ltd.) at a distance of 50nm of 1: 1, and spaced electron rays. After the irradiation, the substrate was heated at the respective predetermined temperatures for 90 seconds and developed in a 2.38 wt% aqueous solution of TMAH for 60 seconds. Then, the resist was washed with water for 30 seconds and dried to form a positive resist pattern. The obtained lines and spaces were observed by a scanning electron microscope (S-4800, manufactured by Hitachi ハイテクノロジー Co., Ltd.). In addition, the dose at this time (. mu.C/cm)²) As the sensitivity.

(2-2) evaluation of Pattern shape

1: 1, and evaluation was performed.

A: rectangular pattern (good pattern)

B: roughly rectangular pattern (roughly good pattern)

C: non-rectangular pattern (bad pattern)

(2-3) evaluation of Line Edge Roughness (LER)

At 1: 1 at an arbitrary 300 points in the longitudinal direction (0.75 μm) of the line and space, the distance between the edge and the reference line was measured using the hitachi semiconductor SEM ターミナル PC V5 offline length measuring software (manufactured by hitachi サイエンスシステムズ, ltd.). The standard deviation (3. sigma.) was calculated from the measurement results.

A: LER (3 sigma) ≦ 3.0nm (good LER)

B: 3.0nm < LER (3 σ) < 3.5nm (approximately good LER)

C: 3.5nm < LER (3 sigma) (poor LER)

(2-4) measurement of the amount of outgas

The coated resist film was irradiated over an area of 1.2X 1.2mm with the dose (. mu.C/cm) calculated in (2-1)²) 2 times of the electron beam. Then, the difference in film thickness between the portion irradiated with the electron beam and the portion not irradiated with the electron beam was measured by a scanning probe microscope, and the difference in film thickness was used as an index of the amount of outgassing. The results were compared with the amount of film reduction obtained when 50 mol% of Polyparahydroxystyrene (PHS) in which a hydroxyl group was substituted with a tert-butoxycarbonyl group was used as a compound.

A: the reduction in the film was not more than that in the case of using PHS in which 50 mol% of the hydroxyl groups were substituted with tert-butoxycarbonyl groups

C: the amount of reduction in the film was larger than that in the case of using PHS in which 50 mol% of the hydroxyl groups were replaced with tert-butoxycarbonyl groups

(3) Safe solvent solubility test of Compounds

Solubility test of the compound obtained in Synthesis example 2 in a safe solvent was conducted at 23 ℃. The amount of dissolution in the most soluble solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, anisole, butyl acetate, ethyl propionate, ethyl lactate, and cyclohexanone was evaluated.

A: 10.0 wt% or less dissolved amount

B: 1.0% by weight ≦ dissolved volume ≦ 10.0% by weight ≦

C: the dissolution amount is less than 1.0 wt%

[ Table 1]

TABLE 1-1

[ Table 2]

TABLE 1-2

[ Table 3]

Tables 1 to 3

Comparative Compounds

BOC75CR-11

The following CR-11 was obtained by the same synthesis using 4-hydroxybenzaldehyde instead of 4-isopropylbenzaldehyde in Synthesis example 1, and the target material BOC75CR-11 (substitution rate of phenolic hydroxyl group for t-butoxycarbonyl group: 75 mol%) was obtained using CR-11 instead of CR-1 in Synthesis example 2.

BOC50CR-12

The following CR-12 was synthesized in the same manner using acetaldehyde instead of 4-isopropylbenzaldehyde in Synthesis example 1, and the target BOC50CR-12 (the substitution rate of the phenolic hydroxyl group with the t-butoxycarbonyl group was 50 mol%) was obtained using CR-12 instead of CR-1 in Synthesis example 2.

BOC50CR-13

The following CR-13 was similarly synthesized using 4-tert-butylbenzaldehyde instead of 4-isopropylbenzaldehyde in Synthesis example 1, and the target material BOC50CR-13 (the substitution rate of a phenolic hydroxyl group for a tert-butoxycarbonyl group was 50 mol%) was obtained using CR-13 instead of CR-1 in Synthesis example 2.

[ chemical formula 117]

[ chemical formula 118]

[ chemical formula 119]

Acid generator C

P-1: triphenylphenylsulfonium nonafluorobutanesulfonate salt

(みどり chemical strain)

P-2: triphenylphenylsulfonium triflate

(みどり chemical strain)

P-3: diphenyl (trimethyl) phenyl sulfonium p-toluenesulfonate

(Heguang pure chemical industry (strain))

Acid diffusion controlling agent E

Q-1: trioctylamine (Tokyo chemical industry (strain))

Q-2: luofanine (Tokyo chemical industry (strain))

Other component F (surfactant)

D-1: メガファック R08 (manufactured by Nippon ink chemical Co., Ltd.)

D-2: BYK-302(ビック, ケミージャパン (manufactured by KAYAKU Co., Ltd.))

Solvent(s)

S-1 propylene glycol monomethyl ether (Tokyo Kasei Kogyo)

[ Table 4]

TABLE 2-1

[ Table 5]

TABLE 2-2

[ Table 6]

TABLE 2-3

PEB: temperature at the time of heating after electron beam irradiation

Synthesis example 1A Synthesis of C10-24 benzaldehyde having substituent containing alicyclic or aromatic Ring

74.3g (3.71mol) of anhydrous HF and 50.5g (0.744mol) of BF were added ₃The contents were stirred in an autoclave (made of SUS 316L) having an internal volume of 500ml and capable of controlling the temperature, and the pressure was increased to 2MPa with carbon monoxide while maintaining the liquid temperature at-30 ℃. Then, after supplying a raw material mixed with 57.0g (0.248mol) of 4-cyclohexylbenzene and 50.0g of n-heptane at a liquid temperature of-30 ℃ under a holding pressure of 2MPa for 1 hour, the content was extracted from ice, diluted with benzene, and the oil layer obtained by neutralization treatment was analyzed by gas chromatography, and the reaction result was found to be 100% conversion of 4-cyclohexylbenzene and 97.3% selectivity of 4-cyclohexylbenzaldehyde. The target component was isolated by simple distillation, and as a result of GC-MS analysis, the molecular weight of the target substance, 4-cyclohexylbenzaldehyde (hereinafter referred to as CHBAL), was 188. In addition, in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.6(m, 10H), 2.55(m, 1H), 7.36(d, 2H), 7.8(d, 2H), 10.0(s, 1H).

[ chemical formula 120]

Synthesis of Cyclic Polyphenol Compound A of Synthesis example 2A

An ethanol solution was prepared by charging resorcinol (22g, 0.2mol) produced by Kanto chemical, 4-cyclohexylbenzaldehyde (46.0g, 0.2mol) synthesized in Synthesis example 1A, and absolute ethanol (200ml) into a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer, and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, under a nitrogen gas flow. The solution was heated to 85 ℃ with a mantle resistance heater while stirring. Then, 75ml of concentrated hydrochloric acid (35%) was added dropwise over 30 minutes via a dropping funnel, Stirring was continued at 85 ℃ for 3 hours. After the reaction, the reaction mixture was cooled to room temperature and then cooled in an ice bath. After standing for 1 hour, a pale yellow crude crystal of interest was produced, which was isolated by filtration. The crude crystals were washed 2 times with 500ml of methanol, separated by filtration, and dried under vacuum to give the desired product (hereinafter referred to as CR-1A) (50g, yield 91%). The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 1121. In addition, in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 1.9(m, 56H), 5.5,5.6(d, 4H), 6 to 6.8(m, 24H), 8.4,8.5(m, 8H).

[ chemical formula 121]

Synthesis of cyclic Compound B of Synthesis example 3A

Synthesis of BOC50CR-1A

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 8.7g (40mmol) of di-tert-butyl dicarbonate was dropped under a nitrogen gas flow into a solution composed of 11.2g (10mmol) of CR-1A synthesized in Synthesis example 2A, 0.1g (1mmol) of 4, 4' -dimethylaminopyridine and 500ml of acetone. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. 13.0g in total of BOC50CR-1A in which 50 mol% of the phenolic hydroxyl group was substituted with tert-butoxycarbonyl was obtained.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 1.9(m, 92H), 5.5,5.6(d, 4H), 6 to 6.8(m, 24H), 8.4,8.5(m, 4H).

Synthesis of tBu50CR-1A

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, a solution of 11.2g (10mmol) of CR-1A synthesized in Synthesis example 2A, 13.8g of potassium carbonate and 400ml of THF was added dropwise thereto a solution of 7.7g (40mmol) of t-butyl bromoacetate in 100ml of THF under a nitrogen gas flow. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. 12.9g in total of tBu50CR-1A in which 50 mol% of the phenolic hydroxyl group was replaced by a tert-butoxycarbonylmethyl group was obtained.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 1.9(m, 92H), 4.7(s, 8H), 5.5,5.6(d, 4H), 6 to 6.8(m, 24H), 8.4,8.5(m, 4H).

Synthesis of MAD50CR-1A

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, a solution of 11.4g (40mmol) of methyladamantyl bromoacetate in 100ml of THF was dropwise added under a nitrogen gas flow to a solution composed of 11.2g (10mmol) of CR-1A synthesized in Synthesis example 2A, 13.8g of potassium carbonate and 400ml of THF. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 14.0g in total of MAD50CR-1A in which 50 mol% of the phenolic hydroxyl groups were replaced with methyl adamantyloxycarbonylmethyl groups was obtained.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 2.1(m, 124H), 4.7(s, 8H), 5.5,5.6(d, 4H), 6 to 6.8(m, 24H), 8.4,8.5(m, 4H).

Synthesis of EE50CR-1A

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 2.9g (40mmol) of ethyl vinyl ether was dropped under a nitrogen gas flow into a solution composed of 11.2g (10mmol) of CR-1A synthesized in Synthesis example 2A, 2.5g of pyridinium p-toluenesulfonate and 400ml of acetone. The reaction solution was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 11.2g of EE50CR-1A was obtained in which 50 mol% of the phenolic hydroxyl groups were replaced with ethoxyethyl groups.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 1.9(m, 80H), 3.5(m, 8H), 5.5,5.6(d, 8H), 6 to 6.8(m, 24H), 8.4,8.5(m, 4H).

Synthesis of CE50CR-1A

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 5.0g (40mmol) of cyclohexyl vinyl ether was dropped under a nitrogen gas flow into a solution composed of 11.2g (10mmol) of CR-1A synthesized in Synthesis example 2, 2.5g of pyridinium p-toluenesulfonate and 400ml of 1, 3-dioxolane. The reaction solution was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 12.2g of CE50CR-1A in which 50 mol% of the phenolic hydroxyl groups were replaced with cyclohexyloxyethyl groups was obtained.

In deuterated dimethyl sulfoxide solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 1.9(m, 108H), 3.5(m, 4H), 5.5,5.6(d, 8H), 6 to 6.8(m, 24H), 8.4,8.5(m, 4H).

Examples 1A to 20A

The components shown in Table 1A were prepared to prepare a homogeneous solution, which was then filtered through a Teflon membrane filter having a pore size of 0.2 μm to prepare a resist composition. The acid generator C, the acid diffusion controller E, the other additives F and the solvent were evaluated in the same manner as described above in the pattern formation test, except that the following evaluations were performed in the pattern formation test.

(2-3) evaluation of Line Edge Roughness (LER)

A: LER (3 sigma) ≦ 3.5nm (good LER)

B: 3.5nm < LER (3 σ) < 4.5nm (approximately good LER)

C: 4.5nm < LER (3 sigma) (poor LER)

In addition, in the test of the solubility in a safe solvent of the compound (3), it was confirmed that the amount of all the compounds dissolved was 2.5 wt% or more.

[ Table 7]

1A table

[ Table 8]

2A table

PEB: temperature at the time of heating after electron beam irradiation

Synthesis example 1B Synthesis of Compound for introducing acid-dissociable functional group

Synthesis of methyl adamantane bromoacetate

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 20ml of a THF solution of bromoacetyl bromide (12.65g/62.7mmol) was added dropwise to a solution composed of 2-methyl-2-adamantanol (8.31g/50mmol) (manufactured by Wako Junyaku chemical industries, Ltd.), pyridine (5.0g/62.7mmol) and 100ml of THF under a nitrogen gas flow at 0 ℃. The reaction solution was stirred at room temperature for 72 hours.

After completion of the reaction, insoluble matter was removed by filtration, the solvent was removed from the filtrate, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 50/1. 9.0g (yield 62%) of the following methyladamantyl bromoacetate was obtained.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 2.5(m, 17H) and 4.5(m, 2H).

Synthesis of ethyl adamantane bromoacetate

The following ethyl adamantane bromoacetate was synthesized in the same manner as methyl adamantane bromoacetate except that 2-methyl-2-adamantanol in the synthesis example of methyl adamantane bromoacetate was replaced with 2-ethyl-2-adamantanol (manufactured by Mitsubishi gas chemical corporation).

Synthesis of ethyl adamantane ester bromopropionate

The following ethyl adamantane bromopropionate was synthesized in the same manner as methyl adamantane bromoacetate except that 2-methyl-2-adamantanol in the synthesis example of methyl adamantane bromoacetate was replaced with 2-ethyl-2-adamantanol (manufactured by Kingjinxiang chemical Co., Ltd.) and bromoacetyl bromide was replaced with bromopropionic acid bromide.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 2.5(m, 19H) and 4.5(m, 2H).

[ chemical formula 122]

As shown below, the aldehyde compound a1 is synthesized first, followed by the cyclic compound.

Synthesis of aldehyde Compound A1 in Synthesis example 2B

Synthesis of AD1-HBA

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, a solution of p-hydroxybenzaldehyde (12.2g/100mmol), potassium carbonate (13.8g/100mmol) and 200ml of THF was added dropwise with a solution of 28.6g (100mmol) of methyladamantyl bromoacetate in 100ml of THF under a stream of nitrogen gas. The reaction solution was stirred under reflux for 24 hours.

After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 29.0g of the following AD1-HBA in which the phenolic hydroxyl group was replaced with a methyladamantyloxycarbonylmethyl group was obtained.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 17H), 4.9(s, 2H), 7.8 to 8.4(m, 4H), 10.0(m, 1H).

Synthesis of AD2-HBA

Synthesis was carried out in the same manner as for AD1-HBA except that methyladamantyl bromoacetate in the synthesis example of AD1-HBA was replaced with ethyladamantyl bromoacetate. As a result, 30.1g of the following AD2-HBA in which the phenolic hydroxyl group was replaced with ethyl adamantyloxycarbonylmethyl group was obtained. Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 19H), 4.9(s, 2H), 7.8 to 8.4(m, 4H), 10.0(m, 1H).

Synthesis of AD3-HBA

Synthesis was carried out in the same manner as AD1-HBA except that methyladamantyl bromoacetate in the synthesis example of AD1-HBA was replaced with ethyladamantyl bromopropionate. As a result, 31.1g of AD3-HBA whose phenolic hydroxyl group was replaced by ethyl adamantyloxycarbonylethyl group was obtained. Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 19H), 2.7(m, 2H), 4.9(s, 2H), 7.8 to 8.4(m, 4H), 10.0(m, 1H).

[ chemical formula 123]

Synthesis of cyclic Compound of Synthesis example 3B

Synthesis of AD1-CR-1

Resorcinol (5.5g, 50mmol) from Kanto chemical, AD1-HBA (16.4g, 50mol) synthesized in Synthesis example 2B, and ethanol (330ml) were charged in a stream of nitrogen gas, sufficiently dried A four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade was dried and replaced with nitrogen gas to prepare an ethanol solution. Then, 75ml of concentrated hydrochloric acid (35%) was added dropwise over 60 minutes at room temperature through a dropping funnel, and stirring was continued at room temperature for 6 hours. After the reaction, the reaction mixture was cooled by an ice bath, and the pale yellow crude crystals were separated by filtration. The crude crystals were washed 2 times with 300ml of distilled water and then 300ml of methanol, separated by filtration, and dried under vacuum to give the desired product (hereinafter referred to as AD1-CR-1) (20.2 g). The structure of the compound was analyzed by LC-MS, which revealed that the molecular weight of the target substance was 1681. In addition, in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 68H), 4.9(s, 8H), 5.4 to 5.7(m, 4H), 6.1 to 6.5(m, 24H), 7.8 to 8.4(m, 8H).

Synthesis of AD2-CR-1

Synthesis was carried out in the same manner as for AD1-CR-1, except that AD1-HBA in the synthesis example of AD1-CR-1 was replaced with AD 2-HBA. As a result, 30.0g of AD2-CR-1 was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 1733. Method for preparing product in deuterated chloroform solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 25H), 4.9(s, 2H), 7.8 to 8.4(m, 4H), 10.0(m, 1H).

Synthesis of AD3-CR-1

Synthesis was carried out in the same manner as for AD1-CR-1, except that AD1-HBA in the synthesis example of AD1-CR-1 was replaced with AD 3-HBA. As a result, 32.0g of AD3-CR-1 was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 1793. In addition, the obtained product is in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 25H), 2.7(m, 8H), 4.9(s, 2H), 7.8 to 8.4(m, 4H), and 10.0(m, 1H).

[ chemical formula 124]

[ chemical formula 125]

[ chemical formula 126]

Synthesis of comparative Compound AD4-CR-2

After CR-11 was obtained in comparative example 1, in a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, a solution of 11.4g (40mmol) of methyladamantyl bromoacetate in 100ml of THF was added dropwise under a nitrogen gas flow to a solution composed of 11.2g (10mmol) of CR-2, 13.8g of potassium carbonate and 400ml of THF. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 14.0g of AD4-CR-2 in which 50 mol% of the phenolic hydroxyl groups were replaced with methyl adamantyloxycarbonylmethyl groups was obtained.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 102H), 4.9(s, 12H), 5.4 to 5.7(m, 4H), 6.1 to 6.5(m, 24H), 7.8 to 8.4(m, 6H).

Synthesis of aldehyde Compound A1d in Synthesis example 4B

Synthesis of MADM-4HBA

In a four-necked flask (1000mL) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, a solution of p-hydroxybenzaldehyde (12.2g/100mmol), potassium carbonate (13.8g/100mmol) and 200mL of THF was added dropwise a solution of 28.6g (100mmol) of methyladamantyl bromoacetate in 100mL of THF under a stream of nitrogen gas. The reaction solution was stirred under reflux for 24 hours.

After completion of the reaction, the solvent was removed, and the obtained solid was purified by column chromatography using a mixed solvent of hexane/ethyl acetate 1/3. Thus, 29.0g of MADM-4HBA in which the phenolic hydroxyl group was replaced with a methyl adamantyloxycarbonylmethyl group was obtained.

In deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 17H), 4.9(s, 2H), 7.8 to 8.4(m, 4H), 10.0(s, 1H).

Synthesis of tBuM-4HBA

Synthesis was carried out in the same manner as for MADM-4HBA except that methyladamantyl bromoacetate in the example of synthesis of MADM-4HBA was replaced with t-butyl bromoacetate. As a result, 20.0g of tBuM-4HBA in which the phenolic hydroxyl group was substituted with a tert-butoxycarbonylmethyl group was obtained. In deuterated DMSO solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.4(s, 9H), 5.0(s, 2H), 7.1-7.9(m, 4H), 9.9(s, 1H).

Synthesis of tBuM-3HBA

Synthesis was carried out in the same manner as for MADM-4HBA except that in the synthesis example of MADM-4HBA, methyladamantyl bromoacetate was replaced with t-butyl bromoacetate and p-hydroxybenzaldehyde was replaced with m-hydroxybenzaldehyde. As a result, 20.0g of tBuM-3HBA in which the phenolic hydroxyl group was substituted with a tert-butoxycarbonylmethyl group was obtained. In deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.4(s, 9H), 4.9(s, 2H), 7.3-7.6(m, 4H), 10.0(s, 1H).

Synthesis of tBuM-2HBA

Synthesis was carried out in the same manner as for MADM-4HBA except that methyladamantyl bromoacetate was replaced with t-butyl bromoacetate and p-hydroxybenzaldehyde was replaced with o-hydroxybenzaldehyde in the example of the synthesis of MADM-4 HBA. As a result, 20.0g of tBuM-2HBA in which the phenolic hydroxyl group was substituted with a tert-butoxycarbonylmethyl group was obtained. In deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.4(s, 9H), 4.9(s, 2H), 7.1-7.8(m, 4H), 10.5(s, 1H).

Synthesis of tBuM-3Br4HBA

Synthesis was carried out in the same manner as for MADM-4HBA except that in the synthesis example of MADM-4HBA, methyladamantyl bromoacetate was replaced with t-butyl bromoacetate and p-hydroxybenzaldehyde was replaced with 3-bromo-4-hydroxybenzaldehyde. As a result, 19.5g of tBuM-3Br4HBA in which the phenolic hydroxyl group was replaced with a tert-butoxycarbonylmethyl group was obtained. In deuterated DMSO solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.4(s, 9H), 5.0(s, 2H), 7.2-8.2(m, 3H), 9.9(s, 1H).

Synthesis of MeM-4HBA

Synthesis was carried out in the same manner as for MADM-4HBA, except that methyladamantyl bromoacetate in the example of synthesizing MADM-4HBA was replaced with methyl bromoacetate. As a result, 15.2g of MeM-4HBA in which the phenolic hydroxyl group was substituted with a methoxycarbonylmethyl group was obtained. In deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 3.7(s, 3H), 5.0(s, 2H), 7.1-7.9(m, 4H), 9.9(s, 1H).

EtM-4 synthesis of HBA

Synthesis was carried out in the same manner as for MADM-4HBA except that methyladamantyl bromoacetate in the example of synthesizing MADM-4HBA was replaced with ethyl bromoacetate. As a result, EtM-4HBA in which the phenolic hydroxyl group was replaced with ethoxycarbonylmethyl group (15.8 g) was obtained. In deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.3(t, 9H), 4.3(m, 2H), 4.8(s, 2H), 7.1-7.9(m, 4H), and 9.9(s, 1H).

Synthesis of Compound A3 having a Halomethyl Ether group in Synthesis example 5B

Synthesis of ADCME

In a four-necked flask (100mL) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, 92% paraformaldehyde (1.20g/20mmol) was added to a solution composed of 1-adamantylmethanol (3.32g/10mmol) and 63mL of chloroform under a nitrogen gas flow. Then, the mixture was stirred for 2.5 hours while blowing a hydrogen halide gas under ice cooling.

After the reaction was completed, the blowing of the hydrogen halide gas was stopped, the reaction mixture was returned to room temperature, the insoluble layer was separated with a separatory funnel, anhydrous sodium sulfate was added to the n-hexane layer, and the mixture was stirred at room temperature and then filtered. The solvent was removed from the obtained filtrate to obtain 4.1g of ADCME as a target substance.

Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.6(m, 15H), 3.3 to 3.6(m, 2H), and 5.5(s, 2H).

Synthesis of CHCME

The synthesis was carried out in the same manner as ADCME except that cyclohexanol was used instead of 1-adamantyl methanol in the ADCME synthesis example. As a result, a target product (hereinafter referred to as CHCME) (6.0g) was obtained. Method for preparing product in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.4 to 1.6(m, 10H), 2.8(m, 1H), 5.5(s, 2H).

Synthesis of cyclic Compound B0 in Synthesis example 6B

As shown below, cyclic compound a0 was synthesized first, followed by cyclic compound B0.

Synthesis of CM-CR-1

In a four-necked flask (1000L) equipped with a dropping funnel, a Dietzia condensation tube, a thermometer, and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, resorcinol (5.5g, 50mmol) manufactured by Kanto chemical Co., Ltd., MADM-4HBA (16.4g, 50mmol) synthesized in Synthesis example 1B, and ethanol (330ml) were charged under a nitrogen gas flow to prepare an ethanol solution. Then, 75ml of concentrated hydrochloric acid (35%) was added dropwise over 60 minutes at room temperature through a dropping funnel, followed by stirring at 80 ℃ for 48 hours. After completion of the reaction, the reaction mixture was returned to room temperature, and an aqueous sodium hydroxide solution was added thereto and stirred for 24 hours. Then, the solution was transferred to a separatory funnel, and diethyl ether was added thereto for separation, and the aqueous layer was separated and neutralized with hydrochloric acid, and the precipitated solid was separated by filtration and dried under vacuum to obtain the desired product (hereinafter referred to as CM-CR-1) (10.2 g). The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 1088. In addition, in deuterated DMSO solvents ¹Chemical shift values (. delta.ppm, TMS group) for H-NMRQuasi) is 4.5-4.6(t, 8H), 5.3-5.5(t, 4H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H), 12.7(brs, 4H).

[ chemical formula 127]

Synthesis of CM-CR-1-2

Synthesis was carried out in the same manner as CM-CR-1 except that in the synthesis example of CM-CR-1, MADM-4HBA was replaced by tBuM-4 HBA. As a result, the intended product (hereinafter referred to as CM-CR-1) (10.2g) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 1088. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 4.5-4.6(t, 8H), 5.3-5.5(t, 4H), 6.1-6.5(m, 24H), 8.4-8.5(t, 8H), 12.7(brs, 4H).

Synthesis of CM-CR-2

Synthesis was carried out in the same manner as CM-CR-1 except that in the synthesis example of CM-CR-1, MADM-4HBA was replaced by tBuM-3 HBA.

As a result, the intended product (hereinafter referred to as CM-CR-2) (10.0g) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 1088. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 4.3 to 4.4(d, 8H), 5.5 to 5.6(s, 4H), 6.1 to 6.9(m, 24H), 8.5(brs, 8H), 12.9(brs, 4H).

[ chemical formula 128]

Synthesis of CM-CR-3

Synthesis was carried out in the same manner as CM-CR-1 except that BuM-2HBA was used instead of MADM-4HBA in the synthesis example of CM-CR-1.

As a result, the eye was obtainedThe target product (hereinafter referred to as CM-CR-3) (10.0 g). The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 1088. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 4.1(t, 8H), 5.8-5.9(t, 4H), 6.0-7.0(m, 24H), 8.0(brs, 8H), 12.5(brs, 4H).

[ chemical formula 129]

Synthesis of CM-CR-4

Synthesis was carried out in the same manner as CM-CR-1 except that in the synthesis example of CM-CR-1, MADM-4HBA was replaced by tBuM-3Br4 HBA. As a result, the target product (hereinafter referred to as CM-CR-1) (11.0g) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the target substance was 1400. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 4.7(s, 8H), 5.2-5.5(t, 4H), 6.0-6.8(m, 20H), 8.6(brs, 8H), 12.9(brs, 4H).

[ chemical formula 130]

Synthesis of CM-CR-5

Synthesis was carried out in the same manner as for CM-CR-1 except that MADM-4HBA used in the synthesis example of CM-CR-1 was replaced with 4-formylbenzoic acid (reagent manufactured by アルドリッチ).

As a result, 5.0g of the desired product (hereinafter referred to as CM-CR-5) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 968. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 5.5 to 5.7(t, 4H), 6.1 to 7.7(m, 24H), 8.6 to 8.8(t, 8H), 12.3(brs, 4H).

[ chemical formula 131]

Synthesis of ADM-CR-1

A tetrahydrofuran solution was prepared by charging 100ml of THF of ADCME (8.6g, 40mmol) synthesized in Synthesis example 5B into a solution of synthesized CM-CR-1(10.9g, 10mmol), 13.8g of potassium carbonate and THF (330ml) in a four-necked flask (1000L) equipped with a dropping funnel, a Dietz condenser, a thermometer and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, under a nitrogen gas flow. Subsequently, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the reaction mixture was concentrated, purified by column chromatography, the column developing solvent was distilled off, and the resulting solid was separated by filtration and dried under vacuum to obtain the desired product (hereinafter referred to as ADM-CR-1) (15.2 g). The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 1801. In addition, in deuterated DMSO solvents ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.6(m, 60H), 3.3 to 3.6(m, 8H), 4.5 to 4.6(t, 8H), 5.3 to 5.5(m, 12H), 6.1 to 6.5(m, 24H), 8.4 to 8.5(t, 8H).

[ chemical formula 132]

Synthesis of ADM-CR-2

Synthesis was carried out in the same manner as ADM-CR-1 except that CM-CR-1 in the synthesis example of ADM-CR-1 was replaced with CM-CR-2.

As a result, 9.2g of the desired product (hereinafter referred to as ADM-CR-2) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 1801. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm, based on TMS) of H-NMR were 1.0 to 1.6(m, 60H), 3.3 to 3.6(m, 8H), 4.3 to 4.4(t, 8H), 5.3 to 5.6(m, 12H), 6.1 to 6.9(m, 24H), 8.4 to 8.5(t,8H)。

[ chemical formula 133]

Synthesis of ADM-CR-3

Synthesis was carried out in the same manner as ADM-CR-1 except that CM-CR-1 in the synthesis example of ADM-CR-1 was replaced with CM-CR-3.

As a result, 9.8g of the desired product (hereinafter referred to as ADM-CR-3) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 1801. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.6(m, 60H), 3.3 to 3.6(m, 8H), 4.1 to 4.2(t, 8H), 5.8 to 5.9(m, 12H), 6.0 to 7.0(m, 24H), 8.1(t, 8H).

[ chemical formula 134]

Synthesis of ADM-CR-4

Synthesis was carried out in the same manner as ADM-CR-1 except that CM-CR-1 in the synthesis example of ADM-CR-1 was replaced with CM-CR-4.

As a result, 11.2g of the desired product (hereinafter referred to as ADM-CR-4) was obtained. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 2112. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.6(m, 60H), 3.3 to 3.6(m, 8H), 4.7(t, 8H), 5.2 to 5.5(m, 12H), 6.0 to 6.8(m, 20H), 8.6(brs, 8H).

[ chemical formula 135]

Synthesis of ADM-CR-5

Synthesis was carried out in the same manner as ADM-CR-1 except that CM-CR-1 in the synthesis example of ADM-CR-1 was replaced with CM-CR-5.

As a result, the desired product (hereinafter referred to as ADM-CR-5) was obtained (6.2 g). The structure of the compound was analyzed by LC-MS, which revealed that the molecular weight of the target substance was 1680. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.6(m, 60H), 3.3 to 3.6(m, 8H), 5.3 to 5.5(m, 12H), 6.1 to 7.7(m, 24H), 8.6 to 8.8(t, 8H).

[ chemical formula 136]

Synthesis of CHM-CR-1

Synthesis was carried out in the same manner as ADM-CR-1 except that ADCME in the synthesis example of ADM-CR-1 was replaced by CHCM.

As a result, the desired product (hereinafter referred to as CHM-CR-1) (10.1g) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 1537. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.4 to 1.6(m, 40H), 2.8(m, 4H), 4.5 to 4.6(t, 8H), 5.3 to 5.5(m, 12H), 6.1 to 6.5(m, 24H), 8.4 to 8.5(t, 8H).

[ chemical formula 137]

Synthesis of CHM-CR-4

Synthesis was carried out in the same manner as ADM-CR-4 except that in the synthesis example of ADM-CR-4, ADCME was replaced by CHCME.

As a result, the desired product (hereinafter referred to as CHM-CR-4) (10.2g) was obtained. The structure of the compound was analyzed by LC-MS, and the results showed the separation of the target substanceThe quantum is 1848. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.4-1.6(m, 40H), 2.8(m, 4H), 4.7(t, 8H), 5.2-5.5(m, 12H), 6.0-6.8(m, 20H), 8.6(brs, 8H).

[ chemical formula 138]

Synthesis of NOM-CR-1

Synthesis was carried out in the same manner as ADM-CR-1 except that ADCME in the synthesis example of ADM-CR-1 was replaced with n-octyl chloromethyl ether.

As a result, the desired product (hereinafter referred to as NOM-CR-1) was obtained (8.2 g). The structure of the compound was analyzed by LC-MS, and the molecular weight of the objective substance was 1657. In addition, the product obtained is in deuterated DMSO solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.0 to 1.5(60m, 8H), 3.4(m, 8H), 4.5 to 4.6(t, 8H), 5.3 to 5.5(m, 12H), 6.1 to 6.5(m, 24H), 8.4 to 8.5(t, 8H).

[ chemical formula 139]

Synthesis of MADM-CR-1

Synthesis was carried out in the same manner as ADM-CR-1 except that ADCME in the synthesis example of ADM-CR-1 was replaced with 2-methyl-2-adamantane bromoacetate.

As a result, 9.8g of the desired product (hereinafter referred to as MADM-CR-1) was obtained. The structure of the compound was analyzed by LC-MS, and the molecular weight of the objective substance was 1913. In addition, the product obtained is in deuterated DMSO solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 68H), 4.5 to 4.6(t, 8H), 4.9(s, 8H), 5.3 to 5.5(t, 4H), 6.1 to 6.5(m, 24H), 8.4 to 8.5(t, 8H).

[ chemical formula 140]

Synthesis of MADM-CR-5

Synthesis was carried out in the same manner as ADM-CR-5 except that ADCME in the synthesis example of ADM-CR-1 was replaced with 2-methyl-2-adamantane bromoacetate.

As a result, the desired product (hereinafter referred to as MADM-CR-1) was obtained (10.2 g). The structure of the compound was analyzed by LC-MS, and the molecular weight of the target substance was 2224. In addition, the product obtained is in deuterated DMSO solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 1.5 to 2.2(m, 68H), 4.5 to 4.6(t, 8H), 4.9(s, 8H), 5.3 to 5.5(t, 4H), 6.1 to 7.7(m, 20H), 8.4 to 8.5(t, 8H).

[ chemical formula 141]

Examples 1B-44B and comparative example 1B

The components shown in Table 1B were prepared to prepare a homogeneous solution, which was then filtered through a Teflon membrane filter having a pore size of 0.2. mu.m to prepare a radiation-sensitive composition. The acid generator C, the acid diffusion controller E, the other additives F and the solvent were evaluated in the same manner as in examples 1A to 20A. The results are shown in Table 2B.

[ Table 9]

1B-1 Table

[ Table 10]

1B-2 Table

A	C	E		F
						Compound (I)	Acid generator	Acid diffusion controlling agent	Solvent(s)	Surface active agent
(g)	(g)	(g)	(g)	(g)
					Example 19B	ADM-CR-1	P-1	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 20B	ADM-CR-1	P-2	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 21B	ADM-CR-1	P-2	Q-1	S-1	D-1
1.0	0.3	0.03	30.0	0.02
					Example 22B	ADM-CR-1	P-2	Q-1	S-1	—
1.0	0.2	0.02	30.0
					Example 23B	ADM-CR-1	P-2	Q-1	S-1	D-1
1.0	0.2	0.02	30.0	0.02
					Example 24B	ADM-CR-1	P-2	Q-1	S-1	D-2
1.0	0.2	0.02	30.0	0.02
					Example 25B	ADM-CR-2	P-1	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 26B	ADM-CR-2	P-2	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 27B	ADM-CR-3	P-1	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 28B	ADM-CR-3	P-2	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 29B	ADM-CR-4	P-1	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 30B	ADM-CR-4	P-2	Q-1	S-1	—
1.0	0.3	0.03	30.0
					Example 31B	ADM-CR-4	P-2	Q-1	S-1	D-1
1.0	0.3	0.03	30.0	0.02
					Example 32B	ADM-CR-4	P-2	Q-1	S-1	—
1.0	0.2	0.02	30.0

[ Table 11]

Tables 1B-3

[ Table 12]

Table 2B-1

[ Table 13]

Table 2B-2

	PEB	Sensitivity of the device	Figure shape	LER
					(℃)	(μC/cm²)
Example 19B	100	7.5	A	A

Example 20B	100	10	A	A

Example 21B	100	7.5	A	A

Example 22B	100	7.5	A	A

Example 23B	100	7	A	A

Example 24B	100	7	A	A

Example 25B	100	7.5	A	A

Example 26B	100	10	A	A

Example 27B	100	7.5	A	A

Example 28B	100	10	A	A

Example 29B	100	6.5	A	A

Example 30B	100	9	A	A

[ Table 14]

2B-3 table

	PEB	Sensitivity of the device	Figure shape	LER
					(℃)	(μC/cm²)
Example 31B	100	6.5	A	A

Example 32B	100	6.5	A	A

Example 33B	100	6	A	A

Example 34B	100	6	A	A

Example 35B	100	7.5	A	A

Example 36B	100	10	A	A

Example 37B	100	7.5	A	A

Example 38B	100	10	A	A

Example 39B	100	6.5	A	A

Example 40B	100	9	A	A

Example 41B	100	7.5	B	A

Example 42B	100	10	B	A

Example 43B	110	7.5	A	A

Example 44B	110	10	A	A

PEB: temperature at the time of heating after electron beam irradiation

Synthesis of cyclic Compound A of Synthesis example 1D

CR-1 to CR-10 and CR-11 and CR-12, which are cyclic compounds A, were prepared in the same manner as in examples 1 to 57.

Examples 1D to 43D and comparative examples 1D and 2D

The components shown in Table 1D were prepared to prepare a homogeneous solution, which was then filtered through a Teflon membrane filter having a pore size of 0.2 μm to prepare a resist composition. The comparative compound, the acid generator C, the acid diffusion controller E, and the solvent were evaluated in the same manner as in examples 1 to 57. The results are shown in Table 2D.

[ Table 15]

1D-1 table

[ Table 16]

1D-2 Table

[ Table 17]

1D-3 table

Acid crosslinking agent C

C-1 ニカラック MW-100LM (Sanhe ケミカル (strain))

C-2 ニカラック MX-270 (Sanhe ケミカル strain)

C-3 ニカラック MX-290 (Sanhe ケミカル strain)

C-42, 6-bis (hydroxymethyl) -p-cresol (Tokyo Kasei Kogyo)

[ Table 18]

2D-1 table

[ Table 19]

2D-2 table

PEB: temperature at the time of heating after electron beam irradiation

Examples 1E-10E and comparative examples 1E-2E

Benzaldehyde having 10 to 24 carbon atoms and having an alicyclic or aromatic ring-containing substituent and cyclic compound A were synthesized in the same manner as in examples 1A to 20A.

The components shown in Table 1E were prepared to prepare a homogeneous solution, which was then filtered through a Teflon membrane filter having a pore size of 0.2 μm to prepare a resist composition. The comparative compound, the acid generator C, the acid crosslinking agent G, the acid diffusion controlling agent E, and the solvent were evaluated in the same manner as in examples 1D to 43D, except that the following evaluations were performed in the pattern formation test.

(2-3) evaluation of Line Edge Roughness (LER)

A: LER (3 sigma) ≦ 3.5nm (good LER)

C: 3.5nm < LER (3 sigma) (poor LER)

[ Table 20]

1E table

[ Table 21]

2E table

PEB: temperature at the time of heating after electron beam irradiation

Synthesis example 1F aldehyde

(1) Synthesis example of 4- (4-n-propylcyclohexyl) benzaldehyde

74.3g (3.71mol) of anhydrous HF and 50.5g (0.744mol) of BF were added₃The contents were stirred in an autoclave (made of SUS 316L) having an internal volume of 500ml and capable of controlling the temperature, and the pressure was increased to 2MPa with carbon monoxide while maintaining the liquid temperature at-30 ℃. Then, a raw material mixed with 50.0g (0.248mol) of (trans-4-n-propylcyclohexyl) benzene (having a purity of 98% or more, manufactured by Kanto chemical Co., Ltd.) and 50.0g of n-heptane was supplied at a liquid temperature of-30 ℃ under a holding pressure of 2MPa, and after holding for 1 hour, the content was extracted from ice, diluted with benzene, and the oil layer obtained by neutralization treatment was analyzed by gas chromatography to obtain the reaction result The conversion of (trans-4-n-propylcyclohexyl) benzene was 100%, and the selectivity for 4- (trans-4-n-propylcyclohexyl) benzaldehyde was 95.2%. The objective compound, 4- (trans-4-n-propylcyclohexyl) benzaldehyde, was isolated by simple distillation and analyzed by GC-MS to find that the molecular weight was 230. In addition, in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9(t, 3H), 1.0-1.6(m, 9H), 1.9(m, 4H), 2.55(m, 1H), 7.36(d, 2H), 7.8(d, 2H), 10(s, 1H). The purity of 4- (4-n-propylcyclohexyl) benzaldehyde was 98.3%, and the purity of trans-isomer was 99.0%.

(2) Synthesis example of 4- (trans-4-n-pentylcyclohexyl) benzaldehyde

The formylation reaction and treatment of the reaction mixture were carried out in the same manner as in (1) except that a mixture of 57.0g (0.248mol) of (trans-4-n-pentylcyclohexyl) benzene and 57.0g of n-heptane was added as a starting material. The oil layer obtained was analyzed by gas chromatography to determine the reaction results, the conversion of (trans-4-n-pentylcyclohexyl) benzene was 100%, and the selectivity for 4- (trans-4-n-pentylcyclohexyl) benzaldehyde was 96.2%.

(3) Synthesis example of 4-cyclohexylbenzaldehyde

The formylation reaction and treatment of the reaction mixture were carried out in the same manner as in (1) except that a mixture of 57.0g (0.248mol) of 4-cyclohexylbenzene and 57.0g of n-heptane was added as a starting material. The oil layer thus obtained was analyzed by gas chromatography to determine the reaction result, and the conversion of 4-cyclohexylbenzene was 100%, and the selectivity for 4-cyclohexylbenzaldehyde was 97.3%.

Synthesis of underlayer coating Forming composition

Synthesis example 2F Synthesis example of Cyclic Compound (hereinafter referred to as "CR")

(1) Synthesis example of CR-1F

An ethanol solution was prepared by charging resorcinol (22g, 0.2mol) produced by Kanto chemical, 4- (4-n-propylcyclohexyl) benzaldehyde (46.0g, 0.2mol) synthesized in Synthesis example 1F, and absolute ethanol (200ml) into a four-neck flask (1000L) equipped with a dropping funnel, a Dietzia condenser, a thermometer, and a stirring blade, which was sufficiently dried and replaced with nitrogen gas, under a nitrogen gas flow.The solution was heated to 85 ℃ with a mantle resistance heater while stirring. Then, 75ml of concentrated hydrochloric acid (35%) was added dropwise over 30 minutes through a dropping funnel, and the stirring was continued at 85 ℃ for 3 hours. After the reaction, the reaction mixture was cooled to room temperature and then cooled in an ice bath. After standing for 1 hour, a pale yellow crude crystal of interest was produced, which was isolated by filtration. Washing the crude crystals with 500ml of methanol 2 times, separating by filtration, and drying in vacuo to give all R of the formula (4)⁴CR-1F (58g, 91% yield), both n-propyl. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the target substance was 1289. In addition, in deuterated chloroform solvent ¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.9 to 1.9(m, 68H), 5.5,5.6(d, 4H), 6 to 6.8(m, 24H), 8.4,8.5(m, 8H).

The change in the thermogravimetric amount at the temperature of CR-1F raised to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(2) Synthesis example of CR-2F

Synthesis was carried out in the same manner as in the synthesis example of CR-1F except that 4- (4-n-propylcyclohexyl) benzaldehyde used in the synthesis example of CR-1F was replaced with 4- (trans-4-n-pentylcyclohexyl) benzaldehyde used in the synthesis example 2F. As a result, all R's in the formula (4) are obtained⁴CR-2F (63.0g, 90% yield), both n-pentyl. The structure of the compound was analyzed by LC-MS, and the result showed that the molecular weight of the objective substance was 1401. In addition, in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 1.9(m, 84H), 5.5,5.6(d, 4H), 6 to 6.8(m, 24H), 8.4,8.5(m, 8H).

The change in the thermogravimetric amount at the temperature of CR-2F increased to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(3) Synthesis example of CR-3F

Synthesis was carried out in the same manner as in CR-1F except that 4- (4-n-propylcyclohexyl) benzaldehyde was used instead of 4-cyclohexylbenzaldehyde in the Synthesis example 2F in the Synthesis example of CR-1F. As a result, all R's in the formula (3) are obtained ³CR-3F each representing a hydrogen atom (yield: 87%). The structure of the compound is determined by NMR measurement, IR measurement, elemental analysis, and the like. The structure of the compound was analyzed by LC-MS, and the results were shownThe molecular weight of the target substance is 1117. In addition, in deuterated chloroform solvent¹The chemical shift values (. delta.ppm based on TMS) of H-NMR were 0.8 to 1.9(m, 56H), 5.5,5.6(d, 4H), 6 to 6.8(m, 24H), 8.4,8.5(m, 8H).

The change in the thermogravimetric amount at the temperature of CR-3F increased to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(4) Synthesis example of CR-4F

Synthesis was carried out in the same manner as in the synthesis example of CR-1F except that 4- (4-n-propylcyclohexyl) benzaldehyde was replaced with cuminaldehyde manufactured by Mitsubishi gas chemical Co. As a result, all R's in the formula (2) are obtained²CR-4F, both isopropyl (47% yield). The structure of the compound is determined by NMR measurement, IR measurement, elemental analysis, and the like.

The change in the thermogravimetric amount at the temperature of CR-4F increased to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(4) Synthesis example of CR-5F

Synthesis was carried out in the same manner as in the synthesis example of CR-1F except that 4- (4-n-propylcyclohexyl) benzaldehyde used in the synthesis example of CR-1F was replaced with n-propylbenzaldehyde manufactured by Mitsubishi gas chemical corporation. As a result, all R's in the formula (2) are obtained ²CR-5F, both n-propyl (63.0, 90% yield). The structure of the compound is determined by NMR measurement, IR measurement, elemental analysis, and the like.

The change in the thermogravimetric amount at the temperature of CR-5F increased to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(6) Synthesis example of CR-6F

Synthesis was carried out in the same manner as in the synthesis example of CR-1F except that 4- (4-n-propylcyclohexyl) benzaldehyde used in the synthesis example of CR-1F was replaced with t-butylbenzaldehyde manufactured by アルドリッチ. As a result, all R's in the formula (2) are obtained²CR-6F, both tert-butyl (30% yield). The structure of the compound is determined by NMR measurement, IR measurement, elemental analysis, and the like.

The change in the thermogravimetric amount at the temperature of CR-6F increased to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(7) Synthesis example of CR-7F

Synthesis was carried out in the same manner as in the synthesis example of CR-1F except that 4- (4-n-propylcyclohexyl) benzaldehyde used in the synthesis example of CR-1F was replaced with 1-decanol manufactured by Kanto chemical Co. As a result, all R's in the formula (1) are obtained¹CR-7F, both n-nonyl (67% yield). The structure of the compound is determined by NMR measurement, IR measurement, elemental analysis, and the like.

The change in the thermogravimetric amount at the temperature of CR-7F increased to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(8) Synthesis example of CR-8F

CR-1F gave, by a known method, a phenolic hydroformylation resin CR-8F having a repeating unit via the methylene group. As a result of GPC measurement, Mw was 9100 and Mw/Mn was 5.8.

The change in the thermogravimetric amount at the temperature of CR-8F increased to 200 ℃ was 1% or less, and it was confirmed that the sublimability was small.

(9) Synthesis of comparative Compound 1

The synthesis was carried out in the same manner as in the synthesis example of CR-1F except that 4- (4-n-propylcyclohexyl) benzaldehyde was replaced with 1,3, 5-benzenetricarboxylic acid, resorcinol was replaced with 2,3, 6-trimethylphenol, and concentrated hydrochloric acid in a toluene solvent was replaced with 1ml of concentrated sulfuric acid in the synthesis example of CR-1F. As a result, a compound represented by the following formula was obtained (yield: 85%). The structure of the compound is determined by NMR measurement, IR measurement, elemental analysis, and the like.

[ chemical formula 142]

(10) Synthesis of comparative Compound 2

The synthesis was carried out in the same manner as in the synthesis of comparative compound 1 except that 1,3, 5-benzenetricarboxylic aldehyde was replaced with 2-adamantanone. As a result, a compound represented by the following formula was obtained (yield: 81%). The structure of the compound is determined by NMR measurement, IR measurement, elemental analysis, and the like.

[ chemical formula 143]

Production of underlayer coating of production example 1F

The Mw of the poly-p-hydroxystyrene (hereinafter referred to as PHS) manufactured by CF-1F to CF-8F and comparative compounds 1 to 2 and アルドリッチ was: 8000 or m-cresol novolak resin (Mw: 8800) (hereinafter referred to as phenol) was dissolved in a solvent PGME (propylene glycol monomethyl ether) at a ratio of 5 mass%, and filtered through a 0.1 μm fluororesin filter to prepare a solution for forming an underlayer film.

Subsequently, the solution for forming an underlayer coating in the container was spin-coated on a silicon substrate, and baked at 110 ℃ for 90 seconds to obtain an underlayer coating having a thickness of 200nm (hereinafter referred to as underlayer coating 1-9 and comparative underlayer coating 1-4). The measurement of each lower film was carried out with a variable incident angle spectroscopic ellipsometer (VASE) of J.A. ウーラム Co., Ltd. at a wavelength of 193 nm. The refractive index n and the extinction coefficient k of the lower layer films 1 to 9 and the lower layer films 1 to 4 of the comparative example were obtained by correcting the measured absorption values with a Gaussian Oscillator approximation (Gaussian Oscillator approximation) using a General Oscillator Model (General Oscillator Model), and the results are shown in table 1F.

[ Table 22]

TABLE 1F

Acid generators: triphenylsulfonium nonafluoromethanesulfonate (TPS109)

A crosslinking agent: ニカラック MX270 manufactured by Sanhe ケミカル Co

Next, a solution of a material for forming an underlayer film was applied to SiO with a film thickness of 300nm₂The substrate was baked at 250 ℃ for 60 seconds to form an underlayer film having a thickness of 200 nm. Then, a resist solution for ArF was applied and baked at 130 ℃ for 60 seconds to form a resist layer with a thickness of 200 nm. In addition, the ArF resist solution incorporates a compound of the following formula (110): 5 parts, TPS 109: 1 part, tributylamine: 2 parts, PGMEA: 92 portions for conditioning.

Next, the resist was exposed to light by an electron beam lithography apparatus (manufactured by エリオニクス, ELS-7500, 50keV), baked (PEB) at 115 ℃ for 90 seconds, and developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds to obtain a positive pattern. The pattern shape of 60nmL/S (1: 1) of the obtained pattern was observed, and the results are shown in Table 2F.

[ Table 23]

TABLE 2F

	Underlayer film	Resolution power	Sensitivity of the device
				Examples	1	60nmL&S	12μC/cm²
Examples	2	60nmL&S	12μC/cm²
				Examples	3	60nmL&S	12μC/cm²
Examples	8	60nmL&S	12μC/cm²
				Examples	9	60nmL&S	12μC/cm²
Comparative example	Is free of	80nmL&S	26μC/cm²

[ chemical formula 144]

Next, the resist pattern obtained by the above electron beam exposure and development was transferred onto the underlayer film under the following conditions. The etching conditions are as follows.

An etching device: エリオニクス products of society

Voltage: 400V

Current density: 0.9mA/cm²

Time: 2min

Argon flow: carbon tetrafluoride gas flow: oxygen flow rate 10: 1: 1 volume ratio

The cross section of the pattern was observed by an electron microscope (S-4800) manufactured by Hitachi, Ltd, and the shape was compared.

It can be confirmed that: the shape of the developed lower layer film in the multilayer resist processing is good after the oxygen etching and the substrate processing etching; when used as a single-layer resist hard film, the shape after development and substrate processing and etching is also good.

Industrial applicability

The invention is applicable to: the cyclic compound is used for an acid-proliferating non-polymer resist material, a resist compound represented by a specific chemical structural formula, a radiation-sensitive composition containing the cyclic compound, an underlayer film using the radiation-sensitive composition, and a method for forming a resist pattern.

Claims

1. A radiation-sensitive composition comprising a cyclic compound B represented by the following formula (19-1) and a low-molecular-weight dissolution promoter D, wherein the low-molecular-weight dissolution promoter D is incorporated in an amount such that the total of the cyclic compound B and the low-molecular-weight dissolution promoter D is 50 to 99.999 wt% based on the total amount of solid components, the cyclic compound B has a molecular weight of 800-5000, the low-molecular-weight dissolution promoter D is selected from cyclic compounds A obtained by a condensation reaction of one OR more compounds selected from the group consisting of aromatic carbonyl compounds A1 with one OR more compounds selected from the group consisting of phenolic compounds A2, and the cyclic compound A and OR of the cyclic compound B¹R in (1)¹The cyclic compounds all of which are hydrogen atoms are the same,

in the formula (19-1), R ¹Independently an acid dissociable functional group selected from the group consisting of methoxymethyl, ethoxymethyl, 1-cyclopentyloxymethyl, 1-cyclohexyloxymethyl, 1-ethoxyethyl, 1-diethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, 1-cyclopentyloxyethyl, 1-cyclohexyloxyethyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, and compounds in which n is an integer of 1 to 4 as described in the following formula (9), or a hydrogen atomAnd at least one R¹Is an acid dissociable functional group;

R⁴is a functional group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and not being a t-butyl group, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms;

p is 1;

in the formula (9), R²Is hydrogen or C1-4 straight chain or branched chain alkyl, and n is an integer of 0-4.

2. The radiation-sensitive composition according to claim 1, wherein the cyclic compound B is selected from compounds represented by the following formula (20),

In the formula, R¹As described above.

3. The radiation-sensitive composition according to claim 1, wherein the cyclic compound B is selected from compounds represented by the following formula (21),

in the formula, R¹As described above.

4. The radiation-sensitive composition according to claim 1, wherein the aromatic carbonyl compound a1 is cumene formaldehyde, n-propyl benzaldehyde, bromobenzaldehyde, dimethylaminobenzaldehyde, cyclohexylbenzaldehyde, or benzaldehyde; the phenolic compound A2 is phenol, catechol, resorcinol or hydroquinone.

5. The radiation-sensitive composition according to any one of claims 1 to 4, wherein the low-molecular-weight dissolution promoter D is incorporated in an amount such that the sum of the cyclic compound B and the low-molecular-weight dissolution promoter D is 60 to 99% by weight of the total amount of solid components.

6. The radiation-sensitive composition according to any one of claims 1 to 4, wherein the low-molecular-weight dissolution promoter D is incorporated in an amount such that the sum of the cyclic compound B and the low-molecular-weight dissolution promoter D is 80 to 99% by weight of the total amount of solid components.