WO2006132139A1

WO2006132139A1 - Compound for resist and resist composition

Info

Publication number: WO2006132139A1
Application number: PCT/JP2006/311066
Authority: WO
Inventors: Masatoshi Echigo; Dai Oguro
Original assignee: Mitsubishi Gas Chemical Company, Inc.
Priority date: 2005-06-06
Filing date: 2006-06-02
Publication date: 2006-12-14
Also published as: JPWO2006132139A1; JP2012093784A; JP5182411B2; JP2012068652A; TW200710567A; JP5218682B2; JP2012118551A; JP5110210B2; JP4998261B2

Abstract

Resist compound (A) (a) produced by reacting a reagent for introduction of a crosslinking reaction group capable of directly or indirectly inducing a crosslinking reaction upon exposure to any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, extreme ultraviolet (EUV), electron beam, X-ray and ion beam with a polyphenol compound produced by condensation reaction between a C5-C45 aromatic ketone or aromatic aldehyde and a C6-C15 compound having 1 to 3 phenolic hydroxyls, and (b) having a molecular weight of 300 to 5000, wherein (c) at least one crosslinking reaction group mentioned above is present in each molecule thereof. There is provided a resist composition comprising at least one type of resist compound (A), and provided compounds usable therein. This resist composition has high sensitivity, thereby enabling preparation of a resist pattern of high resolution and enabling manufacturing of a semiconductor device of high integration degree with high productivity.

Description

Description Resist compound and resist composition

Technical field

[0001] The present invention relates to a resist composition that is useful as a non-polymeric resist material and that includes a resist compound that satisfies specific conditions and has a crosslinking reactive group. The resist composition of the present invention is used as a radiation-sensitive material sensitive to radiation such as ultraviolet rays, far-ultraviolet rays, electron beams, extreme ultraviolet rays (EUV), and X-rays. The present invention relates to a resist composition capable of producing a high-resolution resist pattern and capable of producing a highly integrated semiconductor device with high productivity, and a resist compound suitable for it.

Background art

Conventional general resist materials are polymer materials capable of forming an amorphous thin film. For example, by irradiating a resist thin film prepared by applying a polymethylmetatalate solution on a substrate with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays (EUV), X-rays, etc., 0 .: L A line pattern of about m is formed.

However, since the polymer resist has a large molecular weight distribution of about 10,000 to 100,000, the lithography using the polymer resist generates roughness on the surface of the fine pattern and controls the pattern size. Becomes difficult and the yield decreases. Therefore, there is a limit to miniaturization in lithography using a conventional polymer resist material. Various low molecular weight resist materials have been disclosed for producing finer patterns.

[0003] Examples of non-polymer resist materials include: (1) Fullerene force-induced positive and negative resists, (2) Calixarene force-induced positive and negative resists, (3) Starburst type Positive resist derived from compounds, (4) Posi resist that also induces dendrimarkers, (5) Dendrimer Z calixarene force-induced positive resist, (6) Starburst compound with high branching degree Force-induced positive resists, (7) Starburst compound forces that have ester bonds with trimesic acid as the central skeleton, and (8) Negative-type resists that induce cyclic polyphenolic compound forces. Resist, (9) polyph Enol compound power induced negative resist and (10) calix resorcinarene force induced negative resist.

[0004] With regard to (1), the etching resistance is good, but the applicability and sensitivity have not reached the practical level (see Patent Documents 1 to 5). Regarding (2), a force excellent in etching resistance is poor in solubility in a developing solution, so that a satisfactory pattern cannot be obtained (see Patent Documents 6 to 8). Regarding (3), the image may be distorted during heat treatment after exposure due to low heat resistance (see Patent Documents 9 to 11). Regarding (4), the manufacturing process is complicated and the heat resistance is low, so the image may be distorted during the heat treatment after exposure, and it cannot be said that it is practical (see Non-Patent Document 1). ) o (5) is also not practical because the manufacturing process is complicated and the raw materials are expensive (see Patent Documents 12 and 13). Regarding (6), the manufacturing process is complicated and the raw materials are expensive. For (7), the heat resistance is low, so the image may be distorted during the heat treatment after exposure, and the substrate adhesion is insufficient, so it cannot be said that it is practical ( (See Patent Document 14). As for (8) and (9), improvement that amorphous properties and etching resistance are not sufficient is desired (see Patent Documents 15 to 17). The (10), amorphous, safety solvent solubility sufficiently at Nag improvement is desired (see Patent Document 18 to 19.) ₀

[0005] Patent Document 1 Japanese Patent Application Laid-Open No. 7-134413

Patent Document 2 Japanese Patent Laid-Open No. 9 211862

Patent Document 3 Japanese Patent Laid-Open No. 10-282649

Patent Document 4 Japanese Patent Laid-Open No. 11-143074

Patent Document 5 Japanese Patent Laid-Open No. 11-258796

Patent Document 6 Japanese Patent Laid-Open No. 11-72916

Patent Document 7 Japanese Patent Laid-Open No. 11-322656

Patent Document 8 Japanese Patent Application Laid-Open No. 9236919

Patent Document 9 Japanese Patent Laid-Open No. 2000-305270

Patent Document 10: Japanese Patent Laid-Open No. 2002-99088

Patent Document 11: Japanese Patent Laid-Open No. 2002-99089

Patent Document 12: JP 2002-49152 Patent Document 13: Japanese Unexamined Patent Publication No. 2003-183227

Patent Document 14: Japanese Patent Laid-Open No. 2002-328466

Patent Document 15: JP-A-11-153863

Patent Document 16: Japanese Patent Laid-Open No. 2003-207893

Patent Document 17: Japanese Patent Application Laid-Open No. 2004-334106

Patent Document 18: JP-A-9 236919

Patent Document 19: Japanese Unexamined Patent Application Publication No. 2004-18421

Non-Patent Document 1: Proceedings of SPIE vol.3999 (2000) P1202-1206 Disclosure of Invention

Problems to be solved by the invention

The object of the present invention is not only for ultraviolet rays such as i-line and g-ray, but also for radiation such as visible light, excimer laser light such as KrF, electron beam, extreme ultraviolet (EUV), X-ray, ion beam, etc. It is an object of the present invention to provide a sensitive resist composition. Still another object of the present invention is to provide a high-sensitivity, high-resolution, high-heat-resistant, solvent-soluble, non-polymeric radiation-sensitive resist composition and a resist compound suitable for the same in a simple manufacturing process. There is to do.

Means for solving the problem

[0007] As a result of extensive research, the present inventors have found that a composition containing a compound that satisfies a specific condition is useful for solving the above problems.

That is, the present invention was produced by a condensation reaction of (a) an aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups. Polyphenolic compound, visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, and ion beam force are selected. Direct or indirect by irradiation with any radiation Is produced by reacting a reagent that introduces a crosslinking reactive group that causes a crosslinking reaction,

(b) The force is 300-5000.

(c) The present invention relates to a resist composition containing at least one resist compound (A) having at least one crosslinking reactive group in the molecule.

The present invention also provides a compound that can be used in the resist composition. is there.

The invention's effect

[0008] The compound of the present invention and the resist composition containing the compound are highly sensitive, heat-resistant and solvent-soluble, can produce a high-resolution resist pattern, and produce a highly integrated semiconductor element. It becomes possible to produce with the property.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The radiation-sensitive resist composition of the present invention contains a resist compound (A). The resist compound (A) in the present invention satisfies the following conditions (a), (b) and (c) simultaneously.

[0010] Condition (a): The resist compound (A) is an aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms (hereinafter referred to as aromatic carbo-louis compound (A1)), and 6 carbon atoms. To 15 and a polyphenolic compound produced by condensation reaction of a compound containing 1 to 3 phenolic hydroxyl groups (hereinafter referred to as phenolic compound (A2) t 、), visible light, ultraviolet light, excimer Laser, extreme ultraviolet (EUV), electron beam, X-ray, and ion beam force group force An agent that introduces a cross-linking reactive group that causes a cross-linking reaction directly or indirectly by irradiation with any selected radiation It is produced by reacting the cross-linking reactive group introduction reagent (A3) with i).

The resist compound (A) has a tertiary or quaternary carbon atom in the molecule, and two phenols and one or more aromatic rings are bonded to the tertiary or quaternary carbon atom. It has a chemical structure. This chemical structure can provide a stable amorphous property (non-crystalline, non-crystallizable (hard)) property for a long period of time, and is necessary for pattern formation as a resist material. Features such as excellent film formability, light transmission, solvent solubility, and excellent etching resistance.

[0011] Condition (b): The molecular weight of the resist compound (A) is 300 to 5,000.

The molecular weight is 300 to 5000, preferably <300 to 2000, more preferably <300 to 1000, particularly preferably 300 to 699. By making it in the above range, it is possible to impart good film forming properties, and it is possible to improve resolution and alkali development performance.

[0012] Condition (c): Visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X Line and ion beam force Group force It has at least one cross-linking reactive group in the molecule that causes a cross-linking reaction directly or indirectly by irradiation with any selected radiation. By having the cross-linking reactive group, the resist compound of the present invention can selectively insolubilize the exposed portion by the cross-linking reaction, and is used for a negative resist composition. . Here, the cross-linking reaction means a chemical reaction in which a plurality of reaction points in the resist compound are linked by a covalent bond. The number of the cross-linking reactive groups in the molecule is preferably 2, more preferably 2-15, and particularly preferably 3-15. By setting this range, the resolution and development performance can be further improved.

[0013] Examples of the crosslinking reactive group include a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogen-phenyl group, and a halogenated methyl group. Among these, a carbon-carbon multiple bond group, an epoxy group, and a halogenated methyl group are preferred, and a carbon-carbon multiple bond group and a halogenated methyl group are more preferred.

Carbon As the carbon multiple bond group, for example, a bur group (CH 2 = CH 3), a aryl group (CH

2

= CH— CH—), a bilene group-containing group (R ⁷ — CH = CH), an allyloyl group (CH 2 = C

2 2 2

H—CO 2), methacryloyl group (CH 2 = C (CH 2) —CO 2), crotonyl group (CH—CH

2 3 3 2

= CH—CO), fumaroyl groups (trans type R ⁷ —OC—CH = CH—CO 2), maleyl groups (cis type R ⁷ —OC—CH = CH—CO 2), carbon-carbon double bonds, and pronorgi And carbon-carbon triple bonds such as a ruthenium group (CH≡C) and an acetylene group (R ⁷ —C≡C). Of these, carbon-carbon double bonds such as vinyl group, aryl group, berylene group, acryloyl group, and methacryloyl group, and carbon-carbon triple bonds such as propargyl group and acetylene group are more preferable. Most preferred are a group, an allyloyl group, a methacryloyl group, and an open pargyl group. Examples of the epoxy group include a glycidyl group (CH (

2

— O—) CHCH—). When long-term stability is required, the epoxy group

2

It is not preferable. Examples of the halogenomethyl group include chloromethyl group (C1CH-),

2 Examples include momethyl group (BrCH-) and methyl iodide group (ICH-).

twenty two

R ⁷ is a group in which an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl power having 6 to 10 carbon atoms are also selected.

[0014] The resist compound (A) satisfying the above conditions (a), (b) and (c) has a conjugate double bond of 5 to 28. And preferably contain a conjugated structure involving unbonded electron pairs of Z or 1-2 heteroatoms, more preferably 5-12 conjugated double bonds.

By having the above conjugated structure, it is possible to impart performance such as film forming property, high etching resistance, low outgas amount during exposure, and high sensitivity due to a sensitizing effect even though it is a low molecular compound. This sensitization effect is thought to be due to the absorption of part of the energy of radiation such as electron beams and extreme ultraviolet (EUV), and then the absorbed energy contributes to the crosslinking reaction.

[0015] The conjugated structure includes a biphenyl structure, a naphthalene structure, a fluorene structure, a phenylfluorene structure, a difluorofluorene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, a benzopyrene structure, an acenaphthene structure, an acenaphthylene structure, and a 1-keto. Acenaphthene structure, 9-keto 9, 10-dihydrophenanthrene structure, benzophenone structure, xanthene structure, thixanthene structure, flavone structure, isoflavone structure, indane structure, indene structure, indacene structure, phenalene structure, biphenylene structure, Coronene structure, Talycene structure, Trinaphthylene structure, Hexaphen structure, Hexacene structure, Rubicene structure, Fluoracene structure, Acephenanthrylene structure, Perylene structure, Picene structure, Pentaphene structure, Heptaphene Structure, heptacene structure, pyranthrene structure, phenacene structure, naphthacene structure, pentacene structure, aceanthrene structure, acetophenanthrene structure, azulene structure, triphenylene structure, ρ-terfel structure, m-terfel structure, 1,3,5-triphenylbenzene structure, 1,2,3-triphenylbenzene structure, 1,2,4-triphenylbenzene structure, phenylnaphthalene structure, binaphthalene structure, ovalene structure, etc. , Biphenyl structure, naphthalene structure, anthracene structure, phenanthrene structure, fluorene structure, phenol-fluorene structure, diphenylfluorene structure, pyrene structure, acetnaphthene structure, 1-ketoacenaphthene structure, benzophenone structure, xanthene structure, thixanthene structure, p-terphenyl Structure and m-turfell structure It is preferable to have at least one structure selected from manufacturing because it is possible to introduce relatively inexpensive raw material power.

Among these, a condensed polycyclic structure is more preferable. By having a conjugated structure that is a condensed polycyclic structure, the resist composition has good film formability, high etching resistance, and low exposure. Performance such as high sensitivity can be imparted due to the outgas amount and further sensitization effect. Preferable examples of the condensed polycyclic structure include at least one structure selected from naphthalene structure, pyrene structure, isenaphten structure, and 1-ketoacenaphthene structure strength.

The condensed polycyclic structure has high absorption of 248 nm light from KrF excimer laser and 193 nm light from ArF excimer laser, so it can be used as a material for removal of standing wave and antireflection film in lithography process.

[0017] The resist compound (A) comprises (a) a polyphenol obtained by a condensation reaction between an aromatic carbonyl compound (A1) having a conjugated structure and a phenolic compound (A2) having no synergistic structure. It is preferable that the surface area is a Louis compound.

[0018] The resist compound (A) preferably satisfies F≤3.0 (F represents the total number of atoms Z (total number of carbon atoms-total number of oxygen atoms)), and more preferably F≤ 2.5, more preferably F≤2.3, particularly preferably 1.8≤F≤2. By satisfying the above conditions, dry etching resistance is excellent.

[0019] The resist compound (A) is selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, carsol, butyl acetate, ethyl acetate, and ethyl acetate. The solvent having the highest solubility in the product (A) is preferably at least 1 wt%, more preferably at least 3 wt%, even more preferably at least 5 wt%, particularly preferably at 10 wt% at 23 ° C. % Or more dissolve. By satisfying the above conditions, a safe solvent can be used in the semiconductor manufacturing process.

[0020] The resist compound (A) used in the present invention includes, for example, a visible light, an ultraviolet ray, and a polyphenol compound produced by a condensation reaction of an aromatic carbonyl compound (A1) and a phenolic compound (A2). , Excimer laser, extreme ultraviolet (EUV), electron beam, X-ray, and group power that also has ion beam power Introduced a cross-linking reactive group that causes a cross-linking reaction directly or indirectly by irradiation of any selected radiation It is produced by an acid-catalyzed condensation reaction in which a reagent (crosslinking-reactive group introduction reagent (A3)) is reacted.

Acid-catalyzed condensation reactions are known, for example, aromatic carbocyclic compounds (A1) and phenolic compounds (A2) are converted to thioacetic acid or | 8-mercaptopropionic acid, and acid catalysts (hydrochloric acid). Or in the presence of sulfuric acid) (see JP-A-2001-206862). For example Using 1 to 16 moles of phenolic compound (A2) per mole of aromatic carbonyl compound (Al), thioacetic acid or j8-mercaptopropionic acid, and an appropriate amount of acid catalyst, 70 to 120 ° C for 20 minutes By maintaining for about 20 hours, the reaction proceeds advantageously.

Next, in order to introduce a crosslinking reactive group such as an attalyloyl group, a crosslinking reactive group introduction agent (A3) such as an alicyclic alkyl halide is added in the presence of a base catalyst such as triethylamine at atmospheric pressure and at room temperature. Incubate for 4 hours. Distilled water is added to the reaction solution to precipitate crystals, which are then washed with distilled water, purified by Z, column chromatography, high performance liquid chromatography, or the like, and dried to obtain a resist compound (A).

[0021] Examples of the crosslinking reactive group-introducing agent (A3) include carboxylic acid derivative compounds such as acids, acid chlorides, acid anhydrides and dicarbonates having a crosslinking reactive group, and alkylnos and rides. . Specific examples of the crosslinking reactive group include, as described above, a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogen phenyl group, as described above. And a chloromethyl group and the like.

The solvent used in the above reaction is not particularly limited as long as the polyphenolic compound obtained by the acid-catalyzed condensation reaction of the aromatic carbonyl compound (A1) and the phenolic compound (A2) is dissolved. A conventionally known aprotic polar solvent or the like can be used. For example, dimethylformamide, dimethylacetamide and the like can be mentioned. These may be used alone or in admixture of two or more.

[0022] The base catalyst used in the above reaction may be an alkaline compound, for example, mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic It is preferable to use at least one of amine compounds such as amines, tetramethylammonium hydroxide (TMAH), choline and other alkaline compounds, alkylammonium salts and alcoholates. Of these, trialkylamines such as triethylamine, triisopropylamine and tributylamine are preferred, and triethylamine is particularly preferred.

[0023] Examples of the aromatic carbocycle compound (A1) include acetophenone, benzophenone, α-acetonaphthone, 13-acetonaphthone, 9-fluorenone, 3-phenylone 9-fluorenone, 1, 3 diphenyl- 9 fluorenone , Acenaphthenone, naphthoquinone, anthraquinone, acenaphthenequinone, phenanthrenequinone, benzoylbiphenyl, benzoylnaphth Talen, Asilbiphenyl, Acylanthracene, Acylphenanthrene, Acylpyrene, Acylbenzopyrene, Acyllucanaphthylene, Acylnaphthacene, Acylpentacene, Acyltriphenylene, Asylfuran, Acylvirol, Acylvalen, Indanone, Tetralone, Atalidone, Flavone, isoflavone, dicetylbenzene, dicetylnaphthalene, diacetylbiphenyl, dibenzoylbenzene, dibenzoylnaphthalene, dibenzobibiphenyl, difluorenone, dibenzobibiphenyl, disilbiphenyl, Diacylanthracene, diacylphenanthrene, diacylpyrene, diacylbenzopyrene, diacylacenaphthylene, diacylnaphthacene, diacylpentacene, diacyltriphenylene, diacylfuran , Diacino levironore, diacylvalene, flavanone, triacylbenzene, tribenzoylbenzene, triacyltoluene, tribenzoyltoluene, triacylbiphenyl, triacylnaphthalene, triacylterphenyl, triacyltriphenylene, triacyl Xylene, tribenzoyl xylene, triacylbenzene, triacylbiphenyl, tribenzobibiphenyl, tribenzoylnaphthalene, tribenzoylterphenyl, triacylanthracene, tribenzoylanthracene , Triacyl bilene, tribensyl bilylene, triacyl phenalene, tribenzoyl phenanthrene, triacyl phenanthrene, tribenzyl phenanthrene, triacyl naphthenylene, tribensyl lucennaphthylene, tri A Rupiritrin, tribenzoylpyritrin, triacetylimidazole, tribenzoylimidazole, triformyl furan, triacyl furan, tribenzoyl furan, triacyl flavone, tribenzoyl flavone, triacyl indacene, tribenzo Ilindacene, triacyl isoflavone, tribenzoyl isoflavone, triacylpentacene, tribenzoylpentacene, tribenzoyltriphenylene, triacylthiazole, tribenzoylthiazole, tetraacylbenzene, tetra Aromatic ketones such as acylbiphenyl, tetraacylnaphthalene, tetrasil terphel, tetrasiltriphenyl; and benzaldehyde, tolaldehyde, anisaldehyde, 1 naphthaldehyde, 2-naphthaldehyde , Anthraldehyde, biphenyl aldehyde, formylfluorene, formylphenanthrene, formylpyrene, formylbenzopyrene, formylacenaphthylene, formylnaphthacene, formylpentacene, formyltriphenylene, formylvalene, diformyl Benzene, diformyl biphenyl, diformyl naphthalene, diformyl terphenyl, diformyl tri Phenol, toldialdehyde, anisdialdehyde, anthradialdehyde, diformylfluorene, diformyl phenanthrene, diformyl pyrene, diformyl benzopyrene, diformyl acenaphthylene, diformyl naphthacene, diformyl pentacene , Diformylvalene, triformylbenzene, triformylbiphenyl, triformylnaphthalene, triformylterphenyl, triformyltriphenylene, tetraformylbenzene, tetraformylbiphenyl, tetraformylnaphthalene, tetraformylterphenyl, tetraformylthiophene Diene, Triformyltoluene, Triformylxylene, Triformylbiphenyl, Triformylterphenyl, Triacylterphenyl, Triformylanthracene, Trifo Milphenanthrene, triformylpyrene, triformylindacene, triformylphenalene, triformyl naphthenylene, triformylphenalene, triacylphenalene, tribenzylphenalene, triformylnaphthacene, triacylnaphthacene, tribe Nzoylnaphthacene, triformylpentacene, triformyltriphenylene, triacyltriphenylene, triformylthiazole, triformylpyriline, triformylimidazole, triformylflavone, triformylisoflavone, tetraformylbenzene, tetra Aromatic aldehydes such as formylbiphenyl, tetraformylnaphthalene, tetraformyl terfal, and tetraformyl triphenylene are listed.

[0024] Among the above aromatic ketones, α-acetonaphthone, j8-acetonaphthone, 9 fluorenone, acetylenthracene, acetilbilene, acenaphthenone, acenaphthenequinone, anthraquinone, and among the aromatic aldehydes, 1 naphthaldehyde, 4-bif ヱ-Aldehyde is preferred because it is available at low cost, has a relatively high reactivity and is easy to produce. Among the above aromatic aldehydes, formyl biphenyl, formyl phenanthrene, formyl pyrene, formyl triphenyl, 3 ferro 9 fluorenone, 1, 3 -diphen 9 fluorenone, phenanthrenequinone, Difluorenone, diformylbiphenyl, diformylnaphthalene, diformylterphenyl, triformylbenzene, triformylbiphenyl, triformylnaphthalene, triformylterphenyl, triformyltriphenyl, tetraformylbenzene, tetraformylnaphthalene have good sensitivity and solution It is preferable because it can add image quality.

[0025] Examples of the phenolic compound (A2) include phenol, C alkylphenol (for example, O cresol, m-cresol, p-taresol and other talesols), dialkylphenol (eg, 2,3 dimethylphenol, 2,5 dimethylphenol, 2,6-dimethylphenol, 2,6 di tert butylphenol), Trialkylphenols (eg, 2, 3, 6 trimethylphenol), alkoxyphenols (eg, oleols such as o-methoxyphenol), arylphenols (eg, o-phenolphenol, m-phenolphenol, etc.) Phenol-phenols), cycloalkyl phenols (eg 2-cyclohexylphenol), halogenated phenols (eg black-mouthed phenols, dichlorophenols, black-cresenoles, bromophenols, dibromophenols) Nonore), polyvalent (thio) phenols (for example, , Catechol, alkylcatechol, chlorocatechol, resorcinol, alkylresorcinol, hydroquinone, alkylhydroquinone, chlororesonoresinole, chlorohydroquinone, pyrogalonore, anorequinolepirogalol, phloroglicinol, 1, 2, 4 trihydroxyphenol, and compounds obtained by substituting the OH group of these compounds with SH groups). The above compounds may be used alone or in combination of two or more. The purity is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

Of the above phenolic compounds (A2), phenol, C alkylphenol, particularly preferred

1-6

2—C alkylphenols (such as o-taresole), arylphenols (such as o-phenol)

1-6

For example, chelphenol, etc., cycloalkylphenol (2-cyclohexylphenol, etc.), catechol, resorcinol, pyrogallol are preferred. Also, the phenolic compound (A2) having a bulky substituent at the o-position of the phenolic hydroxyl group and Z or an electron-donating functional group reduces the crystallinity of the resist compound (A) and improves the film-forming property. Let Examples of such bulky substituents and Z or electron donating functional groups include methyl, tert-butyl, cyclohexyl, phenyl, methoxy, isopropoxy, phenoxy and the like. Further, it is particularly preferable because it provides a resist pattern with high sensitivity, resolution and residual film ratio while reducing crystallization of the 2, 3, 6 trimethylphenol resist compound (A).

[0027] The resist compound (A) is !, a so-called geminal bisphenol, that is, a compound having at least one carbon atom to which two funols are bonded (diminally substituted carbon atom). It is. The dieminally substituted carbon atom corresponds to the carbonyl carbon of the aromatic carbo-louis compound (A1). When the aromatic carbonyl compound (A1) has two or more carbonyl groups, the resist compound (A) has two or more dieminally substituted carbon atoms.

The resist compound (A) in the present invention is preferably one represented by the following formula (1-1).

[Chemical 1]

(In the formula (1 1),

R ² is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarboxoxy group, an alkylcarboxoxy group, an arylcarboxoxy group, or a cyano group. A group force consisting of, and -tro groups

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁵ is a monovalent group having 10 to 30 carbon atoms having a biphenyl structure, a terphenyl structure, a naphthalene structure, a phenanthrene structure, or a pyrene structure;

Alternatively, R ⁴ and R ⁵ are combined to form a fluorene structure, a phenol fluorene structure, a diphenyl fluorene structure, a naphthenic structure, a 1-keto acenaphthene structure, a 9 keto-9, 10- dihydrophenanthrene structure, or a benzophenone structure. A divalent group having 10 to 30 carbon atoms;

A is a group in which an aryloxy group, an talyloxy group, a glycidyloxy group, and a halogenomethyloxy group are also selected, and at least one of A is an aryloxy group, an talyloxy group, a glycidyloxy group And a group selected from a halogenated methyloxy group;

pl and ql are integers from 0 to 3;

p2 and q2 are integers from 0 to 4; l≤pl + p2≤5, l≤ql + q2≤5, l≤pl + ql≤6, and a plurality of R ² and A may be the same or different.

In the formula (1-1), the carbons in the ortho position with respect to —CI ^ R ⁵ — of the two benzene rings may be bonded via an oxygen atom or a sulfur atom. )

In the above R ² , 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 group, ethyl group, propyl group, n-propyl group, n butyl group, isobutyl group, sec butyl group and tert butyl group. Examples of the cycloalkyl group include a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl groups. Examples of the aralkyl group include a benzyl group. Examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, n butoxy group, isobutoxy group, sec butoxy group, and tert butoxy group. Groups. Examples of the alkenyl group include alkenyl groups having 2 to 4 carbon atoms such as a bur group, a propenyl group, a allyl group, and a butenyl group. The acyl group has 1 carbon atom such as formyl, acetyl, propionyl, petityl, valeryl, isovaleryl, and bivaloyl.

And aliphatic acyl groups of ˜5 and aromatic acyl groups such as benzoyl group and toluoyl group. Alkoxycarboxoxy groups include methoxycarboxoxy group, ethoxycarboxyloxy group, propoxycarbonyloxy group, isopropoxycarboxoxy group, n-butoxycarboxoxy group, isobutoxycarboxoxy group, sec butoxycarbonyloxy group. Examples thereof include an alkoxycarboxoxy group having 2 to 5 carbon atoms such as a xy group and a tert butoxycarboxoxy group. Examples of the alkylcarboxoxy group include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, bivalyloxy group and the like. Examples of arylcarboxoxy groups include benzoyloxy groups.

[0030] Also, it is preferable that R ² is substituted with the adjacent position of A U. The adjacent R ² lowers the crystallinity of the resist compound and improves the film formability. R ² is preferably a bulky group and a Z or electron-donating group. Such groups include methyl, ethyl, isopropyl, t Alkyl groups such as butyl group; cycloalkyl groups such as cyclohexyl group, norbornyl group and adamantyl group; aryl groups such as phenyl group; aralkyl groups such as benzyl group; methoxy group, ethoxy group and isopropoxy group And alkoxy groups such as phenoxy group. R ² is preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group, and more preferably a methyl group.

[0031] In the above formula (1-1), the carbons in the ortho position with respect to CR ⁴ R ^5- of the two benzene rings are bonded via an oxygen atom or a sulfur atom, and the following formula (12) The xanthene structure or thixanthene structure represented may be formed. Sensitivity may be improved by having such a structure.

[0032] [Chemical 2]

(In the formula (1-2), R ² , R ⁴ , R ° and A are the same as above;

el and fl are integers from 0 to 2;

e2, f2 are integers from 0 to 3;

satisfies l≤el + e2≤4, l≤fl + f2≤4, l≤el + fl≤2;

X is an oxygen atom or a sulfur atom. However, the plurality of R ² and A may be the same or different).

[0033] The xanthene structure or thixanthene structure of the formula (12) is a compound having 2 or 3 phenolic hydroxyl groups or thiophenolic mercapto groups among the above-mentioned phenolic compounds (A2), preferably a polyvalent (thio). It can be introduced by using phenols. As polyvalent (thio) phenols, (thio) catechol, (thio) resorcinol, and (thio) pyrogallol are preferred because of the availability of raw materials!

Although the compound of formula (1-2) is a low molecular compound, it has film formability, heat resistance, and dry etching. Since the resisting resistance is good and the outgas is small, it can be used as a main resist component, and a resist composition having high resolution, high sensitivity, and low line edge roughness can be obtained.

In the above formulas (1-1) and (1-2)! /, R ⁵ is the following formula:

[Chemical 3]

[0035] It is preferable to be a group represented by a deviation! /.

In the above formula, R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. Examples of the alkyl group 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, a pentyl group, and a hexyl group; P3 is an integer of 0-4, q3 is an integer of 0-3, and satisfies 0≤p3 + q3≤7. r3 is an integer of 0-2. A plurality of p3, q3, and r3 may be the same or different from each other

[0036] R ⁵ having the above structure includes, as an aromatic carbonyl compound (A1), a-acetonaphthone, β-acetonaphthone, 1-naphthaldehyde, 2-naphthaldehyde, biphenyl-aldehyde, formylphenanthrene, formylpyrene, and the like. It can be introduced by use. In the above formulas (1-1) and (1-2), the divalent group formed by combining R ⁴ and R ⁵ is T 3 self formula:

[Chemical 4]

[0038] A group represented by any one of the above is preferred.

In the above formula,

p3, q3, and r3 are the same as above, Y is a single bond or a carbo group, and Z is a methylene group or a carbo group. A plurality of p3 and q3 may be the same or different.

The above divalent groups are, as aromatic carbo compounds (A1), 9 fluorenone, 3 ferrules, 9 fluorenone, 1, 3 diphenol, 1 fluorenone, acenaphthenone, acenaphthenequinone, phenanthrenequinone. Etc. can be introduced.

In addition, the resist compound (A) in the present invention is represented by the following formula (2-1) obtained by using an aromatic diketone or an aromatic dialdehyde as the aromatic carbonyl compound (A1). Compounds are preferred. The compound of the formula (2-1) is particularly preferable because it further improves heat resistance, sensitivity, and resolution.

Examples of the aromatic diketone and aromatic dialdehyde include difluorenone, diformol Examples include milbiphenyl, diformylnaphthalene, diformyl terphenyl, diformyl triphenyl: len and the like.

[Chemical 5]

(In the formula (2-1),

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁶ is a divalent group having 10 to 30 carbon atoms having a biphenyl structure, terphenyl structure, naphthalene structure, phenanthrene structure, or pyrene structure;

Or two R ⁴ and R ⁶ are bonded together to form a fluorene structure, a phenol fluorene structure, a diphenyl fluorene structure, a naphthenic structure, a 1-keto naphthenic structure, a 9-keto-9, 10-dihydrophenanthrene, or A tetravalent group having 10 to 30 carbon atoms and having a benzophenone structure;

A is a group in which an allyloxy group, an talyloxy group, a glycidyloxy group, and a halogenomethyloxy group are also selected, and at least one of A is an allyloxy group, an talyloxy group, a glycidyloxy group And a group selected from a halogenated methyloxy group;

ml, nl, tl, si are integers from 0 to 3;

m2, n2, t2, s2 are integers from 0 to 4; l≤ml + m2≤5, l≤nl + n2≤5, l≤tl + t2≤5, l≤sl + s2≤5, l≤ml + nl + tl + sl≤6, multiple R ² may be the same or different.

In the formula (2-1), the carbon in the ortho position with respect to —CR— of the two benzene rings bonded via —CR ⁴ ! ^ — Is bonded via an oxygen atom or a sulfur atom. ! / ヽ)

[0042] In the above formula (2-1), the carbons of the two benzene rings in the ortho position with respect to -CR ⁴ R ^6- are bonded via an oxygen atom or a sulfur atom to form the following formula (2-2 A xanthene structure or a thixanthene structure represented by) may be formed. Sensitivity may be improved by having such a structure.

[0043] [Chemical 6]

(In the formula (2-2), R ² , R ⁴ , R ° and X are the same as above;

al, bl, cl, dl are integers from 0 to 2;

a2, b2, c2, d2 are integers from 0 to 3;

l≤al + a2≤4, l≤bl + b2≤4, l≤cl + c2≤4, l≤dl + d2≤4, l≤al + bl + cl + dl≤4, multiple, R ⁴ may be the same or different. In formula (2-2), it is preferable that al, bl, cl, and dl each be 1 because sensitivity and resolution are improved.

In the above formulas (2-1) and (2-2)! /, R ⁶ represents the following formula:

[Chemical 7]

(In the above formula, R ³ and q3 are the same as described above, and a plurality of R ³ and q3 may be the same or different.)

of! It is preferable to be represented by a gap! /.

[0045] R ⁶ having the above structure should be derived from the use of diformyl biphenyl, diformyl naphthalene, diformyl terfal, diformyl triphenyl, etc. as the aromatic carbonyl compound (A1). Can do.

In the above formulas (2-1) and (2-2), a tetravalent group represented by the combination of R ⁶ and two R ⁴ is represented by the following three formulas:

[Chemical 8]

(In the above formula, R ³ , Y, q3 and r3 are the same as described above, and a plurality of R ³ and q3 may be the same or different from each other.)

The group represented by these is preferable.

The above structure can be introduced by using difluorenone or the like as the aromatic carbonyl compound (A1).

The resist compound (A) in the present invention is represented by the following formula (3) obtained by using an aromatic triketone or aromatic trialdehyde as the aromatic carbonyl compound (A1). Compounds are preferred. The compound of the formula (3) is particularly preferable because it further improves heat resistance, sensitivity, and resolution.

Examples of the aromatic triketone or aromatic trialdehyde include triformylbenzene, triformylbiphenyl, triformylnaphthalene, triformylterphenyl, triformyltriphenylene, triacetylbenzene, triacetylbiphenyl, triacetyl naphtha. Examples include lenth, triacetyl turf, and triacetyl phenylene.

[0048] [Chemical 9]

[0049] (In Formula (3),

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁸ is a trivalent group having 10 to 30 carbon atoms having a biphenyl structure, terphenyl structure, naphthalene structure, phenanthrene structure, or pyrene structure;

Or two R ⁴ and R ⁸ are bonded together to form a fluorene structure, a phenol fluorene structure, a diphenyl fluorene structure, a naphthenic structure, a 1-keto naphthenic structure, a 9-keto-9, 10-dihydrophenanthrene, or A hexavalent group having 10 to 30 carbon atoms and having a benzophenone structure;

A is a group in which an aryloxy group, an talyloxy group, a glycidyloxy group, and a halogenomethyloxy group are also selected, and at least one of A is an aryloxy group , A group selected from the group consisting of taliloyloxy group, glycidyloxy group, and halogenated methyloxy group;

m4, n4, j4, k4, x4, y4 are integers from 0 to 3;

m5, n5, j5, k5, x5, y5 are integers from 0 to 4;

I≤m4 + m5≤5, 1≤η4 + η5≤5, I≤j4 + j5≤5, I≤k4 + k5≤5, l≤x4 + x 5≤5, I≤y4 + y5≤5, I meet the ≤m4 + n4 + j4 + k4 + x4 + y4≤ 18, a plurality of R ² may be the same or different! /ヽbe good!ヽ)

In the formula (3), R ⁸ represents the following formula:

[Chemical 10]

of! It is preferable to be represented by a gap! /.

[0051] R ⁸ is an aromatic carbocycle compound (A1) such as triformylbenzene, triformylbiphenyl, triformylnaphthalene, triformylterphenyl, triformyltriphenylene, triacetylbenzene, triacetylbiphenyl, It can be introduced by using triacetylnaphthalene, triacetyl terephthal, triacetyl phenylene, etc.

[0052] Among the above-mentioned compounds, the resist compound (A) is represented by the following formulas (13) to (112), (2)

3) to (2-6), and (3-1) to (3-2) are preferably at least one compound selected from the compounds represented by

[0053] [Chemical 11]

[Zl ^ [00]

990llC / 900Zdf / X3d zz 6 £ i / 900Z OAV

[0055] [Chemical 13]

[0056] [Chemical 14]

[0057] [Chemical 15]

[0058] [Chemical 16]

In the compounds represented by the above formulas (1 3) to (1 12), (2-3) to (2-6), and (3-1) to (3-2), R ² to R ⁴ , X, Y, Z, A, pl ~ p3, ql ~ q3, pl + p2, ql + q2, pi + ql, el ~ e2, fl ~ f2, el + e2, fl + f2, el + fl, p3, q3, p3 + q3, ml, nl, tl, sl, m2, n2, t2, s2, ml + m2, nl + n2, tl + t2, sl + s2, ml + nl + tl + sl, al, bl, cl, dl, a2, b2, c2, d2, al + a2, bl + b2, cl + c2, dl + d2, al + bl + cl + dl, r3, m4, n4, j4, k4, x4, y4, m5, n5, j5, k5, x5, y5, m4 + m5, n 4 + n5, j4 + j5, k4 + k5, x4 + x5, y4 + y5, m4 + n4 + j4 + k4 + x4 + y4 are the same as described above.

[0060] Among the above resist compounds (A), the formulas (1-3), (1-6), (1-7), (19), (110), (1-11), (2 — The compounds represented by 3) and (3-2) are particularly preferred. When a compound has a condensed ring, sensitivity and resolution are improved.

It is more preferable that the cross-linking reactive group A of the resist compound (A) is a group in which an talyloxy group, an aryloxy group, a glycidyloxy group, and a chloromethyloxy group are also selected. More preferably, it is a group selected from a xy group, an aryloxy group and a chloromethyloxy group. When such a crosslinking reactive group A is used, high sensitivity and high resolution can be obtained, and the storage stability of the resist compound (A) is improved.

[0061] The resist composition of the present invention contains one or more resist compounds (A) described above. When one type of such resist compound is used, high sensitivity and high resolution can be obtained, and when two or more types are used, film formability and substrate adhesion are further improved.

[0062] In the resist composition of the present invention, the solid component is preferably 1 to 80% by weight and the solvent 20 to 99% by weight, more preferably 1 to 50% by weight of the solid component and 50 to 99% by weight of the solvent. The solid component is preferably 2 to 40% by weight and the solvent 60 to 98% by weight, particularly preferably the solid component 2 to LO weight% and the solvent 90 to 98% by weight.

The amount of the resist compound (A) is preferably 3 to 96.9% by weight of the total weight of the solid component, more preferably 50 to 96.9% by weight, still more preferably 65 to 96.9% by weight. %, Particularly preferably 81 to 96.9% by weight. With the above blending ratio, a high resolution is obtained and the line edge roughness is reduced.

[0063] The resist composition of the present invention is directly applied by irradiation with any one of the selected group powers of visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, and ion beam power. Alternatively, it is desirable to add a compound (B) that indirectly generates radicals or cations.

[0064] Among the compounds (B), as a compound (B-1) that generates radicals, a compound that mainly generates radicals by interacting with a radical initiator and a photoexcited sensitizer, mainly, There are compounds that have both sensitization by ultraviolet light and radical generation ability. I can get lost. Examples of the radical initiator include peroxides such as benzoyl peroxide, peroxide tert butyl, lauroyl peroxide, acetyl peroxide, tert butyl hydroperoxide, tamen hydroperoxide; azobisisobutyoxy-tolyl, azobiscyclohexane Azo compounds such as tolyl, phenol triphenylmethane; persulfates such as potassium persulfate and ammonium persulfate; triethylaluminum, trimethylaluminum, ethylaluminum dichloride, jetylaluminum chloride, etc. Organoaluminum compounds; other organometallic compounds such as tetraethyl lead, jetyl zinc, jetyl cadmium, tetraethyl tin; titanium tetrachloride, trisalt-titanium, salt-aluminum, aluminum bromide, stannic chloride, salt Zinc fluoride, boron trifluoride, boron trifluoride Examples thereof include chlorides such as thioetherate and phosphorus pentafluoride. Examples of the compounds that generate radicals by interacting with the photoexcited sensitizer are described in, for example, JP-A-59-152396 and JP-A-61-151197. (Specifically, di-cyclopentagel Ti didichloride, di-cyclopentagel Ti bis-phenyl, di-cyclopentagenyl Ti-bis 1, 3, 4, 5, 6 Pentafluorophenyl 1-yl, di-cyclopentagenyl Ti-bis-1, 2, 5, 5, 6-Tetrafluorophenyl 1-yl, di-cyclopentagenyl Ti-bis-1, 4, 6 trifluorophenyl 1—yl, dicyclopentagenyl—Ti— 2, 6 di-fluorophenyl 1—yl, di-cyclopentagenyl Ti—bis-1, 2, 4 difluorophenyl 1-il, di-methyl methyl mouth pentagenyl Ti-Bi 1, 2, 4, 4, 5, 6 Pentafluorophenyl 1-yl, di-methylcyclopentagenyl Ti-bis-1,6 Difluorophenyl 1-yl, di-cyclopentageninole 1 Ti-Bis 1 2, 6 Diphnoroleo 3— (Pinole 1-inore) 1-Fe 1-il, etc.), Bull. Chem. Soc. Japan. 33, 565 (1960) and J. Org. 16] Hexaary monobiimidazoles that can be easily synthesized by the method disclosed in 2262 (1971) (specifically, 2, 2 ′ bis (o chlorophenyl) —4, 4 ′, 5, 5 '— Tetra (p-fluorophenol) biimidazole, 2, 2' — Bis (o bromophenol) 4, 4 ', 5, 5' — Tetra (p-phenol) biimidazole, 2, 2 '— Bis (O-black mouth file) one 4, 4 ', 5, 5'-tetra (p black mouth naphthyl) biimidazole, 2, 2 '-bis (. One mouth mouth file) one 4, 4' , 5, 5 '—Tetra (p Russia opening Hue - Le) Biimi Dazole, 2, ₂ / — bis (.one bromophenol) — ₄ , ₄ ', 5, 5' — tetra (p chlorophene P-methoxyphenol) biimidazole, 2, 2 '— bis (o chloro) 1) 4, 4 ', 5, 5' — Tetra (o, p dichlorophenol) biimidazole, 2, 2 '— Bis (o black mouth phenol) 4, 4', 5, 5 '— Tetra (o, p dibromophenol) biimidazole, 2, 2' -bis (o bromophenol) 1, 4, 4 ', 5, 5' — Tetra (o, p dichlorophenol) biimidazole, 2 , 2 '— Bis (o, p dichlorophenyl) 1, 4, 4', 5, 5 '— Has a halogen substituent on the benzene ring such as tetra (o, p dichlorophenyl) biimidazole Hexaarylbiimidazoles, etc.), halogenated hydrocarbon derivatives, diarylhodonium salts, organic peroxides and the like. Examples of the compound having both the sensitization effect mainly by ultraviolet light and the radical generation ability thereof include 2,2-dimethoxy 1,2-diphenylethane 1-on, 2-isopropoxy 1,2-diphenylethane 1 ON, (1'-Hydroxycyclohexyl) phenol ketone, 2-Methyl 1- (4'-Methylthiophenol) —2—Morpholinopropane 1-one, 2-Benzyl 1- (N, N Dimethylamino) — 1— (4 'morpholinophenol) butane 1-one, 2-hydroxy-2 methyl-1 phenylpropane 1-one, 2, 4, 6 trimethylbenzoyldiphenylphosphine oxide, 1— [ 4 '— (2 hydroxyethoxy) phenol] —phenol derivatives such as 2-hydroxy-1,2-methyl-1, propan-1one, 4 (N, N dimethylamino) benzoic acid isoamyl ester, 4 (N, N— Dimethylamino) Benzoic acid esters such as benzoic acid ethyl ester, (7? ⁵ — 2, 4-cyclopentagen 1 yl) [(1, 2, 3, 4, 5, 6-7?) — (1-isopropylbenzene) Examples thereof include organometallic compounds such as one iron hexafnoroleolophosphate and heteroaromatic compounds such as 2,4 jetylthioxanthone.

Among the compounds (B), the compound (B-2) that generates cations includes at least one selected from the group forces represented by the following formulas (51) to (58).

[Chemical 17]

In formula (51), R may be the same or different and each independently represents a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a carbon number. A 3-12 cyclic alkyl group, a linear alkoxy group having 1-12 carbon atoms, a branched alkoxy group having 3-12 carbon atoms, a cyclic alkoxy group having 3-12 carbon atoms, a hydroxyl group, or a halogen atom. Yes, a sulfonate ion having an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a halogen-substituted aryl group having 6 to 12 carbon atoms Or halide ions.

The compound represented by the formula (51), bird whistle - Rusuruho - © beam triflate Ruo b methanesulfonate, bird whistle - Rusuruho - © beam nonafluorobutyl over n- butane sulfonate, bird whistle - Le sulfo - © beam perfluoro over _n - octane Sulfonate, Diphenyl 4-Methylphenol sulfo-trifluoromethanesulfonate, Diphenyl 2,4,6 Trimethylphenylsulfo-trifluoromethanesulfonate, Diphenyl 4t Butoxyphenyl-sulfo-trifluoromethane Sulfonate, diphenyl 4-t-butoxyphenyl sulfone nonafluorobutane sulphonate, diphenyl 4-hydroxyphenylsulfo-trifluoromethyl sulfonate, bis (4 fluorophenyl) -4-deoxyphenyl sulfone Mutrifluoromethanesulfonate, di 4-Hydroxyphenylsulfo-ummonafluoro-n-butanesulfonate, bis (4-hydroxyphenol) monophenylsulfo-trifluoromethanesulfonate, tris (4-methoxyphenol) sulfo -Um trifluoromethane sulfonate, tris (4-fluorophenyl) sulfur trifluoromethane sulfonate, triphenyl sulfo-mu p-toluene sulfonate, triphenyl sulfo-mu benzene sulfonate, diphenol 2, 4, 6 Trimethylphenol p-toluenesulfonate, diphenol 2, 4, 6 Trimethylphenol Sulfo-um 2 trifluoromethylbenzene sulfonate, diphenol 2, 4, 6— Trimethyl phenol sulfo-mu 4 Trifluoromethyl benzene sulfonate, diphenol 2, 4, 6 Trimethyl phenol sulfo-um 2, 4 Difluorobenzene sulfonate, diphenyl 2, 4, 6 Trimethylphenol sulfo-hexafluorobenzen sulfonate, diphenylnaphthylsulfo-mutrifluoromethane sulfonate, diphenylenolate 4 -Hydroxyphenyl-norethnorephonium p-tolerenesnorephonate, triphenyl-noresulfo-sulfur 10-camphor sulfonate, and diphenyl-hydroxy 4-hydroxyphenyl sulfo-mono 10-camphor sulfonate Preferably at least one kind.

[0067] [Chemical 18]

(52)

In the formula (52), X— and R ²⁴ are the same as X— and R ^{23 in the} formula (51).

[0068] The compound represented by the above formula (52) is bis (4-tert-butylphenol) iodine trifluoromethanesulfonate, bis (4tert-butylphenol) iodide-munonafluoro- n Butanesulfonate, bis (4 t-butylphenol) odoperperfluoro n-octanesulfonate, bis (4 tert-butylphenol) iodide-um p-toluenesulfonate, bis (4 t-butylphenol) Odonium benzene sulfonate, bis (4 t-butylphenol) odonium 2 trifluoromethylbenzene sulfonate, bis (4 tert-butylphenol) odonium 4 trifluoromethylbenzene sulfonate, bis (4 t butylphenol) Le) odo-um 2, 4 difluorobenzenesulfonate, bis (4 tert-butylphenol) , Bis (4-t Buchirufue - Le) Yodoniumu - 10-camphorsulfonate, Jifue - Ruyo one Denis © beam triflate Ruo b methanesulfonate, Jifue - Ruyodo - © beam nonafluorobutyl over _n - butane Sno Reho sulfonate, Jifue - Noreyodo - Nupper noreo n octanes norephonate, jihue nore honde um p tono rens nore honate, jihue nore honde-um benzenes nore honate, jihue nore honde noum 10-camphors nore honedo -UM 2 Trifluoromethyl benzene sulfonate, diphenol rhododonium 4 Tote Fluoromethyl benzene sulfonate, diphenol rhododonium 2, 4 Difluoro benzene sulfonate, diphenyl sulfonate benzene sulfonate Bis (4 trifluoronoroleomethylphenol) odo-umtrifureololeomethane sulphonate, bis (4 trifluoromethylphenol) odo-umnonafluoro-n-butanesulfonate, bis ( 4 trifluoromethyl phenol) iodine perfluoro-n-octanesulfonate, bis (4 trifluoromethyl phenol) iodine-um p-toluenesulfonate, bis (4 trifluoromethyl) (Fuel) Jodnium benzene sulfonate and bis (4 trifluoromethyl phenol) It is preferred group force consisting © beam 10 camphorsulfonate also at least one kind selected - over de.

[0069] [Chemical 19]

0

II 0

, ¹¹ ς

CT ヽ N— 0—S—FT ⁵ (53)

C II II 0

0

[0070] In the formula (53), Q is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, or an alkyleneoxy group having 1 to 12 carbon atoms (—R ′ ——, where R ′ is an alkylene group having 1 to 12 carbon atoms, and R ²⁵ is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, or a carbon number. 6 to 12 halogen-substituted aryl groups.

[0071] The compound represented by the formula (53) includes 、 (trifluoromethylsulfo-loxy) succinimide, Ν— (trifluoromethylsulfo-loxy) phthalimide, Ν— (trifluoromethylsulfo-loxy) diphenol- Lumaleimide, Ν— (Trifluoromethylsulfo-loxy) bicyclo [2.2.1] hept-5-1,2-dicarboximide, Ν— (Trifluoromethylsulfo-loxy) naphthylimide, Ν- (10— Camphorsulfuroxy) succinimide, Ν— (10-camphorsulfo-loxy) phthalimide, Ν— (10—force sulfo-loxy) diphenylmaleimide, Ν— (10-camphorsulfo-loxy) bicyclo [2. 2. 1] Hepto 1-5 3,3 dicarboximide, Ν— (10—force N- (n-octanesulfo-loxy) naphthylimide, N- (n-octanesulfo-loxy) naphthylimide, N- (n-octanesulfo-loxy) naphthylimide, N- (n-octanesulfo-loxy) naphthylimide, N— (p Toluenesulfo-loxy) bicyclo [2. 2. 1] Hepto-5 Nen— 2, 3 Dicarboximide, N— (p Toluenesulfo-loxy) naphthylimide, N- (2-Trifluoromethyl Benzenesulfo-loxy) bicyclo [2. 2. 1] hept-5ene— 2, 3 dicarboximide, N— (2 trifluoromethylbenzenesulfo-loxy) naphthylimide, N- (4 trifluoromethylbenzene Sulfo-loxy) bicyclo [2. 2. 1] hepto-5-- 2, 3 dicarboximide, N— (4-trifluoromethylbenzenesulfo-loxy) naphthylimide, N- (perfluoro Nzensulfo-loxy) bicyclo [2.2.1] hepto-5-ene-1,3 dicarboximide, N- (perfluorobenzenesulfo-loxy) naphthylimide, N- (1 naphthalenesulfo-loxy) bicyclo [ 2. 2. 1] Hepto-5 1,2-dicarboximide, N— (1-Naphthalenesulfo-loxy) naphthylimide, N— (Nonafluoro-n-butanesulfo-loxy) bicyclo [2. 2. 1] Hepto 5 1,3-dicarboxyimide, N- (nonafluoro-n-butanesulfo-loxy) naphthylimide, N- (perfluoro- _n -octanesulfo-loxy) bicyclo [2. 2. 1] hepto-2 Preferably, the group force consisting of 3-dicarboximide and N- (perfluoro-n-octanesulfo-loxy) naphthylimide is also at least one selected.

[0072] [Chemical 20] (54)

[0073] In the formula (54), R ²⁶ may be the same or different and each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a carbon number of 3 A cycloalkyl group having 12 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Each of the above groups may be substituted with an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, a halogen, or a haloalkyl group having 1 to 12 carbon atoms.

[0074] The compound represented by the formula (54) is diphenyl disulfone, di (4 methylphenol) ) Disulfone, dinaphthyl disulfone, di (4 tert butylphenol) disulfone, di (4-hydroxyphenyl) disulfone, di (3-hydroxynaphthyl) disulfone, di (4-funoleo mouth fue-nore) disnolephone, Preferably, it is at least one selected from the group consisting of di (2 funoleo mouth fu-nore) dysnophone and di (4 trifluoromethylphenol) disulfone.

[0075] [Chemical 21]

0

R ²⁷ — C = N— 0— S— R ²⁷ (55)

I II

CN 0

In formula (55), R ²⁷ may be the same or different and each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or 3 carbon atoms. A cycloalkyl group having 12 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Each of the above groups may be substituted with an alkyl group having 1 to 12 carbon atoms, halogen, or an alkoxyl group having 1 to 12 carbon atoms!

[0077] The compound represented by the formula (55) includes α (methylsulfo-luoxyimino) -fluoroacetonitrile, at- (methylsulfo-ruxitimino) -4-methoxyphenylsulfatonitrile, α- (trifluoromethylsulfo-luoximino) ) -Phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfo-ruximino) -4-methoxyphenylacetonitrile, at- (propylsulfo-ruximino) -4 methylphenol -Luacetonitrile, and α (methylsulfoxy-imino) -4-bromophenol-luacetonitrile force is preferably at least one type selected.

[0078] [Chemical 22]

R ²⁸

I I (56)

R ²⁸ CR ⁸

II

O

[0079] In the formula (56), R ²⁸ may be the same or different and each independently represents one or more chlorine atoms. And a halogenated alkyl group having one or more bromine atoms. The number of carbon atoms in the halogenated alkyl group is preferably 1-5.

The compound represented by the formula (56) includes monochloroisocyanuric acid, monobromoisocyanuric acid, dichloroisocyanuric acid, dib-mouthed moisocyanuric acid, triclo-mouthed isocyanuric acid, and tribromoisocyanuric acid. It is preferable that the group power is at least one kind selected.

[0080] [Chemical 23]

In Formulas (57) and (58), R ²⁹ and R ^3Q are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group; a cyclopentyl group A cycloalkyl group having 3 to 12 carbon atoms such as a cyclohexyl group; an alkoxyl group having 1 to 3 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group; a phenyl group, a tolyl group and a naphthyl group And preferably an aryl group having 6 to 10 carbon atoms. L ²⁹ and L ³ ° are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include 1,2-naphthoquinonediazido 4-sulfol group, 1,2-naphthoquinonediazido 5-sulfol group, 1, 2- Preferred examples include 1,2-quinonediazidosulfol groups such as naphthoquinonediazido6-sulfol group. In particular, a 1,2-naphthoquinonediazide-4-sulfol group and a 1,2-naphthoquinonediazido5-sulfol group are preferred. p is an integer from 1 to 3, q is an integer from 0 to 4, and l≤p + q≤5. J ²⁹ is a single bond, a polymethylene group having 2 to 4 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, a phenylene group having 6 to 10 carbon atoms, the following formula (59):

[0082] [Chemical 24]

R ^a — C (= 0) —R ^b , one R ^a C (= 0) —O—R ^b —, —R ^a —C (= 0) —NH—R ^b —, or R ^c - O- R ^d - (provided that represent R ^a and R ^b is an alkylene group Yogu each independently a single bond or a 1 to 3 carbon atoms which may be the same or different, charcoal R ^a and R ^b The sum of prime numbers is 0 to 3; and R ^d may be the same or different and each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, and the sum of carbon numbers of R ^d is 0 Y ²⁹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and X ²⁹ and X ³ ° are respectively represented by the following formulae: (60):

[0083] [Chemical 25]

In formula (60), each independently represents an alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ³² represents a carbon atom. An alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms, and r is an integer of 0 to 3.

It is group shown by these.

[0084] Other compounds (B) include bis (p-toluenesulfol) diazomethane, bis (2,4-dimethylphenolsulfol) diazomethane, bis (tert-butylsulfol) diazomethane, bis (n —Bisulsulfol) diazomethane, bis (isobutylsulfol) diazomethane, bis (isopropylsulfol) diazomethane, bis (n-propylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, etc. -Ludiazo methanes, 2- (4-methoxyphenol) 1, 4, 6- (bistrichloromethyl) 1, 3, 5 triazine, 2— (4-methoxynaphthyl) 4, 6- (bistrichloromethyl) 1 , 3, 5 Triazine, Tris (2, 3 dibromopropyl) 1, 3, 5 Triazine, Tris (2, 3 dibromopropyl) Halogen-containing triazine derivatives such as (oral pill) isocyanurate.

[0085] In addition, the compound (B) may be used alone or in combination of two or more.

In the resist composition of the present invention, a crosslinking agent, a dissolution accelerator, a dissolution controller, a sensitizer, and a surface active agent may be added as the other component (C) as necessary, as long as the object of the present invention is not impaired. One or more additives such as a sex agent can be added.

[0086] [1] Crosslinking agent

In the present invention, in order to increase sensitivity, a compound having a vinyl group, a aryl group, a cinnamoyl group, a vinyl silyl group, an epoxy group, a halogenated methyl group or a halogenated fur group, or a resin is added. You can also.

These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent is preferably 50 parts by weight or less, more preferably 25 parts by weight or less, and particularly preferably 5 parts by weight or less, per 100 parts by weight of the resist compound.

[0087] [2] Sensitizer

The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the compound (B), thereby increasing the generation amount of radicals or cations, and the apparent resist resistance. It is a component that improves sensitivity. Examples of such a sensitizer include triphenylmethane leuco dyes such as leuco crystal violet leucomalachite green disclosed in U.S. Pat. No. 3,479,185, and erythrosine synthase. Photoreducible dyes such as Nyacin Y, Michler's ketone and aminostyryl ketone disclosed in U.S. Pat.No. 3,549,367, U.S. Pat.No. 3,652,275, etc., or Aromatic ketones such as benzophenone and biacetyl, ι8-diketones shown in US Pat. No. 3,844,790, indanones found in US Pat. Ketocoumarins disclosed in JP-A-52-112681, aminostyrene derivatives and amino-vinyl butadiene derivatives disclosed in JP-A-59-56403, US Pat. No. 4,594,310 amino複素 -heterocycles, julolidine heterocycles shown in U.S. Pat.No. 4,966,830, pyromethene dyes, pyrenes, phenothiazines, fluorenes shown in JP-A-5-241338 There are no particular limitations. These sensitizers can be used alone or in combination of two or more. The blending 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 resist compound.

[0088] [3] Surfactant

The surfactant is a component having an action of improving the coating property, striation, developability as a resist, etc. of the resist composition of the present invention. As such a surfactant, any of a cation type, a cation type, a non-one type or an amphoteric type can be used. Of these, preferred surfactants are nonionic surfactants. The nonionic surfactant is more effective than the affinity for the solvent used in the resist composition. Examples of non-ionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenol ethers, polyethylene glycol higher fatty acid diesters, etc., as well as the following trade names: Ftop (Gemcone Earth) , MegaFac (Dainippon Ink & Chemicals), Florard (Sumitomo 3EM), Asahi Guard, Surflon (Asahi Glass), Pepol (Toho Chemical), KP (Shin-Etsu Chemical) Product), polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), etc., but there is no particular limitation.

The blending amount of the surfactant is preferably 2 parts by weight or less as an effective component of the surfactant per 100 parts by weight of the resist compound.

[0089] [4] Other additives other than the above-mentioned crosslinking agent, sensitizer, and surfactant

Furthermore, in the resist composition of the present invention, one or two other additives other than the above-mentioned cross-linking agent, sensitizer, and surfactant are added to the resist composition as necessary, as long as the object of the present invention is not impaired. More than one species can be blended. Examples of other additives include a dissolution accelerator, a dissolution control agent, a dye, a pigment, and an adhesion assistant. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. In addition, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improver, and the like, specifically, 4-hydroxy 4 ′ methyl chalcone and the like. [0090] The resist composition of the present invention is usually dissolved in a solvent to form a uniform solution at the time of use, and then filtered with a filter having a pore diameter of about 0.2 m, if necessary. It is prepared by. In this case, the total solid concentration in the homogeneous solution is usually 50% by weight or less, preferably 1 to 50% by weight, more preferably 1 to 30% by weight, and more preferably 1 to 10% by weight.

[0091] Examples of the solvent used in the preparation of the resist composition of the present invention include, for example, ethylene glycolenomonomethinoatenoreacetate, ethyleneglycolenomethinorenoetenorea cetate, ethyleneglycolenolemonate _n — Ethylene glycol monoolemonoacetate, ethylene glycol monoethanolate, ethylene glycol monoethanolate, ethylene glycol monoethanolate, ethylene glycol monoethanolate, ethylene glycol monoethanolate, etc. Alkyl ethers: propylene glycol noremonomethinoatenore acetate, propyleneglycolenomethenoatenoate acetate, propylene glycol mono-n-propyl ether acetate, Propylene glycol monoalkyl ether acetates such as pyreneglycol monono butyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethinole ether and propylene glycol monoethyl ether; Methyl lactate, Ethyl lactate, n Propyl lactate Lactic acid esters such as lactic acid n-butyl and lactic acid n-amyl; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate Aliphatic carboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, methyl 3-methoxy-2-methylpionate, 3 — Toxibutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionate butyl, 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc. Esters; aromatic hydrocarbons such as toluene and xylene; ketones such as 2 heptanone, 3 heptanone, 4 heptanone, cyclohexanone; N, N dimethylformamide, N-methylacetamide, N, N dimethyla Examples include amides such as cetamide and N-methylpyrrolidone; and latatones such as y-latataton, but are not particularly limited. These solvents are independent Or two or more can be used.

[0092] The resist composition of the present invention is irradiated with visible rays, ultraviolet rays, excimer lasers, extreme ultraviolet rays (EUV), electron beams, X-rays and ion beams, or the like, within a range that does not inhibit the object of the present invention. A compound having a crosslinking reactive group that causes a crosslinking reaction by an induced chemical reaction and Z or rosin can be used in combination. The compound having a crosslinking reactive group and Z or rosin are not particularly limited, but the compound and Z or rosin soluble in the alkaline aqueous solution, visible light, ultraviolet light, excimer laser, extreme ultraviolet ( EUV), electron beam, X-ray and ion beam irradiation or a crosslinkable reactive group-introducing agent that undergoes a crosslink reaction by a chemical reaction induced thereby, reacts in the presence of a base catalyst, and the compound and Z or polymer produced. Or these derivatives etc. are mentioned. The term “crosslinking reactive group introduction reagent” as used herein refers to a compound having a crosslinking reactive group such as an acid, an acid chloride, an acid anhydride, or a dicarbonate, an alkylno or a ride. Of these, acid chlorides are particularly preferred.

Examples of the crosslinking reactive group include a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogen phenyl group, and a halogenated methyl group, and a beryl group, a aryl group, a cinnamoyl group, and the like. Group, butylsilyl group, epoxy group, halogenated methyl group, halogenated phenyl group are preferred. One or more of these may be used in combination.

[0093] The composition of the resist composition of the present invention is usually 40 to 99.998% by weight of the resist compound (A), 0.001 to 10% by weight of the compound (B), and other components (C) in the total solid content. In the total solid content in which 0.001 to 50 weight is preferable, the resist compound (A) 90 to 99.999% by weight, the compound (B) O.001 to LO weight is more preferable. By making it within the above range, the performance such as resolution is excellent. When the compound (B) does not exist in the total solid content and functions as a negative resist, 100% by weight of the resist compound (A) is particularly preferable.

[0094] In the present invention, the resist substrate is a resist substrate in which a resist film made of the composition is formed on the substrate, and the pattern formation substrate is an exposure of the resist film on the resist substrate. A substrate having a resist film obtained by development. The “patterning material” refers to a composition that is formed on a resist substrate and can be patterned by irradiation with light, extreme ultraviolet (EUV), electron beam, or radiation, and is the same as “resist film”. It is righteousness. The “pattern wiring substrate” is a substrate having a patterned wiring obtained by etching a pattern forming substrate.

[0095] In order to form a resist pattern, first, the resist composition of the present invention is applied on a substrate such as a silicon wafer or a wafer coated with aluminum by a coating means such as spin coating, cast coating, or roll coating. By doing so, a resist film is formed. If necessary, a surface treatment agent such as hexamethylene disilazane may be applied on the substrate in advance. Next, the coated substrate is heated as necessary. The heating condition is preferably a force of 20 to 250 ° C., more preferably 20 to 150 ° C., which varies depending on the composition of the resist composition. It is preferable that heating may improve the adhesion of the resist to the substrate. Next, the resist film is exposed to a desired pattern with any radiation selected from visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, and ion beam force. The exposure conditions and the like are appropriately selected according to the composition of the resist composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. The heating condition is preferably a force of 20 to 250 ° C., more preferably 20 to 150, which varies depending on the composition of the resist composition. . It is.

[0096] Next, the exposed resist film is developed with a resist-soluble developer to form a predetermined resist pattern. As the resist friendly溶現image solution, the resist solution same as can be used as the solvent was adjusted, for example, ethylene glycol monomethyl ether § cetearyl over preparative, ethylene glycol Honoré monomethyl E Chino les ether Honoré acetate, ethylene glycol Honoré monomethyl over _n propyl Ethylene glycol monolenoate quinoleate acetates such as noleate nole acetate and ethylene glycol nole mono-n-butinoleate nole acetate; propylene glycol nore monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monomethyl over n-propyl ether acetate, propylene glycol monomethyl over _n - propylene glycol monoalkylene ether acetates such as butyl acetate; methyl lactate E (EL), lactate esters such as n-propyl lactate, n-butyl lactate, n-amyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, Methyl propionate, Aliphatic carboxylic acid esters such as ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxyethyl ethyl pionate, methyl 3-methoxy-2-methylpropionate , 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionate, 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc. Esters; aromatic hydrocarbons such as toluene and xylene; ketones such as 2 heptanone, 3 heptanone, 4 monoheptanone, cyclohexanone; N, N dimethylformamide, N-methylacetamide, N, Amides such as N dimethylacetamide and N-methylpyrrolidone; γ Force particularly limited that can be mentioned Rataton, and the like, such as Rataton is not. These solvents can be used alone or in combination of two or more.

[0097] Further, an appropriate amount of the surfactant may be added to the resist-soluble developer.

This is preferable since the wettability of the developer with respect to the resist can be improved. After forming the resist pattern, a patterned wiring board can be obtained by etching. Etching can be performed by a known method such as dry etching using plasma gas.

Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.

[0098] The resist pattern can be peeled off with an organic solvent having higher solubility than the resist-soluble developer. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (lactic acid ethyl). Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board and may have a small diameter through hole.

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

[0099] The compounds represented by the general formulas (11), (2-1) and (3) of the present invention In addition to the resist compound, other semiconductor element materials such as anti-reflective coatings and base materials, molding materials, casting materials, sealing It can be used for materials, laminated materials, composite materials, paints, adhesives and the like.

Example

[0100] Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

The structure of the compound was confirmed by elemental analysis and ¹ H-NMR measurement. The analysis results are shown in Tables 2 and 3. In Table 2, the number of atoms of each compound is shown as a value of the characteristic formula, and the value of the weight percentage of the element is shown as a calculated value and an actual measurement value. The NMR measurement results are shown in Table 3.

[0101] Synthesis Example 1: Synthesis of Compound 1

The following compound 1 was synthesized as follows.

[Chemical 26]

Phenol 37.6 g / 0.4 mol and fluorenone 18. Og / O. Lmol were mixed and dissolved by heating to about 60 ° C, then 0.1 ml of sulfuric acid, 0.8 ml of 3 mercaptopropionic acid and 10 ml of toluene were added. , Reacted with stirring. After confirming the fluorenone conversion rate of 100%, 100 ml of toluene is cooled, cooled and the precipitated solid is filtered under reduced pressure, then stirred and washed with hot water at 60 ° C and recrystallized to obtain an intermediate compound. It was. Next, the intermediate compound is dissolved in dimethyacetoamide (DMA c), Atari mouth iruku mouthride (ACROS reagent) 2. 12g / 22.5mmol, Triethylamine (Kanto Chemical Co., Ltd. reagent) 2. 29 g was slowly added dropwise and stirred at 23 ° C for 3 hours. The reaction solution is added to a large amount of water, and crystallization is repeated.Then, the mixture is purified by column chromatography using a mixed solvent of hexane Z ethyl acetate ZDMAc = 3Z4Z100, and finally dried under reduced pressure. To obtain the desired product.

Synthesis Example 2 Synthesis of Compound 2

The following compound 2 was synthesized as follows.

[Chemical 27]

[0104] Phenolic 37.6 g / 0.4 mol and fluorenone 18. Og / O. Lmol were mixed and dissolved by heating to about 60 ° C, then 0.1 ml of sulfuric acid, 0.8 ml of 3-mercaptopropionic acid, 10 ml of toluene was added and reacted with stirring. After confirming the fluorenone conversion rate of 100%, 100 ml of toluene is cooled, cooled and the precipitated solid is filtered under reduced pressure, then stirred and washed with hot water at 60 ° C and recrystallized to obtain an intermediate compound. It was. Next, the intermediate compound 0.5 g, 3-bromopropene (ACROS reagent) 3.02 g (25 mmol), potassium carbonate (Kanto Chemical Co., Ltd. reagent) 3.5 g (25 mmol), iodine Sodium hydroxide (reagent manufactured by Kanto Chemical Co., Ltd.) 0.036 g (0.25 mmol) and 30 ml of acetonitrile were added, and the mixture was stirred at 55 ° C. for 24 hours in a nitrogen stream. After completion of the reaction, the salt is filtered, and the solvent is concentrated, then purified by column chromatography using a mixed solvent of hexane Z ethyl acetate ZDMAc = 3/4/100, and finally dried under reduced pressure to produce the desired product. I got a thing.

[0105] Synthesis Example 3 Synthesis of Compound 3

The following compound 3 was synthesized as follows.

[Chemical 28]

[0106] Phenol 37.6 g / 0.4 mol and fluorenone 18. Og / O. After dissolution by heating to ° C, 0.1 ml of sulfuric acid, 0.8 ml of 3-mercaptopropionic acid and 10 ml of toluene were added and reacted while stirring. After confirming the fluorenone conversion rate of 100%, 100 ml of toluene is cooled, cooled and the precipitated solid is filtered under reduced pressure, then stirred and washed with hot water at 60 ° C and recrystallized to obtain an intermediate compound. It was. Next, 0.5 g of the intermediate compound, 1.8 g (92.5 mmol) of epichlorohydrin and 0.73 g of 2-propanol were charged, and the mixture was heated to 40 ° C and dissolved uniformly. 0.52 g of 5% by weight sodium hydroxide aqueous solution was added dropwise over 90 minutes. During this time, the temperature was gradually raised, and after completion of the dropwise addition, the system was adjusted to 65 ° C and stirred for 30 minutes. Next, excess epichlorohydrin and 2-propanol were distilled off under reduced pressure and dissolved in 2 g of methyl isobutyl ketone, and 0.02 g of 48.5 wt% aqueous sodium hydroxide solution was added. Stir at 65 ° C. for 1 hour. Thereafter, an aqueous sodium phosphate solution was added to the reaction solution to neutralize excess sodium hydroxide and washed with water to remove by-product salts. Subsequently, methyl isobutyl ketone was completely removed, and finally, drying under reduced pressure was performed to obtain the desired product.

Synthesis Example 4 Synthesis of Compound 4

The following compound 4 was synthesized as follows.

[Chemical 29]

[0108] Phenols 37.6 g / 0.4 mol and fluorenone 18. Og / 0.1 mol were mixed and dissolved by heating to about 60 ° C, then 0.1 ml of sulfuric acid, 0.8 ml of 3-mercaptopropionic acid, 10 ml of toluene was added and reacted with stirring. After confirming that the fluorenone conversion rate was 100%, further add 3.24 g (25 mmol) of prochlorochloromethane and 2. 29 g of triethylamine (a reagent manufactured by Kanto Yigaku Co., Ltd.) slowly and stir at 23 ° C for 3 hours. did. When the reaction solution was added to a large amount of water and reprecipitation was repeated, a white powder was obtained. The obtained white powder was purified by column chromatography using a mixed solvent of hexane Z ethyl acetate ZDMA c = 3Z4Z100 and finally dried under reduced pressure to obtain the desired product. Synthesis Examples 5 to 54: Synthesis of Compounds 5 to 54

Compounds 5 to 54, which are the resist compound (A), were reacted in the same manner as in Synthesis Examples 1 to 4 according to the crosslinking reactive group introduction reagent using the raw materials listed in Table 1, and the target product was obtained. .

The chemical structural formulas of Compounds 13, 19, 23, 33 and 51 are shown below.

[0110] [Chemical 30]

[0111] [Chemical 31]

Table 1

2] Table 2

F is the total number of atoms Z (total number of carbon atoms, total number of oxygen atoms)

[0114] [Table 3]

Table 3

[0115] Examples 1 to 64 and Comparative Example 1

The resist compound (A), compound (B), cross-linking agent (C) and solvent described in Table 4 were made into a uniform solution, and then filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.2 m to obtain a resist. A composition was prepared. The obtained resist composition was spin-coated on a silicon wafer to form a resist film. Table 6 shows the film formability of each resist film obtained.

[0116] After spin-coating a resist on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven to form a resist film having a thickness of 0.2 m. In Examples 1 to 50, the resist film was exposed with i-line having a wavelength of 365 nm. Examples 51 to 64 and Comparative Example 1 were exposed with an electron beam, and thereafter beta-exposed in an oven (No. 1). 5 table). Development was carried out at 23 ° C for 5 seconds by DMAc by the static method. Thereafter, it was dried to form a negative resist pattern. Each obtained resist pattern was evaluated by the following method. The evaluation results are shown in Table 6. [0117] (1) Safety solvent solubility test for compounds

A solubility test of the resist compound (A) in a safe solvent was performed at 23 ° C. The amount dissolved in the most soluble solvent selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and ethyl lactate was evaluated according to the following criteria.

A: 5% by weight or more dissolved

B: 0.1% to less than 5% by weight dissolved

C: Undissolved force

(2) Evaluation of resist film formability

The resist composition was spin-coated on a silicon wafer with a spin coater to form a resist film, which was then heated on a 110 ° C hot plate for 60 minutes, and the resist film on the 6-inch silicon wafer was evaluated according to the following criteria.

A: Good surface properties

C: Partly whitened or uneven on the surface

(3) Resist pattern evaluation

(S— D S / z mL & S

The developed resist pattern was observed with an optical microscope to confirm the presence or absence of 5 μm line and space, and evaluated according to the following criteria.

A: Confirm

C: Cannot confirm

(3-2) 100nmL & S

The resist pattern after development was observed with an electron microscope, and the presence or absence of lOOnmL & S line and space formation was confirmed and evaluated according to the following criteria.

A: Confirm

C: Cannot confirm

[0118] [Table 4] Table 4— 1

(A) (B) (C)

Example (g) Cg) (g) Solvent Cg) Compound Compound

1 1 0.1 -1 0.01 None 0 S-1 1.89

2 2 0.1 R-1 0.01 None 0 S-1 1.89

3 3 0.1 R-1 0.01 None 0 S-1 1.89

4 4 0.1 R-1 0.01 None 0 S-1 1.89

5 5 0.1 R-1 0.01 None 0 S-1 1.89

6 6 0.1 R-1 0.01 None 0 S-1 1.89

7 7 0.1 R-1 0.01 None 0 S-1 1.89

8 8 0.1 R-1 0.01 None 0 S-1 1.89

9 9 0.1 R-1 0.01 None 0 S-1 1.89

10 10 0.1 R-1 0.01 None 0 S-1 1.89

1 1 1 1 0,1 R-1 0.01 None 0 S-1 1.89

12 1 2 0,1 R-1 0.01 None 0 S-1 1.89

13 1 3 0.1 R-1 0.01 None 0 S-1 1.89

14 14 0.1 R-1 0.01 None 0 S-1 1.89

15 15 0.1 R-1 0.01 None 0 S-1 1.89

16 16 0.1 R-1 0.01 None 0 S-1 1.89

1 7 1 7 0.1 R-1 0.01 None 0 S-1 1.89

18 1 8 0.1 R-1 0.01 None 0 S-1 1.89

19 1 9 0.1 R-1 0,01 None 0 S-1 1 .89

20 20 0.1 R-1 0.01 None 0 S-1 1.89

21 21 0.1 R-1 0.01 None 0 S-1 1.89

22 22 0.1 R-1 0.01 None 0 S-1 1.89

23 23 0.1 R-1 0.01 None 0 S-1 1.89

24 24 0.1 R-1 0,01 None 0 S-1 1.89

25 25 0.1 R-1 0.01 None 0 S-1 1.89

26 26 0.1 R-1 0.01 None 0 S-1 1.89

27 27 0.1 R-1 0.01 None 0 S-1 1.89

28 28 0.1 R-1 0.01 None 0 S-1 1.89

29 29 0.1 R-1 0.01 None 0 S-1 1.89

30 30 0-1 R-1 0.01 None 0 S-1 1.89

31 31 0.1 R-1 0.01 None 0 S-1 1.89

32 32 0.1 R-1 0.01 None 0 S-1 1.89

33 33 0.1 R-1 0.01 None 0 s-t 1.89

34 34 0.1 R-1 0.01 None 0 S-1 1.89

35 35 0.1 R-1 0.01 None 0 S-1 1.89

36 36 0.1 R-1 0.01 None 0 S-1 1.89

37 37 0.1 R-1 0.01 None 0 S-1 1.89

38 38 0.1 R-1 0.01 None 0 S-1 1.89

39 39 0.1 R-1 0.01 None 0 S-1 1.89

40 40 0.1 R-1 0.01 None 0 S-1 1.89

41 41 0.1 R-1 0.01 None 0 S-1 1.89

42 42 0.1 R-1 0.01 None 0 S-1 1.89

43 43 0.1 R-1 0.01 None 0 S-1 1.89

44 44 0.1 R-1 0.01 None 0 S-1 1.89

45 45 0.1 R-1 0.01 None 0 S-1 1.89

46 46 0.1 R-1 0.01 None 0 S-1 1.89

47 47 0.1 R-1 0.01 None 0 S-1 1.89

48 48 0.1 R-1 0.01 None 0 S-1 1.89

49 49 0.1 R-1 0.01 None 0 S-1 1.89

50 50 0.1 R-1 0.01 None 0 S-1 1.89

51 41 0.1 None 0 None 0 S-1 1.89

52 42 0.1 None 0 None 0 S-1 1.89

53 43 0.1 None 0 None 0 S-1 1.89

54 44 0.1 None 0 None 0 S-1 1.89

55 45 0.1 None 0 None 0 S-1 1.89

56 46 0.1 None 0 None 0 S-1 1.89

57 47 0.1 None 0 None 0 S-1 1.89

58 48 0.1 None 0 None 0 S-1 1.89

59 49 0.1 None 0 None 0 S-1 1.89

60 50 0.1 None 0 None 0 S-1 1.89

61 51 0.1 None 0 None 0 S-1 1.89

62 52 0.1 None 0 None 0 S-1 1.89

63 53 0.1 None 0 None 0 S-1 1.89

64 54 0.1 None 0 None 0 S-1 1.89

65 51 0.07 None 0 L-1 0.03 S-1 1.89

66 51 0.07 None 0 and-1 0.03 S-1 1.89 [0119] [Table 5]

Table 4 1 2

[0120] Compound (A)

C-1: Calix resorcinarene derivative B (Production method: see JP-A-9-236919) [Chemical 32]

C-1

[0121] Compound (B)

R-l: Irgacure 907 (2-Methyl-1 [(4-Methylthio) phenol] 2 morpholinopropane 1-one, manufactured by Chipa Specialty Chemicals)

Cross-linking agent (C)

L-1: 1,6 hexanediol diglycidyl ether (Sakamoto Pharmaceutical Co., Ltd.) Solvent

S-1: Propylene glycol monomethyl monoacetate (Tokyo Chemical Industry Co., Ltd.)

S-2: Methylene chloride (Kanto Chemical Co., Inc.)

[Table 6] Table 5 1

[0122] [Table 7]

[0123] [Table 8]

Table 5-3

[0124] [Table 9]

Table 6 1

5Aim Example Deposition property

Test & S

1 A A A

2 A A A

3 A A A

4 A A A

5 A A A

6 A A A

7 A A A

8 A A A

9 A A A

10 A A A

11 A A A

12 A A A

13 A A A

14 A A A

15 A A A

16 A A A

17 A A A

18 A A A

19 A A A

20 A A A

21 A A A

22 A A A

23 A A A

24 A A A

25 A A A

26 A A A

27 A A A

28 A A A

29 A A A

30 A A A

31 A A A

32 A A A

33 A A A

34 A A A

35 A A A

36 A A A

37 A A A

38 A A A

39 A A A

40 A A A

41 A A A

42 A A A

43 A A A

44 A A A

45 A A A

46 A A A

47 A A A

48 A A A

49 A A A

50 AAA [0125] [Table 10]

Table 6 1 2

[0126] [Table

Industrial applicability

[0127] As described in detail above, the compound of the present invention and the resist composition containing the compound are highly sensitive, heat-resistant and solvent-soluble, can produce a high-resolution resist pattern, and have a high degree of integration. A high semiconductor element can be manufactured with high productivity. The resist composition of the present invention is useful as a radiation-sensitive material that is sensitive to radiation such as ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays (EUV), and X-rays. It is.

Claims

The scope of the claims

[1] (a) Polyphenol produced by a condensation reaction of an aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms and a compound having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups Cross-linking that causes a cross-linking reaction directly or indirectly by irradiation of any selected radiation to a compound, visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, and ion beam power Manufactured by reacting a reagent that introduces a reactive group,

(b) The force is 300-5000.

(c) A resist composition comprising at least one resist compound (A) having at least one crosslinking reactive group in the molecule.

[2] A compound represented by the following formula (11).

[Chemical 1]

(In the formula (1— 1),

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

Alternatively, R ⁴ and R ⁵ are bonded to form a fluorene structure, a phenol fluorene structure, a diphenyl fluorene structure, a naphthenic structure, a 1-keto naphthenic structure, a 9 keto-9, 10- dihydrophenanthrene structure, or a benzophenone structure. Having 10-30 carbon atoms A valent group;

pl and ql are integers from 0 to 3;

p2 and q2 are integers from 0 to 4;

Satisfying l≤pl + p2≤5, l≤ql + q2≤5, l≤pl + ql≤6, and a plurality of R ² and A may be the same or different.

In the formula (1-1), carbons in the ortho position with respect to —CR ⁴ R ⁵ — of the two benzene rings may be bonded via an oxygen atom or a sulfur atom. )

A compound represented by the following formula (2-1).

[Chemical 2]

(In formula (2-1),

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁶ is biphenyl structure, terphenyl structure, naphthalene structure, phenanthrene structure, or Or a divalent group having 10 to 30 carbon atoms and having a pyrene structure;

ml, nl, tl, si are integers from 0 to 3;

m2, n2, t2, s2 are integers from 0 to 4;

l≤ml + m2≤5, l≤nl + n2≤5, l≤tl + t2≤5, l≤sl + s2≤5, l≤ml + nl + tl + sl≤6, multiple R ² may be the same or different.

In the formula (2-1), the carbon in the ortho position with respect to —CR ⁴ R ⁶ — of the two benzene rings bonded via —CR ⁴ R ⁶ — is bonded via an oxygen atom or a sulfur atom. Join! )

A compound represented by the following formula (3).

[Chemical 3]

(In Formula (3),

R ² is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, A group selected from an alkoxy group, an alkyl group, an acyl group, an alkoxycarboxoxy group, an alkylcarboxoxy group, an arylcarboxoxy group, a cyano group, and a -tro group;

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

Alternatively, two R ⁴ and R ⁸ are bonded to each other, and a fluorene structure, a phenol fluorene structure, a diphenyl fluorene structure, a naphthenic structure, a 1-keto naphthenic structure, a 9 keto-9, 10 dihydrophenanthrene, or a benzophenone. A hexavalent group of 10 to 30 carbon atoms having a structure;

m4, n4, j4, k4, x4, y4 are integers from 0 to 3;

m5, n5, j5, k5, x5, y5 are integers from 0 to 4;

R ^{5 in the} above formula (11) is represented by the following formula:

[Chemical 4]

(Where

R ³ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms; p3 is an integer of 0 to 4;

q3 is an integer from 0 to 3;

r3 is an integer from 0 to 2;

0≤p3 + q3≤7 is satisfied, and multiple, p3, q3, r3 may be the same or different)

The compound of Claim 2 represented by either.

[6] The divalent group formed by combining R ⁴ and R ^{5 in} the formula (11) has the following formula:

[Chemical 5]

(Where

R ³ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms;

Υ is a single bond or a carbo group;

Ζ is a methylene group or a carbonyl group;

ρ3 is an integer from 0 to 4;

q3 is an integer from 0 to 3;

r3 is an integer from 0 to 2;

0≤p3 + q3≤7 is satisfied, and multiple, p3 and q3 may be the same or different)

of! 3. A compound according to claim 2, which is expressed as:

R ^{6 in the} above formula (2-1) is the following formula:

[Chemical 6] (R ³ ) q3 (R ³ ) 3

(R ³ ) q3, ^(R) q3

(Where

R ³ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms; q3 is an integer of 0 to 3;

A plurality of q3 may be the same or different)

of! 4. The compound according to claim 3, which is represented by any deviation.

[8] Tetravalent basic force formed by combining two R ⁴ and R ^{6 of the} above formula (2-1) The following formula:

(Where

R ³ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms; Y is a single bond or a carbocycle group;

q3 is an integer from 0 to 3;

r3 is an integer from 0 to 2;

4. The compound according to claim 3, wherein 0 ≦ q3 + r3 ≦ 7 is satisfied, and a plurality of q3 may be the same or different.

[9] R ^{8 in the} above formula (3) is represented by the following formula:

[Chemical 8]

(Where

A plurality of q3 may be the same or different)

of! The compound according to claim 4, which is represented by any deviation.

[10] The compound according to any one of claims 2 to 4, which is a group selected from an A force, an allyloyloxy group, an aryloxy group, a glycidyloxy group, and a chloromethyloxy group.

[11] The compound according to any one of claims 2 to 4, which is a group in which an A force, an allyloyloxy group, an aryloxy group and a chloromethyloxy group force are also selected.

12. The resist composition according to claim 1, wherein the resist compound (A) has two or more crosslinking reactive groups in the molecule.

13. The resist composition according to claim 1, comprising a conjugated structure in which the resist compound (A) has a conjugated double bond having a force of 5 to 28 and a non-bonded electron pair of Z or 1 to 2 heteroatoms. object.

[14] The conjugated structure is a biphenyl structure, a terphenyl structure, a naphthalene structure, an anthracene structure, a phenanthrene structure, a pyrene structure, a fluorene structure, a phenylfluorene structure, a diphenylfluorene structure, a acenaphthene structure, or a 1-keto acenaphthene structure. 14. The resist composition according to claim 13, wherein the resist composition is at least one structure selected from the group consisting of 9-ketoe 9,10-dihydrophenanthrene structure, benzophenone structure, xanthene structure, and thixanthene structure power.

15. The resist composition according to claim 13, wherein the conjugated structure is a condensed polycyclic structure.

[16] The resist compound (A) is (a) an aromatic ketone having a conjugated structure and having 5 to 45 carbon atoms. Or cross-linking reactivity to polyphenol compounds produced by condensation reaction with aromatic aldehydes and compounds having 6 to 15 carbon atoms and 1 to 3 phenolic hydroxyl groups that do not have a conjugated structure. 2. The resist composition according to claim 1, which is a compound into which a group is introduced.

[17] The cross-linking reactive group of the resist compound (A) is selected from the group consisting of a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenol group, and a halogenated methyl group. 2. The resist composition according to claim 1, wherein the resist composition is at least one kind.

18. The resist composition according to claim 1, wherein the cross-linking reactive group of the resist compound (A) is at least one selected from a carbon-carbon multiple bond group, an epoxy group, and a rosin methyl group power. .

[19] The resist composition according to [1], wherein the crosslinking reactive group of the resist compound (A) is at least one selected from the group consisting of a carbon-carbon multiple bond group and a halogenomethyl group.

[20] The resist compound (A) is

2. The resist composition according to claim 1, wherein F≤3 is satisfied (F represents the total number of atoms Z (total number of carbon atoms, total number of oxygen atoms).)

[21] Resist compound (A) force Formula (1 1):

[Chemical 9]

(In the formula (1 1),

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

R ⁵ is biphenyl structure, terphenyl structure, naphthalene structure, phenanthrene structure, or Or a monovalent group having 10 to 30 carbon atoms having a pyrene structure;

pl and ql are integers from 0 to 3;

p2 and q2 are integers from 0 to 4;

In the formula (1-1), the carbon in the ortho position with respect to CR ⁴ R ⁵ — of the two benzene rings may be bonded via an oxygen atom or a sulfur atom. )

The resist composition according to claim 1 represented by:

[22] R ^{5 in the} above formula (11) is represented by the following formula:

[Chemical 10]

() q3

(Where

q3 is an integer from 0 to 3;

r3 is an integer from 0 to 2;

0≤p3 + q3≤7, and multiple R ³ , p3, q3, r3 may be the same or different)

The resist composition according to claim 21, wherein the resist composition is represented by any deviation.

The divalent group formed by combining R ⁴ and R ^{5 in the} above formula (1 1 1) has the following formula:

[Chemical 11]

(Where

R ³ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms; Y is a single bond or a carbonyl group;

Z is a methylene group or a carbonyl group;

p3 is an integer from 0 to 4; q3 is an integer from 0 to 3;

r3 is an integer from 0 to 2;

The resist composition according to claim 21, wherein the resist composition is represented by:!

24. The resist composition according to claim 1, wherein the resist composition is an aromatic ketone having 5 to 45 carbon atoms or an aromatic aldehyde power diketone or dialdehydride.

[25] The resist compound (A) force The following formula (2-1):

[Chemical 12]

(In formula (2-1),

R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

Or two R ⁴ and R ⁶ are bonded together to form a fluorene structure, a phenol fluorene structure, a diphenyl fluorene structure, a naphthenic structure, a 1-keto naphthenic structure, a 9-keto-9, 10-dihydrophenanthrene, or A tetravalent group having 10 to 30 carbon atoms and having a benzophenone structure; A is a group in which an aryloxy group, an talyloxy group, a glycidyloxy group, and a halogenomethyloxy group are also selected, and at least one of A is an aryloxy group, an talyloxy group, a glycidyloxy group And a group selected from a halogenated methyloxy group;

ml, nl, tl, si are integers from 0 to 3;

m2, n2, t2, s2 are integers from 0 to 4;

The resist composition according to claim 1 represented by:

R ^{6 in the} above formula (2-1) is the following formula:

[Chemical 13]

(Where

A plurality of q3 may be the same or different)

26. The resist composition according to claim 25, which is represented by any one of the following:

Tetravalent basic force formed by combining two R ⁴ and R ^{6 of the} formula (2-1).

[Chemical 14]

(Where

q3 is an integer from 0 to 3;

r3 is an integer from 0 to 2;

26. The resist composition according to claim 25, wherein 0≤q3 + r3≤7 is satisfied, and a plurality of q3 may be the same or different.

28. The resist composition according to claim 1, wherein the aromatic ketone or aromatic aldehyde having 5 to 45 carbon atoms is triketone or trialdehyde.

[29] The resist compound (A) force The following formula (3):

[Chemical 15]

(In Formula (3),

R ² is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkenyl group, an acyl group, an alkoxycarboxoxy group, an alkylcarboxoxy group, an arylcarboxoxy group, or a cyano group. A group force consisting of, and -tro groups R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;

m4, n4, j4, k4, x4, y4 are integers from 0 to 3;

m5, n5, j5, k5, x5, y5 are integers from 0 to 4;

The resist composition according to claim 1 represented by:

R ^{8 in the} formula (3) is the following formula:

[Chemical 16]

q ₃

(Where

R ³ is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms; q3 is an integer of 0 to 3; (Several q3 may be the same or different)

30. The resist composition according to claim 29, which is represented by any one of the following:

The above resist compound (A) 1S The following formula (1

[Chemical 17]

(In the formula (1-3), R ^{2 to} R ⁴ , A, pl to p3, ql to q3, pl + p2, ql + q2, pl + ql, and p3 + q3 are the same as above)

The resist composition according to claim 21, represented by:

[32] Regist compound (A) force Formula (1 4):

[Chemical 18]

(In the formula (1-4), R ^{2 to} R ⁴ , A, pl to p3, ql to q3, pl + p2, ql + q2, pl + ql, and p3 + q3 are the same as above)

The resist composition according to claim 21, represented by:

[33] The resist compound (A) is represented by the formula (1-5):

[Chemical 19]

(In the formula (1-5), R ^{2 to} R ⁴ , A, pl to p3, ql to q3, pl + p2, ql + q2, pl + ql, and p3 + q3 are the same as above)

The resist composition according to claim 21, represented by:

[34] Regist compound (A) force Formula (16):

[Chemical 20]

(In the formula (1-6), R ^{2 to} R ⁴ , A, pl to p3, ql to q2, pl + p2, ql + q2, and pl + ql are the same as above)

The resist composition according to claim 21, represented by:

[35] Regist compound (A) force Formula (17):

[Chemical 21]

(In the formula (1-7), R ^{2 to} R ⁴ , A, pl to p2, ql to q2, pl + p2, ql + q2, pl + ql, r3 are the same as above)

The resist composition according to claim 21, represented by:

[36] Resist compound (A) force Formula (1-8):

[Chemical 22]

(Wherein (in ^{1- 8), R 2, R} \ A, Y, pl~p3, ql~q2, pl + p2, ql + q2, pl + ql is as before Symbol)

The resist composition according to claim 21, represented by:

The resist compound (A) is represented by the following formula (1-9):

[Chemical 23]

(Wherein (in ^{1- 9), R 2, R} 3, A, Z, pl~p2, ql~q3, pl + p2, ql + q2, pl + ql is as before Symbol)

The resist composition according to claim 21, represented by:

The resist compound (A) has the following formula (110):

[Chemical 24]

(Wherein (in 1-10), similarly to the ^{R \ R 3, A, Y} , pl~p3, ql~q3, pl + p2, ql + q2, pl + ql, Contact and p3 + q3 are the)

The resist composition according to claim 21, represented by:

[39] The resist compound (A) is represented by the following formula (111):

[Chemical 25]

(In the formula (1-11), R ² , R ³ , A, Y, pl to p3, ql to q2, pl + p3, ql + q2, pl + ql, and r3 are the same as above)

The resist composition according to claim 21, represented by:

[40] The resist compound (A) force The following formula (1 12): [Chemical 26]

(Wherein (in ^{1- 12), R 2, R} 3, A, Z, pl~p3, ql~q2, pl + p2, ql + q2, pl + ql is as before Symbol)

The resist composition according to claim 21, represented by:

[41] The resist compound (A) force The following formula (2-3):

[Chemical 27]

(In the formula (2-3), R ^{2 to} R ⁴ , A, ml, nl, tl, sl, m2, n2, t2,

Tl + t2, sl + s2, ml + nl + tl + sl, q3 is the same as above)

The resist composition according to claim 25, represented by:

[42] Regist compound (A) force Formula (2-4):

[Chemical 28]

(In the formula (2-4), R to R, A, ml, nl, tl, sl, m2, n2, t2, tl + t2, sl + s2, ml + nl + tl + sl, q3 are The resist composition of Claim 25 represented by these.

The above resist compound (A) force The following formula (2-5):

[Chemical 29]

(In the formula (2-5), R ^{2 to} R ⁴ , A, ml, nl, tl, sl, m2, n2, t2, tl + t2, sl + s2, ml + nl + tl + sl, q3 are Same as above) The resist composition according to claim 25, represented by:

[44] The resist compound (A) force The following formula (2-6):

[Chemical 30]

(In formula (2-6), R ² , R ³ , A, Y, ml, nl, m2, η2, ml + m2, nl + n2, ml + nl, q 3, and r3 are the same as above)

The resist composition according to claim 25, represented by:

Resist compound (A) force Formula (3-1):

[Chemical 31]

(In the formula ^{(3- 1), R 2,} R ', A, m4, n4, j4, k4, x4, y4, m5, n5, j5, k5, x5, y5, m 4 + m5, n4 + n5, j4 + j5, k4 + k5, x4 + x5, y4 + y5, m4 + n4 + j4 + k4 + x4 + y4 are the same as above)

30. The resist composition according to claim 29, represented by:

Resist compound (A) force Formula (3-2): [Chemical 32]

(Formula (3-2) ^{^{in, R 2, R 4, A}} , m4, n4, j4, k4, x4, y4, m5, n5, j5, k5, x5, y5, m 4 + m5, n4 + n5, j4 + j5, k4 + k5, x4 + x5, y4 + y5, m4 + n4 + j4 + k4 + x4 + y4 are the same as above)

30. The resist composition according to claim 29, represented by:

[47] The resist composition according to [21], [25] or [29], wherein A of the resist compound (A) is an attaroyloxy group, an aryloxy group, a glycidyloxy group or a chloromethyloxy group.

48. The resist composition according to claim 21, 25, or 29, wherein A in the resist compound (A) is an attaroyloxy group, an aryloxy group, or a chloromethyloxy group.

[49] The resist composition according to claim 1, comprising two or more of the resist compounds (A).

[50] Radicals or cations can be generated directly or indirectly by irradiation with visible light, ultraviolet light, excimer laser, extreme ultraviolet light (EUV), electron beam, X-ray, or any other group power that is also ion beam power. The resist composition according to claim 1, further comprising a generated compound (B).

[51] Further, a compound having one or more selected from the group consisting of a carbon-carbon multiple bond group, a cyclopropyl group, an epoxy group, an azide group, a halogenated phenyl group, and a halogenated methyl group, or 2. The resist composition according to claim 1, comprising greaves.

[52] In all solids, the above-mentioned resist compound (A) 40 to 99.998% by weight, the above-mentioned compound (B) O. 00

1-10 wt ^_0/0, the other component (C) Les resist composition according to claim 50 which is O. 001-50 wt%. [53] In all solids, the resist compound (A) 90 to 99.999% by weight, the compound (B) O. 00

51. The resist composition according to claim 50, wherein the resist composition is 1 to 10% by weight.

54. The resist composition according to claim 1, wherein the resist compound (A) is 100% by weight in the total solid content.

[55] The resist composition according to claim 1, comprising 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent component.

[56] The resist composition according to claim 1, wherein 2, 3, 6-trimethylphenol is used as the compound containing a phenolic hydroxyl group.