JPH1144950A - Improving agent for substrate dependence of resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fine pattern with a good form even on a special substrate and to form a pattern with excellent storage stability and high sensitivity by incorporating a specified compd. having such a structure that at least one bond of -NH- is directly bonded to a specified one in the molecule. SOLUTION: This improving agent for the dependence of a resist on a substrate contains a compd. having at least one structure in the molecule that at lest one bond of -NH- is directly bonded to at least one of -C(=O)-, -C(=S)- and -SO2 -. The compd. is, for example, expressed by the formula. In the formula, X is oxygen atom or sulfur atom, A is a satd. or unsatd. five or six-member ring which may contain oxygen atoms, nitrogen atoms or sulfur atoms as the structural atoms. When this resist compsn. is used as a resist material for exposure on a special substrate, a pattern form with good accuracy or in a quater- micron size can be obtd. while high resolution and high sensitivity are maintained.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate-dependent improving agent useful as a component of a chemically amplified positive (or negative) resist composition used in the production of semiconductor devices and the like, and a resist composition containing the same. And a pattern forming method using the resist composition.

[0001]

2. Description of the Related Art In recent years, due to the demand for ultra-fine processing accompanying high integration of semiconductor devices, an exposure light source used in a lithography process has a shorter wavelength than i-line (365 nm) from KrF.
Excimer lasers (248 nm) have been used. As a result, conventional dissolution-inhibiting resists that required exposure of several hundred mJ could not obtain high energy because the exposure light source was changed from a mercury lamp to an excimer laser.
It cannot be used because it has strong absorption at 248 nm (poor transmittance). Therefore, a chemically amplified resist that has a high transmittance even at 248 nm and can form a pattern with exposure of several tens of mJ has been used. became.

However, this chemically amplified resist has a reaction mechanism in which, when a pattern is formed, a dissolution inhibiting compound such as an alkali-insoluble compound or an alkali-insoluble polymer becomes alkali-soluble by exposure energy, that is, from a photosensitive compound by exposure energy. By generating an acid and causing a chemical reaction with the generated acid, it has a two-step reaction mechanism in which an alkali-insoluble compound or polymer becomes alkali-soluble, and thus is easily affected by the substrate. That is, due to the decrease in the exposure amount, the delicate intensity of the exposure amount at the substrate interface portion and the influence of the basic substance and moisture generated from the substrate are further amplified. Therefore, in manufacturing a device using a chemically amplified resist, a good pattern shape cannot be obtained with a special substrate (TiN, BPSG, etc.), which has conventionally had few problems, and this substrate dependency is a serious problem.

In order to solve these problems, a resist composition to which an organic carboxylic acid is added (for example, JP-A-9-6001, JP-A-9-6002, JP-A-9-6003, and EP-A-679951) No., etc.) have been proposed, and improvements in pattern shapes on special substrates have been reported. However, resist compositions containing these organic carboxylic acids have a problem that the acidity is strong and the performance is deteriorated during storage because the resist composition containing the organic carboxylic acid causes a chemical reaction to improve the dependence on the substrate. In order to make up for this drawback, it is necessary to add a basic compound in an amount equal to or greater than the neutralization amount of the organic carboxylic acid, which causes a problem that the sensitivity is lowered.

[0004] Therefore, it is presently desired to develop a highly sensitive resist composition which can provide a pattern having an excellent shape even on a special substrate, has excellent storage stability, and has a good throughput.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, the problem to be solved by the present invention is to form a pattern using a chemically amplified positive (or negative) resist composition even on a special substrate. Good fine pattern is obtained,
An object of the present invention is to provide a resist composition having excellent storage stability and capable of forming a pattern with high sensitivity.

[0006]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of solving the above problems, and has the following structure. "(1) At least one bond of -NH- is -C (=
O) -, - C (= S) - and -SO ₂ - substrate dependency improving agent resist comprising at least one compound having in the molecule at least one direct bond structure selected from.

(2) A polymer that becomes alkali-soluble by the action of an acid, a compound that generates an acid upon irradiation with radiation, and at least one of —NH— has a bond of —C () O)
-, - C (= S) - and -SO ₂ - and a compound having at least one at least one directly bonded to the structure in the molecule selected from a resist composition comprising a such a soluble solvent, the Stuff.

(3) An alkali-soluble polymer, a compound which becomes alkali-soluble by the action of an acid, a compound which generates an acid upon irradiation with radiation, and at least one bond of -NH- is -C (= O)- , -C (= S) - and -SO ₂
-A resist composition comprising a compound having at least one structure directly bonded to at least one selected from-in a molecule, and a solvent capable of dissolving them.

(4) An alkali-soluble polymer, a compound which crosslinks the polymer by the action of an acid to make the polymer hardly soluble in an alkali, a compound which generates an acid by irradiation with radiation, and at least one bond of --NH-- -C (= O)
-, - C (= S) - and -SO ₂ - and a compound having at least one at least one directly bonded to the structure in the molecule selected from a resist composition comprising a such a soluble solvent, the Stuff.

(5) The above (2) to (4) are formed on a semiconductor substrate.
Applying the resist composition according to any one of the above, a step of forming a resist film by heating, a step of irradiating radiation through a mask, and if necessary, heating and then developing with an alkali developing solution. And a pattern forming method. 』

That is, the present inventors have conducted intensive studies for a chemically amplified resist composition capable of obtaining a fine pattern having a good shape even on a special substrate. As a result, at least one bond of —NH— was obtained. Is -C (= O)-, -C (= S)-
And a compound having at least one structure directly bonded to at least one selected from —SO ₂ — in the molecule has an excellent effect of avoiding the substrate-dependent problem of the existing resist material (ie, the substrate It is extremely effective as a dependency improver), and has found that a resist composition containing the compound can achieve the above object, thereby completing the present invention.

At least one bond of -NH- is -C
A compound having at least one structure directly bonded to at least one selected from (＝ O) —, —C (＝ S) — and —SO ₂ — in the molecule (hereinafter, “compound according to the present invention”
Abbreviated. ) Includes a cyclic compound and a non-cyclic compound. Examples of the cyclic compound according to the present invention (hereinafter abbreviated as “compound C according to the present invention”) include compounds represented by the following general formula [1], general formula [2] or general formula [3]. No.

[0013]

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[In the formula, X represents an oxygen atom or a sulfur atom, and A represents a saturated or unsaturated 5- or 6-membered ring which may contain an oxygen atom, a nitrogen atom or a sulfur atom as a constituent atom. May have a substituent.). ]

[0015]

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[In the formula, X represents an oxygen atom or a sulfur atom, and D represents a saturated or unsaturated 5- or 6-membered ring which may contain an oxygen atom, a nitrogen atom or a sulfur atom as a constituent atom. May have a substituent, and the sulfur atom may have an oxo group.), And E is a saturated or unsaturated 6-membered ring having carbon as a constituent atom or Represents a fused ring, and forms a fused ring between D and E. ]

[0017]

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(Wherein G represents a saturated or unsaturated 6- to 8-membered ring which may contain an oxygen atom as a constituent atom,
J and L both represent a benzene ring, each of which forms a condensed ring with the G ring. ).

In the general formula [1], A is a saturated or unsaturated 5 or 6 which may further contain an oxygen atom, a nitrogen atom or a sulfur atom in addition to a carbon atom and a nitrogen atom.
Is a membered ring, and the carbon atoms constituting the ring may have a substituent.Examples of the substituent of these carbon atoms include an alkyl group, an oxo group, and an oximino group. Any of a chain or a branch, preferably having 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, n-hexyl, isohexyl and the like.

In the general formula [2], D is a saturated or unsaturated 5 or 6 which may further contain an oxygen atom, a nitrogen atom or a sulfur atom in addition to a carbon atom and a nitrogen atom.
And the carbon atoms constituting the ring may have a substituent. The substituents of these carbon atoms are represented by the general formula [4]

[0021]

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[Wherein, Q represents a hydrogen atom or an alkyl group. Or an oxo group represented by the formula:

In the general formula [4], the alkyl group represented by Q may be linear or branched, and preferably has 1 to 6 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group,
Examples include an isobutyl group, a tert-butyl group, a sec-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a 1-methylpentyl group, an n-hexyl group, and an isohexyl group.

The sulfur atom constituting the ring may have one or two oxo groups.

Examples of the saturated or unsaturated 6-membered ring having carbon as a constituent atom represented by E include a benzene ring, a cyclohexane ring, a cyclohexene ring, a cyclohexadiene ring and the like.

Examples of the condensed ring represented by E include a naphthalene ring and an anthracene ring.

In the general formula [3], G is a saturated or unsaturated 6- to 8-membered ring which may contain an oxygen atom in addition to a carbon atom and a nitrogen atom as a constituent component. Form a condensed ring with a benzene ring represented by J and L, respectively.

Specific examples of the compound C according to the present invention include:
For example, those represented by the above general formula [1] include acid imide compounds derived from aliphatic dibasic acids such as succinimide, maleimide, glutarimide, etc .; , 2,4-dioxohexahydro-1,
Examples thereof include 3,5-triazine, parabanic acid, barbituric acid, alloxane, and violuric acid. Examples of the compound represented by the general formula [2] include phthalimide, 1,2,3,6-tetrahydrophthalimide, Acid imide compounds derived from aromatic dibasic acids such as 8-naphthalimide, 2,3-naphthalenedicarboximide, isatin, hydrocarbostyril, carbostyryl, 1,4-benzoxazin-3-one, benzothiazine- 3-one, oxindole, 2-benzoxazolinone, 2-oxobenzo [c, d] indole, phthalimidine, 1-benzylphthalimidine, saccharin, benzyleneurea and the like, represented by the general formula [3] For example, 6 (5H) -phenanthridinone,
Dihydrodibenzoxazepinone, 5,6,11,12-tetrahydrodibenz [b, f] azocin-6-one and the like, which do not belong to any of the general formulas [1] to [3] include For example, pyromellitic diimide, bentazone and the like can be mentioned. Among the compounds C according to the present invention, particularly preferred are acid imide compounds such as succinimide and phthalimide which can improve the dependence on the substrate by adding a small amount.

As the acyclic compound according to the present invention, for example, a sulfonamide derivative (hereinafter abbreviated as “compound A according to the present invention”) or the following general formula [21]

[0030]

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(Wherein, X ₁ and X ₂ each independently represent an alkyl group or a phenyl group which may have a substituent, n represents an integer of 1 to 3, and n Xs each represent (Independently representing an oxygen atom or a sulfur atom) (hereinafter abbreviated as “compound B according to the present invention”), and the like.

The compound A according to the present invention includes, for example, R
₀ SO ₂ NHR ′ (wherein R ₀ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ′ represents a hydrogen atom or an alkyl group. )
And the like.

In R ₀ SO ₂ NHR ′, the alkyl group of the optionally substituted alkyl group represented by R ₀ may be any of linear, branched or cyclic, and is preferably Has 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec
-Butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-
Examples include a hexyl group, an isohexyl group, a cyclohexyl group, and the like.

Examples of the substituent of the alkyl group which may have a substituent represented by R ₀ include a hydroxyl group, for example, a halogen atom such as chlorine, bromine, fluorine and iodine, and an alkoxy group. May be linear or branched, preferably having 1 to 6 carbon atoms, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert -Butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, isohexyloxy group and the like.

Examples of the aryl group of the optionally substituted aryl group represented by R ₀ include a phenyl group and a naphthyl group.

Examples of the substituent of the aryl group which may have a substituent represented by R ₀ include a hydroxyl group, for example, a halogen atom such as chlorine, bromine, fluorine and iodine, an alkyl group and an alkoxy group. The alkyl group may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl Group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n
-Pentyl group, isopentyl group, tert-pentyl group, 1-
Methylpentyl group, cyclopentyl group, n-hexyl group,
Examples include an isohexyl group and a cyclohexyl group. The alkoxy group may be linear or branched, and preferably has 1 to 6 carbon atoms, methoxy group, ethoxy group, n-propoxy group, isopropoxy group,
n-butoxy group, isobutoxy group, tert-butoxy group, sec
-Butoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, isohexyloxy and the like.

In R ₀ SO ₂ NHR ′, the alkyl group represented by R ′ may be any of linear, branched or cyclic, and preferably has 1 to 6 carbon atoms. For example,
Methyl group, ethyl group, n-propyl group, isopropyl group,
Cyclopropyl group, n-butyl group, isobutyl group, tert-
Butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl and the like.

In the general formula [21], the alkyl group of the optionally substituted alkyl group represented by X ₁ and X ₂ may be linear or branched. Having preferably 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group , An isopentyl group, a tert-pentyl group, a 1-methylpentyl group, an n-hexyl group, an isohexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

Examples of the substituent of the optionally substituted alkyl group represented by X ₁ and X ₂ include a halogen atom such as chlorine, bromine, fluorine and iodine, and a nitro group.

Specific examples of the compound represented by R ₀ SO ₂ NHR ′ include, for example, methanesulfonamide, p- (or m
-) Sulfonamides such as toluenesulfonamide, benzenesulfonamide and the like are mentioned, and among them, p- (or m-) toluenesulfonamide, benzenesulfonamide and the like are particularly preferable.

Specific examples of the compound B according to the present invention include:
For example, amides such as N-benzoylbenzamide and diacetamide, for example, diacyl urea derivatives such as diacetyl urea, dipropionyl urea, dibenzoyl urea, and the like, and diacyl thiourea derivatives such as diacetyl thiourea, dipropionyl thiourea, dibenzoyl thiourea, and the like. Among these, amides such as N-benzoylbenzamide and diacetamide, which can improve the dependence on the substrate by adding a small amount, are particularly preferable.

The compounds according to the present invention may be used alone or in combination of two or more.

Examples of the polymer which becomes alkali-soluble by the action of an acid used in the present invention include compounds represented by general formula [5] or general formula [6].

[0044]

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[R and R ₁ each independently represent a hydrogen atom or a lower alkyl group, and R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group optionally substituted with halogen or an allyl group. And R ₂ and R ₃ may be bonded to each other to form an alkylene ring (provided that R ₂ and R ₃ are not both hydrogen atoms), and R ₄ is an alkyl group or an aralkyl group optionally substituted with halogen. R ₅ represents a cyano group, a carboxyl group which may be esterified, or a phenyl group which may have a substituent, m and n ′ each represent a natural number, and k represents 0 or a natural number ( However, m> k.). ]

[0046]

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Wherein R ₆ represents a hydrogen atom or a lower alkyl group, and R ₇ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, an acyloxy group, a saturated heterocyclic oxy group or
₈ O—CO— (CH ₂ ) _Z —O— (where R ₈ represents an alkyl group, z represents 0 or a natural number), and R ₂₁ represents a hydrogen atom or a lower alkyl group. R ₂₂ represents a cyano group, a carboxyl group which may be esterified, or a phenyl group which may have a substituent, p and r each represent a natural number, and f represents 0 or a natural number (provided that
p> f. ). However, when R ₇ is a hydrogen atom or a lower alkyl group, R ₂₂ is an alkoxy group, a 5- to 6-membered saturated heterocyclic group or R ₂₅ O—CO— (CH ₂ ) jO— (in the formula,
R ₂₅ represents a lower alkyl group, and j is 0 or 1. )
Represents a substituted phenyl group substituted with a group represented by ].

In the general formula [5], a lower alkyl group represented by R and R ₁ , and in the general formula [6], R ₆ and R
_The lower alkyl group represented by ₂₁ may be linear or branched, and each independently has 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, te
rt-pentyl group, 1-methylpentyl group, n-hexyl group,
And an isohexyl group.

In the general formula [5], the alkyl group of the alkyl group represented by R ₂ , R ₃ and R ₄ which may be substituted by halogen may be any of linear, branched and cyclic. May preferably have 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec- Butyl group, n-pentyl group, isopentyl group,
Examples include tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, octyl, nonyl, and decyl groups.

The halogen of the alkyl group which may be substituted with a halogen represented by R ₂ , R ₃ and R ₄ includes chlorine, bromine, fluorine and iodine.

The alkylene ring which may be formed by R ₂ and R ₃ preferably has 3 to 6 carbon atoms, such as a propylene ring, a butylene ring, a pentylene ring and a hexylene ring.

The aralkyl group represented by R ₄ includes, for example, a benzyl group, a phenethyl group, a phenylpropyl group,
Examples include a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group.

In the carboxyl group which may be esterified and represented by R ₅ in the general formula [5], the carboxyl group and the hydrogen atom of the carboxyl group are replaced by, for example, an alkyl group having 1 to 6 carbon atoms. And methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl and the like.

Examples of the substituent of the optionally substituted phenyl group represented by R ₅ include a halogen atom such as chlorine, bromine, fluorine and iodine, a linear, branched or cyclic alkyl group. Having preferably 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, te
rt-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, octyl, nonyl , A decyl group or the like, a linear or branched alkoxy group, preferably having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group , Tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, isohexyloxy group and the like, and linear, branched or cyclic carboxylic acids having 2 to 7 carbon atoms Acyl groups derived from acids such as acetyl, propionyl, n-butyryl, isobutyryl, n-pentanoyl, pivaloyl, isovaleryl, And b hexane carbonyl group, for example, tetrahydrofuranyl group, tetrahydropyranyl 5-6 membered saturated heterocyclic oxy group such as a _{group, R 25 O-CO- (CH} 2) jO- ( where, R ₂₅ and j Is the same as described above.). Here, the lower alkyl group represented by R ₂₅ may be linear, branched or cyclic and has 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group. Group, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, cyclobutyl, n-pentyl, isopentyl, tert-
Pentyl group, 1-methylpentyl group, cyclopentyl group,
Examples include an n-hexyl group, an isohexyl group, and a cyclohexyl group. Specific examples of the group represented by R ₂₅ O—CO— (CH ₂ ) jO— include, for example, methyloxycarbonyloxy, ethyloxycarbonyloxy, isopropyloxycarbonyloxy, tert-butyloxycarbonyloxy, isobutyl Oxycarbonyloxy group, tert-pentyloxycarbonyloxy group, ethyloxycarbonylmethyloxy group, tert-butyloxycarbonylmethyloxy group, 1-methylcyclopentyloxycarbonylmethyloxy group, 1-methylcyclohexyloxycarbonylmethyloxy group, etc. No.

The lower alkyl group represented by R ₇ in the general formula [6] is preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms. Preferred examples include isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, tert-pentyl, 1-methylpentyl, and isohexyl.

The lower alkoxy group represented by R ₇ is preferably a linear or branched alkoxy group having 1 to 6 carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-alkoxy group. Examples include a propoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-butoxy group, an n-pentyloxy group, an isopentyloxy group, an n-hexyloxy group, and an isohexyloxy group.

The acyloxy group represented by R ₇ includes
A linear, branched or cyclic carboxylic acid-derived acyloxy group preferably having 2 to 7 carbon atoms, such as an acetyloxy group, a propionyloxy group, an n-butyryloxy group, an isobutyryloxy group, and n -Pentanoyloxy group, pivaloyloxy group, isovaleryloxy group, cyclohexanecarbonyloxy group and the like.

The saturated heterocyclic oxy group represented by R ₇ is preferably a 5- or 6-membered one, and examples thereof include a tetrahydrofuranyloxy group and a tetrahydropyranyloxy group.

R ₈ O—CO— (CH ₂ ) _{Z— represented} by R ₇
As R ₈ of the O- group, a straight-chain having 1 to 10 carbon atoms,
Branched or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, sec-
Butyl, n-pentyl, isopentyl, 1-methylcyclohexyl, tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, octyl, nonyl, A decyl group, and R ₈ O—CO— (CH ₂ ) _Z
Specific examples of the -O- group include, for example, a methyloxycarbonyloxy group, an ethyloxycarbonyloxy group, an isopropyloxycarbonyloxy group, an isobutyloxycarbonyloxy group, a tert-butyloxycarbonyloxy group, a tert-pentyloxycarbonyloxy group , 1-
Methylcyclohexyloxycarbonylmethyloxy group, tert-butyloxycarbonylmethyloxy group, 1-
And a methylcyclopentyloxycarbonylmethyloxy group.

In the carboxyl group which may be esterified and represented by R ₂₂ in the general formula [6], the carboxyl group and the hydrogen atom of the carboxyl group are replaced by, for example, an alkyl group having 1 to 6 carbon atoms. And methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl and the like.

Examples of the substituent of the phenyl group which may have a substituent represented by R ₂₂ include a halogen atom such as chlorine, bromine, fluorine and iodine, a linear, branched or cyclic alkyl group. Having preferably 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, te
rt-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, octyl, nonyl , A decyl group or the like, a linear or branched alkoxy group, preferably having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group , Tert-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, isohexyloxy group and the like, and linear, branched or cyclic carboxylic acids having 2 to 7 carbon atoms Acyl groups derived from acids such as acetyl, propionyl, n-butyryl, isobutyryl, n-pentanoyl, pivaloyl, isovaleryl, And b hexane carbonyl group, tetrahydrofuranyl group, tetrahydropyranyl 5-6 membered saturated heterocyclic oxy group such as a _{group, R 25 O-CO- (CH} 2) jO- ( where, R ₂₅
And j are the same as above. And the like.

[0062] R ₂₂ is a cyano group, it may be any of the esterified carboxyl group which may or may have a substituent phenyl group, when R7 is a hydrogen atom or a lower alkyl group, R ₂₂ Is an alkoxy group, a 5- to 6-membered saturated heterocyclic group or R ₂₅ O—CO— (CH ₂ ) jO— (wherein
R ₂₅ represents a lower alkyl group, and j is 0 or 1. )
Represents a substituted phenyl group substituted with a group represented by

Specific examples of the compound represented by the general formula [5] include poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene] and poly [p- (1-
Benzyloxy-1-methylethoxy) styrene / p-hydroxystyrene, poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene], poly [p- (1-methoxyethoxystyrene) / p-hydroxystyrene ], Poly [p-1-n-butoxyethoxystyrene / p-hydroxystyrene], poly [p- (1,1-dimethylethoxy) -1-methylethoxystyrene / p-hydroxystyrene], poly [p-
(1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / styrene], poly [p- (1-methoxy-1-
Methylethoxy) styrene / p-hydroxystyrene / p-
Chlorostyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-methylstyrene], poly [p- (1-methoxy-1-methylethoxy)
Styrene / p-hydroxystyrene / p-methoxystyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-tert-butoxystyrene], poly [p- (1-methoxy 1-methylethoxy) styrene / p-hydroxystyrene / p-1-methylcyclohexyloxystyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / methyl methacrylate], poly [P- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / methacrylic acid
ert-butyl], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / acrylonitrile], poly [p- (1-benzyloxy-1-methylethoxy) styrene / p-hydroxystyrene / Styrene], poly [p- (1-benzyloxy-1-methylethoxy) styrene / p-hydroxystyrene / p-chlorostyrene], poly [p- (1-benzyloxy-1-methylethoxy) styrene / p -Hydroxystyrene / p-methylstyrene], poly [p- (1-benzyloxy-1-methylethoxy) styrene / p-hydroxystyrene / p-ethoxystyrene], poly [p- (1-benzyloxy-1-) Methylethoxy) styrene / p-hydroxystyrene / p-tert-butoxystyrene], poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / styrene), poly (p-1-ethoxyethoxy) Styrene / p-hydroxystyrene / p-chlorostyrene, poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / m -Methylstyrene), poly (p-1-ethoxyethoxystyrene / p-
Hydroxystyrene / methyl methacrylate), poly (p-
1-ethoxyethoxystyrene / p-hydroxystyrene /
Cyclohexyl methacrylate), poly (p-1-ethoxyethoxystyrene) / p-hydroxystyrene / methacrylic acid
tert-butyl), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / acrylonitrile), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-methoxystyrene), poly (p-1- Ethoxyethoxystyrene / p-hydroxystyrene / p-ethoxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene), poly (p-
1-ethoxyethoxystyrene / p-hydroxystyrene /
Acrylic acid), poly (p-1-ethoxyethoxystyrene) /
p-hydroxystyrene / p-methoxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-ethoxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) / P-isopropoxycarbonyloxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-isobutyloxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-
Hydroxystyrene / p-isobutoxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-
Hydroxystyrene / p-isoamyloxycarbonyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-1-methylcyclohexyloxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxy) Styrene / styrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-methylstyrene), poly (p-1-methoxyethoxystyrene)
p-hydroxystyrene / m-methylstyrene), poly (p-
1-methoxyethoxystyrene / p-hydroxystyrene /
p-chlorostyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-methoxystyrene),
Poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-ethoxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene), poly (p-1- Methoxyethoxystyrene / p-hydroxystyrene / p-1-methylcyclohexyloxystyrene), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / methyl methacrylate), poly (p-1-methoxyethoxystyrene / p -Hydroxystyrene / tert-butyl methacrylate), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / acrylonitrile), poly (p-1-n-butoxyethoxystyrene / p-
Hydroxystyrene / pn-butylstyrene), poly (p-
1-isobutoxyethoxystyrene / p-hydroxystyrene / o-methoxystyrene), poly {p-[(1,1-dimethylethoxy) -1-methylethoxy] styrene / p-hydroxystyrene / m-methoxystyrene}, Poly [p- (1,1-dimethylethoxy) -1-methylethoxystyrene / p-hydroxystyrene / o-methylstyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-acetoxystyrene) , Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-pivaloyloxystyrene), poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-cyclohexanecarbonyloxystyrene), poly [ m-1- (2-chloroethoxy) ethoxystyrene / m-hydroxystyrene / styrene], poly [m-1-
(2-ethylhexyloxy) ethoxystyrene / m-hydroxystyrene / m-methylstyrene], poly [p- (1-methoxy-1-methylethoxy) -α-methylstyrene / p-
Hydroxy-α-methylstyrene / styrene], poly [p- (1-ethoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-methylstyrene], poly (p-1-n-
Propoxyethoxystyrene / p-hydroxystyrene /
p-methoxystyrene), poly [p- (1-methyl-1-n-propoxyethoxy) styrene / p-hydroxystyrene / p-
Methylstyrene], poly (m-1-ethoxypropoxystyrene / m-hydroxystyrene / m-tert-butoxystyrene), poly (m-1-ethoxypropoxystyrene / m-hydroxystyrene / p-methylstyrene), poly [ m- (1-methoxy-1-methylethoxy) styrene / m-hydroxystyrene / m-tert-butoxystyrene], poly [p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tetrahydrofuranyloxystyrene], Poly [p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tetrahydropyranyloxystyrene], poly [p-1-methoxyethoxystyrene / p-hydroxystyrene / p-tetrahydropyranyloxystyrene], poly [ p-1-ethoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene], poly [p-1 -Methoxyethoxystyrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene], poly [p- (1-methoxy-1-methylethoxy) styrene / p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene] ,
Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene / tert-butyl p-vinylphenoxyacetate), poly (p-1-methoxyethoxystyrene / p-hydroxystyrene / tert-butyl p-vinylphenoxyacetate), Poly (p-
1-methoxyethoxystyrene / p-hydroxystyrene /
p-vinylphenoxyacetic acid 1-methylcyclohexyl),
Poly [m-1-ethoxyethoxystyrene / m-hydroxystyrene / m-tert-butoxycarbonyloxystyrene], poly (m-1-ethoxyethoxystyrene / m-hydroxystyrene / m-tert-butoxystyrene), poly ( m-
1-methoxyethoxystyrene / m-hydroxystyrene /
m-tert-butoxystyrene), poly (p-1-ethoxyethoxystyrene / m-1-ethoxyethoxystyrene / p-hydroxystyrene / m-hydroxystyrene / p-tert-butoxystyrene / m-tert-butoxystyrene) , Poly (p-
1-methoxybutoxystyrene / p-hydroxystyrene /
Styrene).

Specific examples of the compound represented by the general formula [6] include poly (p-tert-butoxystyrene / p-hydroxystyrene), poly (1-methylcyclohexyloxystyrene / p-hydroxystyrene), and poly (p-tert-butoxystyrene / p-hydroxystyrene). (M-tert
-Butoxystyrene / m-hydroxystyrene), poly (p-methoxycarbonyloxystyrene / p-hydroxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene), poly (p-isopropoxycarbonyloxystyrene / p-hydroxystyrene),
Poly (p-isobutoxycarbonyloxystyrene / p-hydroxystyrene), poly (m-isobutoxycarbonyloxystyrene / m-hydroxystyrene), poly (p-te
rt-butoxycarbonyloxystyrene / p-hydroxystyrene), poly (m-tert-butoxycarbonyloxystyrene / p-hydroxystyrene), poly (p-isoamyloxycarbonyloxystyrene / p-hydroxystyrene), poly (m- Isoamyloxycarbonyloxystyrene / m-hydroxystyrene), poly (p-tert-amyloxycarbonyloxystyrene / p-hydroxystyrene), poly (p-acetyloxystyrene / p-hydroxystyrene), poly (p-isobutylene) Loyloxystyrene / p-hydroxystyrene), poly (p-pivaloyloxystyrene / p-hydroxystyrene), poly (p-cyclohexanecarbonyloxystyrene / p-hydroxystyrene), poly (p-sec butoxycarbonyloxy) Styrene / p-hydroxystyrene), poly (p -Tetrahydrofuranyloxystyrene / p-hydroxystyrene), poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene), poly (m-tetrahydropyranyloxystyrene / m-hydroxystyrene), poly (p-vinylphenoxy) Tert-butyl acetate / p-hydroxystyrene), poly (1-methylcyclohexyl p-vinylphenoxyacetate / p-hydroxystyrene), poly (styrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p -Methylstyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-methoxystyrene /
p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-methylstyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (m-methylstyrene / p-hydroxystyrene / p-1) -Ethoxyethoxystyrene), poly (p-methoxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-
tert-butylstyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (styrene / p-hydroxystyrene) /
p-1-methoxy-1-methylethoxystyrene), poly (p-
Methylstyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (p-methoxystyrene / p-hydroxystyrene / p-methoxy-1-methylethoxystyrene), poly (p-tert- Butylstyrene / p-
Hydroxystyrene / p-methoxy-1-methylethoxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (styrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene), poly (p-methylstyrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene), poly (p-methoxystyrene / p-hydroxystyrene / p-1-benzyloxy) Ethoxystyrene), poly (p-tert-butylstyrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene /
p-1-benzyloxyethoxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene / p-
1-ethoxyethoxystyrene), poly (p-ethoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (p-tert-
Butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-tert
-Butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-te
rt-butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene / p-1-benzyloxyethoxystyrene) , Poly (p-acetyloxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene),
Poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene / p-1-methoxyethoxystyrene), poly (p-tetrahydropyranyloxystyrene / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly ( p-tetrahydropyranyloxystyrene / p-hydroxystyrene / p-1-methoxy-1-methylethoxystyrene), poly (1-methylcyclohexyl p-vinylphenoxyacetate) / p-hydroxystyrene / p-1-methoxyethoxystyrene ), Poly (1-methylcyclohexyl p-vinylphenoxyacetate / p-hydroxystyrene / p-1-ethoxyethoxystyrene), poly (p-vinylphenoxyacetic acid)
1-methylcyclohexyl / p-hydroxystyrene / p-
1-methoxy-1-methylethoxystyrene) and the like.

Examples of the alkali-soluble polymer according to the present invention include poly (p-hydroxystyrene) and poly (m-
Hydroxystyrene), poly (3-methyl-4-hydroxystyrene), poly (p-tert-butoxystyrene / p-hydroxystyrene) [provided that the number ratio of p-tert-butoxystyrene units to p-hydroxystyrene units is The former is limited to 2 or less, while the latter is limited to 8 or more (hereinafter referred to as 2 ↓: 8 ↑). ], Poly (p-1-ethoxyethoxystyrene / p-hydroxystyrene) [however, the ratio of p-1-ethoxyethoxystyrene units to p-hydroxystyrene units is 2 ↓: 8 ↑]
Is limited to ], Poly (p-tert-butoxycarbonyloxystyrene / p-hydroxystyrene) [provided that p-te
The ratio of rt-butoxycarbonyloxystyrene units to p-hydroxystyrene units is limited to 2 ↓: 8 ↑. ], Poly (p-1-ethoxyethoxystyrene / p-tert)
-Butoxystyrene / p-hydroxystyrene) [However, p
The ratio of the sum of 1-ethoxyethoxystyrene units and p-tert-butoxystyrene units to p-hydroxystyrene units is limited to 2 ↓: 8 ↓. ], Poly (p-1-ethoxyethoxystyrene / styrene / p-hydroxystyrene) [however, the ratio of p-1-ethoxyethoxystyrene units and styrene units to p-hydroxystyrene units is 2 ↓: 8 ↑] Is limited to And the like.

As the compound which becomes alkali-soluble by the action of an acid used in the present invention, for example, a part or all of the phenolic hydroxyl group of the alkali-soluble compound having a phenolic hydroxyl group may be a tert-butoxycarbonyl group or a tert-butoxycarbonyl group. Butyl group, 1-methoxyethyl group, 1-ethoxyethyl group, tetrahydropyranyl group, an alkali-insoluble compound protected with a 1-methylcyclohexyloxycarbonylmethyl group and the like, as specific examples, for example, 2,2-bis (4-tert-butyloxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butyloxyphenyl) propane, 2,2-bis (tetrahydropyranyloxyphenyl) propane, 2,2-bis [4 -(1-methoxyethoxy) phenyl] propane, 2,2-bis [4- (1-ethoxyethoxy) phenyl] propane, 2,2-bis [4- (1-methyl Clohexyloxycarbonylmethyloxy) phenylpropane], 1,1,2-tris (4-tert-butyloxyphenyl) -2-methylpropane, 1,1,2-tris [4- (1-ethoxyethoxy) phenyl ] -2-Methylpropane, 1,1,2-tris (tert-butyloxycarbonyloxyphenyl)-
2-methylpropane and the like.

The compound used in the present invention, which crosslinks with a polymer by the action of an acid to make the polymer hardly soluble in alkali, is represented by the following general formula [7]:

[0068]

Embedded image

[Wherein, R ₃₆ represents an alkyl group, R ₃₇ represents a hydrogen atom or a general formula [8]

[0070]

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(Wherein R ₃₆ is the same as defined above). Or a compound represented by the following general formula [9]:

[0072]

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[Wherein, R ₃₈ represents a hydrogen atom or an alkyl group, and R ₃₉ represents a hydrogen atom or a general formula [10]

[0074]

Embedded image

(Wherein R ₃₈ is the same as defined above). And the like.

The alkyl group represented by R ₃₆ in the general formulas [7] and [8] and the alkyl group represented by R in the general formulas [9] and [10]
_The alkyl group represented by ₃₈ may be linear, branched, or cyclic, and preferably has 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl. Group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group,
Examples include an isopentyl group, a tert-pentyl group, a 1-methylpentyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, and a cyclohexyl group.

Specific examples of the compound which cross-links with the polymer by the action of an acid to make the polymer hardly alkali-soluble include, for example, 1,2,4-tris (cyclohexyloxymethoxy) benzene, 1,2,4-tris (isobutoxy) Methoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, 1,3,5-tris (cyclohexyloxymethoxy) benzene, 1,3,5-tris (isobutoxymethoxy) benzene, 1,3, 5-tris (isopropoxymethoxy) benzene, 1,3-bis (cyclohexyloxymethoxy) benzene, 1,3-bis (isobutoxymethoxy) benzene, 1,3-
Bis (isopropoxymethoxy) benzene, 1,4-bis (cyclohexyloxymethoxy) benzene, 1,4-bis (isobutoxymethoxy) benzene, 1,4-bis (isopropoxymethoxy) benzene, 2,4,6- Tris (N, N-dimethoxymethylamino) -1,3,5-triazine, 2,4-bis (N, N-dimethoxymethylamino) -1,3,5-triazine and the like can be mentioned.

The polymer which becomes alkali-soluble by the action of an acid according to the present invention or the alkali-soluble polymer includes radical polymerization using an organic peroxide or an azo compound as a polymerization initiator, n-butyllithium, naphthalene potassium, or the like. A desired polymer can be obtained by chemically reacting a polymer obtained by living polymerization or the like as required. These polymers are described in, for example, JP-A-4-211258 and JP-A-5-19.
It can be easily obtained by the method described in JP-A-4472.

The molecular weight or dispersity (weight-average molecular weight to number-average molecular weight ratio) of a polymer which becomes alkali-soluble by the action of an acid according to the present invention, or an alkali-soluble polymer.
The weight average molecular weight obtained by GPC measurement using polystyrene as a standard is usually 3,000 to 50,000, preferably 5,000 to 30,000, and the dispersity is usually 1.00.
To 3.00, preferably 1.02 to 2.00.

The compound according to the present invention, which becomes alkali-soluble by the action of an acid, can be easily obtained, for example, by the method described in JP-A-4-88348.

The compound of the present invention which makes a polymer hardly soluble in alkali by crosslinking with a polymer by the action of an acid can be easily obtained, for example, by the method described in JP-A-6-83055.

The acid generator used in the present invention may be any substance which can generate an acid upon irradiation with radiation and does not adversely affect the formation of a resist pattern. Good transparency of the resist material and maintain the high transparency of the resist material
An acid generator capable of increasing the light transmittance around 8.4 nm and maintaining the high transparency of the resist material is preferably exemplified. Particularly preferred acid generators in the present invention include, for example, the following general formulas [11], [12] and [1]
4], general formula [15], general formula [16] and general formula [1]
8].

[0083]

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[Wherein, R ₉ and R ₁₀ each independently represent an alkyl group or a haloalkyl group, and A ′ represents a sulfonyl group or a carbonyl group. ]

[0085]

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[Wherein R ₁₁ is a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkoxy group or a haloalkyl group,
R ₁₂ is an alkyl group, a haloalkyl group, or the following general formula [13]

[0087]

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Wherein R ₁₃ is a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkoxy group, or a haloalkyl group, and q represents 0 or an integer of 1 to 3. Represents｝. ]

[0089]

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[Wherein R ₁₄ is a hydrogen atom, a halogen atom,
R ₁₅ represents an alkyl group, an aralkyl group, an alkoxy group, a phenyl group or a tolyl group; ]

[0091]

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[Wherein R ₁₆ is an alkyl group, a phenyl group,
Substituted phenyl group or an aralkyl group, R ₁₇ and R ₁₈
Each independently represents a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or an aralkyl group, and R ₁₉ represents a fluoroalkyl group, a trifluoromethylphenyl group, a methyl group, or a tolyl group. ]

[0093]

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[Wherein, R ₂₉ represents an alkyl group, a fluoroalkyl group, a phenyl group, a substituted phenyl group or an aralkyl group, Q ′ represents a sulfonyl group or a carbonyl group, and R ₃₀ and R ₃₁ each independently represent Hydrogen atom, methyl group,
A methoxy group, a nitro group, a cyano group, a hydroxyl group or the following general formula [17]

[0095]

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(Wherein R ₃₃ represents an alkyl group, a fluoroalkyl group, a phenyl group, a substituted phenyl group or an aralkyl group, Q ′ represents a sulfonyl group or a carbonyl group), R ₃₂ represents a hydrogen atom, Represents a methyl group or an ethyl group. ]

[0097]

Embedded image

Wherein R ₃₄ represents an alkyl group, a fluoroalkyl group, a phenyl group, a substituted phenyl group or an aralkyl group, and R ₃₅ represents a hydrogen atom, a methyl group, a fluoroalkyl group, a methoxy group, a nitro group, a cyano group , A hydroxyl group or the general formula [17]. ]

In the general formula [11], the alkyl group represented by R ₉ and R ₁₀ and the alkyl group of the haloalkyl group may be any of linear, branched or cyclic, preferably carbon The number is 1 to 10, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-
Butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, etc. Can be

The halogen of the haloalkyl group includes chlorine, bromine, fluorine, iodine and the like.

In the general formula [12], the alkyl group represented by R ₁₁ and the alkyl group of the haloalkyl group may be linear or branched, and preferably have 1 to 5 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert
-Butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, and the like.Examples of the halogen atom or the haloalkyl group represented by R ₁₁ include chlorine, bromine, Examples include fluorine and iodine. The alkoxy group represented by R ₁₁ may be linear or branched and preferably has 1 to 5 carbon atoms, for example, methoxy group, ethoxy group, n-
Examples include a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-butoxy group, an n-pentyloxy group, and an isopentyloxy group. The alkyl group and the alkyl group of the haloalkyl group represented by R ₁₂ may be linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, cyclopentyl , An n-hexyl group, an isohexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and the like, and a halogen of the haloalkyl group includes chlorine, bromine, fluorine and iodine.

In the general formula [13], the alkyl group represented by R ₁₃ and the alkyl group of the haloalkyl group may be linear or branched, and preferably have 1 to 6 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert
-Butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, n-hexyl group, isohexyl group and the like. The alkoxy group having 1 to 6 carbon atoms represented by R ₁₃ may be linear or branched, and preferably has 1 to 5 carbon atoms, for example, a methoxy group, an ethoxy group, and an n-propoxy group. Group,
Isopropoxy group, n-butoxy group, isobutoxy group, te
rt-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, isohexyloxy group, and the halogen atom or the haloalkyl group represented by R ₁₃ is chlorine, bromine, Examples include fluorine and iodine.

In the general formula [14], the alkyl group represented by R ₁₄ may be linear or branched, and preferably has 1 to 5 carbon atoms, for example, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n
-Pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group and the like. Examples of the halogen atom represented by R ₁₄ include chlorine, bromine, fluorine, iodine and the like. The alkyl group represented by R ₁₅ may be linear, branched or cyclic, and preferably has 1 carbon atom.
~ 10, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group,
Isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, 1-methylpentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, heptyl, octyl , Nonyl group, decyl group and the like.

The aralkyl group represented by R ₁₅ includes, for example, a benzyl group, a phenethyl group, a phenylpropyl group,
Examples include a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group. The alkoxy group represented by R ₁₅ may be linear or branched, for example, a methoxy group having 1 to 6 carbon atoms, an ethoxy group, an n-propoxy group,
Isopropoxy group, n-butoxy group, isobutoxy group, te
Examples thereof include rt-butoxy group, sec-butoxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, and isohexyloxy.

In the general formula [15], R ₁₆ , R ₁₇ and R
_The alkyl group represented by ₁₈ may be linear, branched or cyclic, and preferably has 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group , Cyclopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, cyclopentyl group, n-hexyl group, Examples include an isohexyl group, a cyclohexyl group, a heptyl group, and an octyl group.Examples of the substituted phenyl group include a tolyl group, an ethylphenyl group, a tert-butylphenyl group, and a chlorophenyl group.Examples of an aralkyl group include a benzyl group. Phenethyl group, phenylpropyl group, methylbenzyl group, methylphenethyl group, ethylbenzyl group and the like. The alkyl group of the fluoroalkyl group represented by R ₁₉ may be linear or branched, and preferably has 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group , Isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n
-Pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, n-hexyl group, isohexyl group, heptyl group, octyl group, etc., and the total number of substituted fluorine atoms is 1 to 17 are preferred.

In the general formula [16], the alkyl group represented by R ₂₉ may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group And the like.Examples of the substituted phenyl group include a tolyl group, an ethylphenyl group, a tert-butylphenyl group and a chlorophenyl group.Examples of the aralkyl group include a benzyl group,
Examples include a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group. The alkyl group of the fluoroalkyl group may be linear or branched, and preferably has 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, heptyl group, octyl group, etc., and the total number of substituted fluorine atoms Number is 1
To 17 are preferred.

In the general formula [17], the alkyl group represented by R ₃₃ may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group And the like.Examples of the substituted phenyl group include a tolyl group, an ethylphenyl group, a tert-butylphenyl group and a chlorophenyl group.Examples of the aralkyl group include a benzyl group,
Examples include a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group. The alkyl group of the fluoroalkyl group may be linear or branched, and preferably has 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, heptyl group, octyl group, etc., and the total number of substituted fluorine atoms Number is 1
To 17 are preferred.

In the general formula [18], the alkyl group represented by R ₃₄ may be linear, branched or cyclic, and preferably has 1 to 6 carbon atoms. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl And the like.Examples of the substituted phenyl group include a tolyl group, an ethylphenyl group, a tert-butylphenyl group and a chlorophenyl group.Examples of the aralkyl group include a benzyl group,
Examples include a phenethyl group, a phenylpropyl group, a methylbenzyl group, a methylphenethyl group, and an ethylbenzyl group. The alkyl group of the fluoroalkyl group represented by R ₃₄ and R ₃₅ may be linear or branched, and preferably has 1 to 8 carbon atoms, for example, a methyl group, an ethyl group , N-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, heptyl group, octyl group and the like, The total number of substituted fluorine atoms is preferably 1 to 17.

Specific examples of preferred acid generators used in the present invention include, for example, 1-cyclohexylsulfonyl-1-acid as the acid generator represented by the general formula [11].
(1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane , 1-diazo-1-cyclohexylsulfonyl-3,3-dimethylbutan-2-one, 1-diazo-1-methylsulfonyl-4-phenylbutan-2-one, 1-diazo-1- (1,1- Dimethylethylsulfonyl) -3,3-dimethyl-2-butanone,
1-acetyl-1- (1-methylethylsulfonyl) diazomethane and the like.

Examples of the acid generator represented by the general formula [12] include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and bis (p-toluenesulfonyldiazomethane). p-tert-butylphenylsulfonyl) diazomethane, bis (p-chlorobenzenesulfonyl) diazomethane, cyclohexylsulfonyl-p-toluenesulfonyldiazomethane and the like.

Examples of the acid generator represented by the general formula [14] include 1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1- (p-toluenesulfonyl) -3,3-dimethylbutane -2-one, 1-diazo-
1-benzenesulfonyl-3,3-dimethylbutan-2-one,
1-diazo-1- (p-toluenesulfonyl) -3-methylbutan-2-one and the like.

Examples of the acid generator represented by the general formula [15] include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate, diphenyl-p-tolylsulfonium perfluorooctanesulfonate, and tris (p -Tolyl) sulfonium perfluorooctanesulfonate, tris (p-chlorobenzene) sulfonium trifluoromethanesulfonate, tris (p-tolyl) sulfonium trifluoromethanesulfonate,
Trimethylsulfonium ・ trifluoromethanesulfonate, dimethylphenylsulfonium ・ trifluoromethanesulfonate, dimethyl-p-tolylsulfonium ・
Trifluoromethanesulfonate; dimethyl-p-tolylsulfonium perfluorooctanesulfonate;

Examples of the acid generator represented by the general formula [16] include 2,6-di-trifluoromethanesulfonyloxyacetophenone, 2,6-di-trifluoromethanesulfonyloxypropiophenone, 2,3,4- Tris-trifluoromethanesulfonyloxyacetophenone, 2,6-di-
Methanesulfonyloxyacetophenone, 2,6-di-methanesulfonyloxypropiophenone, 2,3,4-tris-
Methanesulfonyloxyacetophenone, 2-trifluoromethanesulfonyloxyacetophenone, 2-methanesulfonyloxyacetophenone, 2-n-butanesulfonyloxyacetophenone, 2,6-di-n-butanesulfonyloxyacetophenone, 2,3,4-tris- n-butanesulfonyloxyacetophenone, 2,6-di-perfluoropropanecarboxyacetophenone, 2,3,4-tris-perfluoropropanecarboxyacetophenone, 2,6-di-p-toluenesulfonylacetophenone, 2,6-di -P-toluenesulfonylpropiophenone, 2,6-di-trifluoroacetyloxyacetophenone, 2-trifluoroacetyloxy-6-methoxyacetophenone, 6-hydroxy-2-
Perfluorobutanesulfonyloxyacetophenone,
Examples thereof include 2-trifluoroacetyloxy-6-nitroacetophenone, 2,3,4-tris-trifluoroacetyloxyacetophenone, and 2,6-di-perfluoropropanoyloxyacetophenone.

Examples of the acid generator represented by the general formula [18] include 1,2,3-tris-methanesulfonyloxybenzene, 1,2,3-tris-p-toluenesulfonyloxybenzene, 1,2,3 3-tris-trifluoromethanesulfonyloxybenzene, 1,2,3-tris-perfluorobutanesulfonyloxybenzene, 1,2,3-tris-cyclohexylsulfonyloxybenzene, 1.2-di-methanesulfonyloxy-3-nitrobenzene, 2,3-di-methanesulfonyloxyphenol, 1,2,4-tris-p-toluenesulfonyloxybenzene, 1,2,4-tris-methanesulfonyloxybenzene, 1,2,4-tris-trifluoromethanesulfonyl Oxybenzene, 1,2,4-tris-cyclohexylsulfonyloxybenzene, 1,2-di-n-butanesulfonyloxy-3-nitrobenzene, 1,2,3-tris-pa -Fluorooctanesulfonyloxybenzene, 1,2-di-perfluorobutanesulfonyloxyphenol and the like.

The acid generator according to the present invention is described in, for example,
No. 210960, JP-A-4-211258, JP-A-5-249682
Can easily be obtained by the method described in Japanese Patent Application Laid-Open No. H10-209, etc.

In the resist composition of the present invention, the mixing ratio of the polymer which becomes alkali-soluble by the action of an acid (hereinafter abbreviated as polymer component (i)) and the compound of the present invention is determined by the polymer component ( i) The compound of the present invention is generally used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 1.0 part by weight, based on 100 parts by weight.

In the resist composition of the present invention, the mixing ratio of the alkali-soluble polymer and the compound which becomes alkali-soluble by the action of an acid is such that the compound which becomes alkali-soluble by the action of an acid is mixed with 100 parts by weight of the polymer. Usually 10-50
Parts by weight, preferably 15 to 40 parts by weight.Furthermore, the mixing ratio of the compound which becomes alkali-soluble by the action of an alkali-soluble polymer and an acid and the compound of the present invention is such that the alkali-soluble polymer and the action of an acid cause The sum of soluble compounds (hereinafter referred to as polymer component (ii)
Abbreviated. ) The compound of the present invention is usually 0.01 to 10 parts by weight, preferably 0.1 to 1.0 part by weight, per 100 parts by weight.

In the resist composition of the present invention, the mixing ratio of the alkali-soluble polymer and the compound which crosslinks the polymer by the action of an acid to make the polymer hardly alkali-soluble is 100 parts by weight of the polymer to 100 parts by weight of the polymer. The compound which makes the polymer hardly soluble in alkali by crosslinking with the polymer by the action of usually 10 to 50 parts by weight, preferably 15 to 40 parts by weight,
Furthermore, the mixing ratio of the compound according to the present invention and the compound that makes the polymer hardly soluble in alkali by crosslinking with a polymer by the action of an alkali-soluble polymer and an acid is such that the polymer is crosslinked with the polymer by the action of an alkali-soluble polymer and an acid. The compound according to the present invention is usually 0.01 to 10 parts by weight, preferably 0.1 to 1.0 part by weight, per 100 parts by weight of the total of the compounds that are hardly soluble in alkali (hereinafter abbreviated as polymer component (iii)). .

In the resist composition of the present invention, the mixing ratio of the polymer component (i) to the acid generator is determined by the polymer component (i)
The acid generator is generally used in an amount of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight.

In the resist composition of the present invention, the mixing ratio of the polymer component (ii) to the acid generator is determined by the polymer component (ii)
The acid generator is generally used in an amount of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight.

In the resist composition of the present invention, the mixing ratio of the polymer component (iii) and the acid generator is determined by adjusting the polymer component (ii)
i) The acid generator is usually 1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight.

The solvent used in the present invention may be any solvent which can dissolve any of the above polymer components (i) to (iii), the acid generator and the compound according to the present invention. Those having good film properties are preferably used. Specific examples of preferred solvents include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, N-methyl-2-pyrrolidone, 2-heptanone,
Examples include cyclohexanone, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and the like.

The amount of the solvent used in the present invention is preferably 2 to 20 times, more preferably 3 to 10 times the weight of the total weight of any of the polymer components (i) to (iii).

The resist composition according to the present invention generally comprises four components [any of the above-mentioned polymer components (i) to (iii), an acid generator, a compound according to the present invention, and a solvent]. In addition, if necessary, a sensitivity adjuster, a surfactant, an ultraviolet absorber, a plasticizer, a solubilizer, or the like may be added.

Examples of the sensitivity adjuster optionally used in the resist composition according to the present invention include polyvinyl pyridine, poly (vinyl pyridine / methyl methacrylate), pyridine, N, N-bis (2- Hydroxyethyl) aniline, monoalkylamines [an alkyl group includes a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, specifically, 2-methylcyclohexylamine, 4-t -Butylcyclohexylamine and the like. ], Dialkylamines [an example of the alkyl group is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and specific examples thereof include dicyclohexylamine and dialkylamine.
-n-octylamine and the like are preferred. ], Trialkylamines [the alkyl group includes 1 to 12 carbon atoms]
Linear, branched or cyclic alkyl group is, specifically, triethylamine, tri-n-propylamine, tri-n-butylamine, trihexylamine,
Trioctylamine, dicyclohexylmethylamine,
Dioctylmethylamine, dimethyloctylamine and the like are preferred. ], Mono-, di- or trialkanolamines [specifically, triethanolamine, triisopropanolamine and the like are preferable. ] Tetraalkylammonium hydroxides [Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and specifically, tetramethylammonium hydroxide, tetra-n-butyl Preferred are ammonium hydroxide and the like. However, it is needless to say that the present invention is not limited to these.

The amount of the sensitivity modifier optionally used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, per 100 parts by weight of any of the polymer components (i) to (iii). Parts are more preferred.

Examples of the surfactant used in the resist composition according to the present invention as needed include, for example, polyethylene glycol distearate, polyethylene glycol dilaurate, polyethylene glycol, polypropylene glycol, polyoxyethylene stearyl ether, and polyoxyethylene stearyl ether. Nonionic surfactants such as oxyethylene cetyl ether, cationic surfactants, and anionic surfactants are exemplified.

Among the above-mentioned surfactants, specific examples which are preferably used from the viewpoint of the film formability of a resist film include, for example, Florard (trade name of Sumitomo 3M Limited), Surflon (trade name of Asahi Glass Co., Ltd.), Unidyne (Daikin Industries, Ltd.)
Product name), Mega Fac (Dai Nippon Ink and Chemicals Co., Ltd. product name), F-top (Tochem Products Co., Ltd. product name)
And other fluorine-containing nonionic surfactants. .

The amount of the surfactant used if necessary is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, per 100 parts by weight of any of the polymer components (i) to (iii). Parts are more preferred.

Examples of the ultraviolet absorber used as needed in the resist composition according to the present invention include 9-diazofluorene, 9- (2-methoxyethoxymethyl) anthracene, and 9- (2-ethoxyethoxy). Methyl) anthracene, 9-fluorenone, 2-hydroxycarbazole, o-naphthoquinone azide, 4-diazo-1,7-diphenylpentane-
3,5-dione and the like.

The amount of the ultraviolet absorber used as required is preferably from 0.001 to 10 parts by weight, more preferably from 0.01 to 5 parts by weight, based on 100 parts by weight of any of the polymer components (i) to (iii). Is more preferred.

Examples of the plasticizer used as needed in the resist composition according to the present invention include di-n-butyl phthalate, bis (2-ethylhexyl) phthalate, dibutyl adipate, diethylene glycol dibenzoate, Examples include butyl oleate, methyl acetyl ricinoleate, paraffin chloride, and alkyl epoxystearate.

The amount of the plasticizer optionally used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, per 100 parts by weight of any of the polymer components (i) to (iii). Is more preferred.

Examples of the solubilizing agent used as necessary in the resist composition according to the present invention include N, N-dimethylformamide, N, N-dimethylacetamide and the like.

The amount of the solubilizing agent optionally used is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of any of the polymer components (i) to (iii). Parts are more preferred.

The pattern formation using the resist composition according to the present invention may be performed, for example, as follows.

SiO ₂ , polysilicon, BPSG, TEOS, TiN, S
The resist composition according to the present invention is spin-coated on a semiconductor substrate such as iN and baked on a hot plate at 50 to 120 ° C. for 0.5 to 2 minutes to obtain a resist film having a thickness of 0.5 to 2 μm. Then, selectively irradiate with radiation (for example, KrF excimer laser light of 248.4 nm, far ultraviolet light of 300 nm or less, electron beam or soft X-ray, etc.) through a mask, and then on a hot plate if necessary. Bake (post-bake) at 50-130 ° C for 0.5-2 minutes. Further, the exposed portion is dissolved and removed by developing with an alkali developing solution by a paddle method, a dipping method, a spray method, or the like, thereby forming a positive pattern.

Examples of the alkali in the alkali developer used in the above-mentioned various pattern forming methods include tetramethylammonium hydroxide, choline, triethanolamine, KOH, and NaOH.
The content is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. Further, a surfactant or the like may be added to the alkali developer.

When a chemically amplified resist composition to which the compound according to the present invention is added is used for a special substrate which is liable to have a shape defect due to the presence of a large amount of a base compound, the action of the base compound is reduced. The effect is obtained that a stable and good pattern shape can be obtained by suppressing. Although a method of using an organic carboxylic acid compound or an organic sulfonic acid compound to suppress the action of the base compound is also known,
In this case, in order to maintain the storage stability of the resist composition, it is necessary to use a base compound in an amount that can neutralize the acid or more. As a result, the sensitivity of the resist decreases, and the practicality decreases. There is. The above-mentioned problems are fully overcome at the same time by the use of the compounds according to the invention.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited by these. Some of the polymers and acid generators used in Examples and Comparative Examples are described in, for example,
No. 210960 (US Pat. No. 5,216,135);
No. 258 (U.S. Pat. No. 5,350,660; European Patent No.
440,374); Japanese Patent Application Laid-Open No. 5-249682 (European Patent
No. 0,520,642); JP-A-4-51259; Y. Endo et al., Che
m. Pharm. Bull., 29 (12), 3753 (1981) M. Desbois
Bull. Chem. Soc. France, 1974, 1956, or CDBea.
Synthesized according to the method described in J. Org. Chem., 38, 3673 (1973).

The polymers used in Examples and Comparative Examples were measured by gel permeation chromatography (GPC), and the weight average molecular weight (M
w) and the ratio of the weight average molecular weight to the number average molecular weight (Mw /
Mn: degree of dispersion) was calculated.

Example 1 A resist composition having the following composition was prepared. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (Mw 20000, dispersity 1.90) 4.5 g Bis (cyclohexylsulfonyl) diazomethane 0.3 g Bis (p-toluenesulfonyl) diazomethane 0.15 g Fluorine-containing nonionic interface Activator (commercially available) 0.05 g tri-n-propylamine 0.05 g propylene glycol monomethyl ether acetate 23 g phthalimide 0.02 g

After mixing and dissolving the above compositions, a pattern was formed as described below using the resist composition obtained through a 0.2 μm filter. A resist composition comprising the above composition is spin-coated on a semiconductor substrate (BPSG substrate) provided with a silicon oxide film doped with boron and phosphorus on a silicon wafer and baked on a hot plate at 90 ° C. for 90 seconds to form a 1 μm film. A thick resist film was obtained. Then 24
After selectively exposing a 8.4 nm KrF excimer laser beam (NA 0.55) through a mask,
Post-bake at 90 ° C for 90 seconds, then add an alkaline developer (2.38
% Tetramethylammonium hydroxide aqueous solution) by a paddle method for 60 seconds to dissolve and remove only the exposed portions of the resist film to obtain a positive pattern. The obtained positive pattern resolved contact holes having a good shape of 0.25 μm as shown in FIG. The exposure amount at this time was 38 mJ / cm ² . After the resist composition having the above composition was stored at 23 ° C. for 3 months, a pattern was formed in the same manner as described above. As a result, an exposure amount of 38 mJ / cm ² was 0.25 μm.
A contact hole having a good shape was formed, and storage stability was confirmed.

Examples 2 to 29 Resist compositions having the compositions shown in Tables 1 to 12 were prepared.

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

A pattern was formed in the same manner as in Example 1 by using the resist compositions having the compositions shown in Tables 1 to 12. The results are shown in Tables 13 and 14.

[0155]

[0156]

Comparative Example 1 A resist composition having the following composition was prepared by removing the compound according to the present invention from the resist composition of Example 1, and a pattern was formed in the same manner as in Example 1. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (Mw 20000, dispersity 1.90) 4.5 g Bis (cyclohexylsulfonyl) diazomethane 0.3 g Bis (p-toluenesulfonyl) diazomethane 0.15 g Fluorine-containing nonionic interface Activator (commercially available) 0.05 g Tri-n-propylamine 0.05 g Propylene glycol monomethyl ether acetate 23 g

As a result, a 0.25 μm contact hole was resolved at an exposure dose of 38 mJ / cm ² , but as shown in FIG. 2, a defective pattern shape with a foot at the bottom of the resist film was obtained.

Comparative Example 2 A resist composition having the following composition including the existing technology was prepared, and a pattern was formed in the same manner as in Example 1. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (Mw 20000, dispersity 1.90) 4.5 g Bis (cyclohexylsulfonyl) diazomethane 0.3 g Bis (p-toluenesulfonyl) diazomethane 0.15 g Fluorine-containing nonionic interface Activator (commercially available) 0.05 g Tri-n-propylamine 0.05 g Propylene glycol monomethyl ether acetate 23 g Salicylic acid 0.02 g

As a result, a contact hole having a good shape of 0.25 μm was resolved at an exposure dose of 38 mJ / cm ² , but after storing the resist composition at 23 ° C. for 2 weeks, a pattern was formed in the same manner as in Example 1. As a result, the unexposed portions were also dissolved at the time of development, so that a desired pattern could not be obtained as shown in FIG. 3 and storage stability was poor.

Comparative Example 3 Tri-n-propylamine was used in the composition described in Comparative Example 2.
A resist composition was prepared by increasing the amount to 0.1 g, and a pattern was formed in the same manner as in Example 1. As a result, on the day and
After storage at 23 ° C for one month, all formed contact holes with good shape of 0.25μm, but the exposure amount was 110mJ / cm
² and low sensitivity.

Comparative Example 4 A resist composition was prepared in the same manner as in Example 1 except that phthalic acid was used in place of salicylic acid in the composition described in Comparative Example 3, and a pattern was formed in the same manner as in Example 1. As a result, as in Comparative Example 3, a contact hole of 0.25 μm was formed even after storage at 23 ° C. for one month, but the exposure was as low as 110 mJ / cm ² .

Example 30 A resist composition having the following composition was prepared. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (Mw 20000, dispersity 1.90) 4.5 g Bis (cyclohexylsulfonyl) diazomethane 0.3 g Bis (p-toluenesulfonyl) diazomethane 0.15 g Fluorine-containing nonionic interface Activator (commercially available) 0.05 g tri-n-propylamine 0.05 g propylene glycol monomethyl ether acetate 23 g phthalimide 0.02 g

After the above compositions were mixed and dissolved, a pattern was formed as described below using a resist composition obtained by passing through a 0.2 μm filter. A resist composition having the above composition was spin-coated on a titanium nitride substrate (TiN substrate) and baked on a hot plate at 90 ° C. for 90 seconds to obtain a 1 μm-thick resist film. Then 248.4nm
KrF excimer laser light (NA 0.55) was selectively exposed through a mask, post-baked on a hot plate at 105 ° C. for 90 seconds, and further subjected to an alkaline developing solution (2.38% aqueous solution of tetramethylammonium hydroxide). ) With paddle method
By developing for 60 seconds, only the exposed portions of the resist film were dissolved and removed to obtain a positive pattern. The obtained positive pattern resolved lines and spaces having a good shape of 0.20 μm as shown in FIG. The exposure amount at this time was 30 mJ / cm ² . Moreover, after storage for 3 months at 23 ° C. The resist composition having the above composition, the the results to the pattern formed in the same manner, an exposure amount of 30 mJ / cm ² 0.20
A line and space having a good shape of μm was formed, and storage stability was confirmed.

Examples 31 to 43 Resist compositions having the compositions shown in Tables 15 to 20 were prepared.

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

Using the resist compositions having the compositions shown in Tables 15 to 20, a pattern was formed in the same manner as in Example 30. Table 21 shows the results.

[0173]

Comparative Example 5 A resist composition having the following composition was prepared by removing the compound according to the present invention from the resist composition of Example 30.
Pattern formation was carried out in the same manner as in 30. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (Mw 20000, dispersity 1.90) 4.5 g Bis (cyclohexylsulfonyl) diazomethane 0.3 g Bis (p-toluenesulfonyl) diazomethane 0.15 g Fluorine-containing nonionic interface Activator (commercially available) 0.05 g Tri-n-propylamine 0.05 g Propylene glycol monomethyl ether acetate 23 g

As a result, a 0.20 μm line-and-space was resolved at an exposure dose of 30 mJ / cm ² , but as shown in FIG. 5, the pattern had a poor pattern with a skirt at the bottom of the resist film.

Comparative Example 6 A resist composition having the following composition including the existing technique was prepared, and a pattern was formed in the same manner as in Example 30. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] (Mw 20000, dispersity 1.90) 4.5 g Bis (cyclohexylsulfonyl) diazomethane 0.3 g Bis (p-toluenesulfonyl) diazomethane 0.15 g Fluorine-containing nonionic interface Activator (commercially available) 0.05 g Tri-n-propylamine 0.05 g Propylene glycol monomethyl ether acetate 23 g Salicylic acid 0.02 g

As a result, at an exposure amount of 32 mJ / cm ² , 0.20 μm
Of the good shape line and spade,
After the resist composition was stored at 23 ° C. for 2 weeks, when a pattern was formed in the same manner as in Example 30, the unexposed portion was also dissolved during development, so that a desired pattern was not obtained as shown in FIG. It was bad.

Comparative Example 7 Tri n-propylamine 0.1 in the composition described in Comparative Example 6
g, a resist composition was prepared, and a pattern was formed in the same manner as in Example 30. As a result, the day and 23 ℃
After storage for one month, a good line and space of 0.20 μm was formed in each case, but the exposure amount was 72 mJ /
cm ² and low sensitivity.

Comparative Example 8 A resist composition was prepared in the same manner as in Example 30, except that phthalic acid was used instead of salicylic acid in the composition described in Comparative Example 6, and a pattern was formed in the same manner as in Example 30. As a result, a line and space having a good shape of 0.20 μm was formed even after storage at 23 ° C. for one month as in Comparative Example 7, but the exposure amount was 72
The sensitivity was as low as mJ / cm ² .

[0180]

As is apparent from the above description, the resist composition of the present invention is used as a resist material for exposure to deep ultraviolet light (300 nm or less) or KrF excimer laser light (248.4 nm) or the like. When used for special substrates such as
A good quarter-micron pattern shape can be obtained without generating footing while maintaining high resolution performance and high sensitivity. Therefore, the present invention is of great value for forming ultrafine patterns in the semiconductor industry and the like. The compound according to the present invention is particularly effective for forming a pattern using far ultraviolet light or KrF excimer laser light as a substrate dependence improving agent.
It can be used satisfactorily in pattern formation using excimer laser light or the like.

[0181]

[Brief description of the drawings]

FIG. 1 is a cross-sectional shape of a contact hole having a good shape obtained by using a resist composition containing a compound according to the present invention.

FIG. 2 is a sectional view of a defective contact hole obtained using a resist composition containing no compound according to the present invention.

FIG. 3 shows a resist composition according to the existing technology at 23 ° C. and 2 ° C.
It is a cross-sectional shape of a contact hole having a poor shape obtained by using after storage for a week.

FIG. 4 is a line and space cross-sectional shape of a good shape obtained by using a resist composition containing the compound according to the present invention.

FIG. 5 is a line-and-space sectional shape of a defective shape obtained by using a resist composition containing no compound according to the present invention.

FIG. 6 shows a resist composition according to the existing technology at 23 ° C. and 2 ° C.
It is a line-and-space sectional shape of a defective shape obtained by using after storage for a week.

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[Procedure amendment]

[Submission date] June 17, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0149

[Correction method] Change

[Correction contents]

[0149]

Claims (14)

[Claims] (1) at least one bond of -NH- is -C
(= O) -, - C (= S) - and -SO ₂ - substrate dependency improving agent resist comprising at least one compound having in the molecule at least one direct bond structure selected from. 2. The substrate-dependent improving agent according to claim 1, wherein said compound is a cyclic compound. 3. The compound according to claim 1, wherein said compound is an acyclic compound.
The substrate dependency improving agent according to 1. 4. The substrate-dependent improving agent according to claim 2, wherein the cyclic compound is a compound represented by the following general formula [1], general formula [2] or general formula [3]. Embedded image [In the formula, X represents an oxygen atom or a sulfur atom, and A represents a saturated or unsaturated 5- or 6-membered ring which may contain an oxygen atom, a nitrogen atom or a sulfur atom as a constituent atom (provided that the ring forms And the carbon atom may have a substituent.). ] [In the formula, X represents an oxygen atom or a sulfur atom, and D represents a saturated or unsaturated 5- or 6-membered ring which may contain an oxygen atom, a nitrogen atom or a sulfur atom as a constituent atom (provided that the ring comprises A carbon atom may have a substituent, and a sulfur atom may have an oxo group.), And E represents a saturated or unsaturated 6-membered ring or fused ring having carbon as a constituent atom. And a fused ring is formed between D and E. ] (Wherein, G represents a saturated or unsaturated 6- to 8-membered ring which may contain an oxygen atom as a constituent atom, J and L each represent a benzene ring, and each represents a condensed ring with the G ring. Is formed.). 5. The substrate-dependent improving agent according to claim 2, wherein the cyclic compound is an acid imide compound derived from an aliphatic dibasic acid. 6. The substrate-dependent improving agent according to claim 2, wherein the cyclic compound is an acid imide compound derived from an aromatic dibasic acid. 7. The substrate-dependent improving agent according to claim 3, wherein the non-cyclic compound is a sulfonamide derivative. 8. The non-cyclic compound is represented by the following general formula [21]: (Wherein, X ₁ and X ₂ each independently represent an alkyl group or a phenyl group which may have a substituent, and n represents 1 to 3)
Wherein n Xs independently represent an oxygen atom or a sulfur atom. 4. The substrate-dependent improving agent according to claim 3, which is a compound represented by the formula: 9. A polymer which becomes alkali-soluble by the action of an acid, a compound which generates an acid by irradiation with radiation,
At least one bond of NH- is -C (= O)-, -C
(= S) - and -SO ₂ - at least one compound having at least one directly bonded to the structure in the molecule selected from a resist composition comprising them and a solvent capable of dissolving the. 10. An alkali-soluble polymer, a compound which becomes alkali-soluble by the action of an acid, a compound which generates an acid by irradiation with radiation, and at least one of --NH-- has --C ((O)-, -C (= S) - and -SO ₂ - at least one compound having at least one directly bonded to the structure in the molecule selected from a resist composition comprising them and a solvent capable of dissolving the. 11. An alkali-soluble polymer, a compound which crosslinks the polymer by the action of an acid to make the polymer hardly alkali, a compound which generates an acid by irradiation with radiation, and at least one bond of --NH-- C (= O)
-, - C (= S) - and -SO ₂ - and a compound having at least one at least one directly bonded to the structure in the molecule selected from a resist composition comprising a such a soluble solvent, the Stuff. 12. At least one bond of —NH— is —
C (= O) -, - C (= S) - and -SO ₂ - compound having at least one at least one directly bonded to the structure in the molecule selected from is a cyclic compound according to claim 9-11
The resist composition according to any one of the above. 13. The method according to claim 13, wherein at least one bond of -NH- is-
C (= O) -, - C (= S) - and -SO ₂ - compound having at least one at least one directly bonded to the structural molecule selected from the acyclic compound, according to claim 9
12. The resist composition according to any of 11. 14. A step of applying the resist composition according to claim 9 on a semiconductor substrate, a step of forming a resist film by heating, and a step of irradiating radiation through a mask. And, if necessary, heating and then developing with an alkali developing solution.