JP2003177537A - Positive resist composition for electron beam, x-ray or euv - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition which improves the profile of a resist pattern and suppresses a variation of line width due to laying in a vacuum chamber. <P>SOLUTION: The positive resist composition for an electron beam, X-rays or EUV (extreme-ultraviolet radiation) comprises (a) a resin which has a structural unit containing an acid-decomposable group of formula (X) and is decomposed by the action of an acid to increase solubility in an alkali developer and (b) a compound which generates an acid upon irradiation with an actinic radiation. In formula (X), R<SB>1</SB>and R<SB>2</SB>may be the same or different and are each H or a 1-4C alkyl; W is a divalent organic group; and R<SB>3</SB>is an alkyl which may have substituents and has 11-20 carbon atoms in total, an aryl which may have substituents and has 11-30 carbon atoms in total or an aralkyl which may have substituents and has 12-30 carbon atoms in total. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor integrated circuit element.
Positive type register used for manufacturing of masks for ICs and integrated circuits
It relates to a strike composition. [0002] 2. Description of the Related Art As a positive photoresist composition, rice
National Patent No. 4,491,628 No. 28, European Patent No. 29,139 No.
There is a chemically amplified resist composition described in the
The Chemically amplified positive resist compositions are used to release deep ultraviolet light, etc.
Irradiation generates acid in the exposed area, and this acid is used as a catalyst.
The reaction between the irradiated part of the active radiation and the non-irradiated part
Change the solubility in the developer to form a pattern on the substrate
It is a pattern forming material to be formed. The above chemically amplified positive resist composition has the following advantages.
Lucari-soluble resin that generates acid when exposed to radiation
Compound (photoacid generator) and alkali having acid-decomposable group
A three-component system consisting of a dissolution inhibiting compound for soluble resins
And a group that decomposes by reaction with an acid and becomes alkali-soluble.
Two-component system consisting of resin and photoacid generator
Resin having acid-decomposable and alkali-soluble group, acid
Low molecular weight dissolution inhibiting compounds having degradable groups and photoacid generation
Broadly divided into hybrid systems consisting of agents. In Japanese Patent Laid-Open No. 9-319092,
Resins with an acetal group with an oxy linkage introduced
It is disclosed that there is an effect on the presence wave reduction effect and the like. Also, in JP-A-10-221854
Discloses resins with substituted acetal group units
ing. However, it has these acetal groups.
When used as an electron beam resist,
The resist pattern obtained by the effect of line backscattering
Became a reverse taper profile. More electronic
Depending on the holding time in the vacuum chamber of the beam irradiation device
Improvement of line width variation was also desired. [0007] The object of the present invention is to provide an electronic
Such as X-ray, X-ray, or EUV (Extreme Ultraviolet)
Pattern obtained as a resist for irradiation with actinic radiation
The shape of the profile is excellent and the vacuum
The line width variation due to the holding time in the chamber is also improved.
To provide a chemically amplified positive resist composition.
The [0008] SUMMARY OF THE INVENTION The present inventor has found such a present situation.
In view of
A positive resist composition having a compound having
Thus, the above object is achieved and the present invention is completed.
It was. That is, the positive resist composition according to the present invention.
Has the following configuration. (1) (a) containing a group represented by the following general formula (X)
It has structural units and decomposes by the action of acid to develop alkali.
A resin with increased solubility in liquid, and (b) active radiation
It contains a compound that generates acid upon irradiation with rays.
Resist composition for positive electron beam, X-ray or EUV
Stuff. [0010] [Chemical 2] In the formula (X), R₁ , R₂Are the same or different
May be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
W represents a divalent organic group, R_ThreeIs the total carbon number 11
Alkyl group which may have a substituent of -20, total carbon number 1
Aryl group optionally having 1 to 30 substituents, total carbon number
Table 12 represents an aralkyl group which may have 12 to 30 substituents.
The The preferred embodiments are described below. (2) (a) Shown by the following general formula (I) and general formula (III)
Having a structural unit that is decomposed by the action of an acid,
Resin with increased solubility in potash developer, and / or
Are represented by the following general formula (I), general formula (II) and general formula (II
Decomposed by the action of an acid having the structural unit represented by I)
A resin having increased solubility in an alkaline developer, and
And (b) a compound that generates an acid upon irradiation with actinic radiation.
Containing positive electron beam, X-ray or EU
Resist composition for V. [0013] [Chemical 3]In the formulas (I) to (III), R21 is a hydrogen atom.
Or represents a methyl group, and R22 is not decomposed by the action of an acid.
R23 represents a hydrogen atom, a halogen atom or an alkyl group.
Group, aryl group, alkoxy group, acyl group or acylo
Represents a xy group. n represents an integer of 1 to 3. W is the above general
The group represented by formula (X) is represented. (3) In the above general formula (X),
R₁, R₂At least one of which is a straight chain having 1 to 4 carbon atoms or
(1) or (1) above, which is a branched alkyl group
Is a register for positive electron beam, X-ray or EUV as described in (2)
Strike composition. (4) (b) By irradiation with actinic radiation
Compounds that generate phosphoric acid are exposed to actinic radiation.
The following general formulas (A-1) and (A-
2), (A-3), (A-4), (A-5), (A-
6) At least of the compounds represented by (A-7)
Any of the above (1) to (3), characterized in that it is one type
Resist for positive electron beam, X-ray or EUV
Composition. [0017] [Formula 4] In the formulas (A-1) and (A-2), R₁~ R
_FiveMay be the same or different, and a hydrogen atom, an alkyl,
Group, cycloalkyl group, alkoxy group, hydroxy
Group, halogen atom, or -SR₆Indicates a group. R₆Is al
A kill group or an aryl group is shown. X^-(A) linear, branched or cyclic
An anion of an alkyl sulfonic acid having 1 to 12 carbon atoms,
Some or all of the hydrogen atoms are replaced with fluorine atoms
Or (b) branched or cyclic carbon number of 8 or less
Selected from the group of the above alkyl and alkoxy groups
Have at least one group, linear, branched or cyclic
Of the group of alkyl groups having 4 to 7 carbon atoms and alkoxy groups
Having at least two groups selected from among, linear or
Is a branched alkyl group having 1 to 3 carbon atoms and alkoxy
Having at least three groups selected from the group of groups,
Having 1 to 5 halogen atoms, or linear or
Is a benzene having a branched ester group having 1 to 10 carbon atoms
Sulfonic acid, naphthalenesulfonic acid or anthracene
An anion of sulfonic acid is shown. [0020] [Chemical formula 5] In the formula (A-3), R₇~ R_TenAre the same
Each of which may be different, hydrogen atom, alkyl group,
A loalkyl group, an alkoxy group, a hydroxy group, or a halo
Gen atom is shown. X^-Is as defined above. m, n,
p and q each represent an integer of 1 to 3. [0022] [Chemical 6] In the formula (A-4), R₁₁~ R₁₃Are the same
May be different, hydrogen atom, alkyl group, cycloa
Alkyl group, alkoxy group, hydroxy group, halogen atom
Or -S-R₆Indicates a group. R₆, X^-Is synonymous with the above
The l, m and n may be the same or different;
Indicates an integer. If l, m and n are each 2 or 3, then 2
~ 3 R₁₁~ R₁₃Two of each of which
5-8 elements including carbocyclic, heterocyclic or aromatic rings
A ring consisting of [0024] [Chemical 7] In the formula (A-5), R₁₄~ R₁₆Are the same
May be different, hydrogen atom, alkyl group, cycloa
Alkyl group, alkoxy group, hydroxy group, halogen atom
Or -S-R₆Indicates a group. R₆, X^-Is as defined above
The l, m and n may be the same or different;
Indicates an integer. If l, m and n are each 2 or 3, then 2
~ 3 R₁₄~ R₁₆Two of each of which
5-8 elements including carbocyclic, heterocyclic or aromatic rings
A ring consisting of [0026] [Chemical 8] In the formula (A-6), Y has a substituent.
Linear, branched, cyclic alkyl groups, which may be substituted
Good aralkyl group, [0028] [Chemical 9] A group represented by (R)₃₁~ R₅₁Is the same
However, they may be different and have a hydrogen atom or a substituent.
Linear, branched, cyclic alkyl groups, alkoxy groups,
Acyl group, acylamino group, sulfonylamino group, ant
Group, acyloxy group, aralkyl group or alkoxy group
Sicarbonyl group, formyl group, nitro group, chlorine source
Child, bromine atom, iodine atom, hydroxyl group, or cyano group
R₃₁~ R₃₅, R₃₆~ R₄₂And R₄₃~ R₅₁Is it
Two of each group are bonded to carbon atoms and / or
A 5- to 8-membered ring composed of a terror atom may be formed). Ma
Y binds to the residue of another imide sulfonate compound.
It may be. X is a linear or branched chain optionally having a substituent.
Alkylene group, optionally substituted hetero atom
A monocyclic or polycyclic alkylene group which may contain, substituted
Linear, branched alkenylene groups, which may be substituted,
May be monocyclic or polycyclic and may contain heteroatoms
A cyclic alkenylene group, an optionally substituted aryle
And an optionally substituted aralkylene group. Ma
Even if X is bonded to another imide sulfonate residue
Good. [0031] Ar₁-SO₂-SO₂-Ar₂        (A-7) In formula (A-7), Ar₁, Ar₂Are the same or different
Or a substituted or unsubstituted aryl group. (5) (b) By irradiation with actinic radiation
Compounds that generate phosphoric acid are exposed to actinic radiation.
The following general formulas (PAG3) and (PA
It is at least one of the compounds represented by G4)
Any one of the above (1) to (3)
Resist composition for positive electron beam, X-ray or EUV. [0033] Embedded image Where Ar¹, Ar²Are each independently substituted
Or an unsubstituted aryl group is shown. R²⁰³, R²⁰⁴, R
²⁰⁵Each independently represents a substituted or unsubstituted alkyl
A group and an aryl group; Z^-Has at least one fluorine atom
A sulfonate anion. Also R²⁰³, R²⁰⁴, R
²⁰⁵Two of them and Ar¹, Ar²Is a single unit for each
Or may be bonded via a substituent. (6) Further, when activated radiation is applied,
A compound capable of generating a sulfonic acid containing no nitrogen atom, and
And a compound that generates carboxylic acid upon irradiation with actinic radiation.
Characterized by containing at least one of the products
Register for positive electron beam, X-ray or EUV described in (5)
Strike composition. (7) Further comprising a cyclic amine compound
The positive electron according to any one of (1) to (6) above
Resist composition for X-ray, X-ray or EUV. (8) Further, fluorine-based surfactant or silicon-based surfactant
Characterized by containing a sex agent or both
The positive electron beam or X-ray according to any one of (1) to (7)
Or a resist composition for EUV. (9) Decomposes by the action of an acid and works against an alkaline developer
Further comprising a compound with increased solubility
The positive electron according to any one of (1) to (8) above
Resist composition for X-ray, X-ray or EUV. (10) Content of acid contained in the resist composition
(1) above, characterized in that is 500 ppm or less
To (9) positive electron beam, X-ray or E
Resist composition for UV. [0037] The present invention will be described in detail below. (A) -1: having a group represented by the general formula (X),
Decomposes by the action of acid, solubility in alkaline developer
Increased resin R in the general formula (X)₁, R₂As the alkyl group of
Methyl group, ethyl group, n-propyl group, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl group,
and an alkyl group having 1 to 4 carbon atoms such as t-butyl group.
It is. The divalent organic group for W is preferred.
Or linear, branched or ring optionally having substituent (s)
Alkylene group, arylene group, heteroarylene
Group, aralkylene group, and -S-, -C (= O)-,
-N (R_Four)-, -SO-, -SO₂-, -CO₂-,-
N (R_Four) SO₂-Or a combination of two or more of these groups
Can be mentioned divalent groups. Where R_FourIs water
Elementary atoms or alkyl groups (specific examples of alkyl groups are
R₁Can be mentioned)
The R_ThreeSubstituents with 11-20 total carbons in
As an alkyl group which may have a total carbon number of 11 to 2,
A chain alkyl group optionally having 0 substituents, total carbon number of 1
And a cyclic alkyl group optionally having 1 to 20 substituents.
It is done. R above_Three11 to 20 carbon atoms, preferably
The chain alkyl group having 11 to 18 carbon atoms is linear
Or may be branched, for example n-undec
Group, i-undecyl group, n-dodecyl group, i-dodecyl group
Group, n-tridecyl group, i-tridecyl group, n-teto
Radecyl group, i-tetradecyl group, n-pentadecyl group
Group, i-pentadecyl group, n-hexadecyl group, i-he
Xadecyl group, n-heptadecyl group, i-heptadecyl group
Group, n-octadecyl group, i-octadecyl group, n-no
And nadecyl group, i-nonadecyl group, etc.
The R above_Three11 to 20 carbon atoms, preferably
As the cyclic alkyl group having 11 to 18 carbon atoms,
Even if a ring is formed with the number of carbon atoms in
Alkyl may be used, for example, cycloundecyl group, cyclo
Dodecyl group, cyclotridecyl group, cyclotridecyl group
Group, cyclotetradecyl group, cyclopentadecyl group,
Clohexadecyl group, cycloheptadecyl group, cycloo
Kutadecyl group, cyclononadecyl group, 4-cyclohexyl
Rucyclohexyl group, 4-n-hexylcyclohexyl
Group, pentanylcyclohexyl group, hexyloxycycle
A hexyl group, a pentanyloxycyclohexyl group, etc.
I can list them. Substituted cyclic alkyls other than those listed here
A kill group can also be used if it exists in the said range. R above_Three11 to 30 carbon atoms, preferably
As the aryl group having 11 to 25 carbon atoms, 4-cyclo
A pentylphenyl group, a 4-cyclohexylphenyl group,
4-cycloheptenylphenyl group, 4-cyclooctani
Ruphenyl group, 2-cyclopentylphenyl group, 2-silane
Chlohexylphenyl group, 2-cycloheptenyl phenyl
Group, 2-cyclooctanylphenyl group, 3-cyclope
Nthylphenyl group, 3-cyclohexylphenyl group, 3
-Cycloheptenylphenyl group, 3-cyclooctanyl
Phenyl group, 4-cyclopentyloxyphenyl group, 4
-Cyclohexyloxyphenyl group, 4-cyclohepte
Nyloxyphenyl group, 4-cyclooctanyloxyf
Enyl group, 2-cyclopentyloxyphenyl group, 2-
Cyclohexyloxyphenyl group, 2-cyclohepteni
Ruoxyphenyl group, 2-cyclooctanyloxyphene
Nyl group, 3-cyclopentyloxyphenyl group, 3-
Chlohexyloxyphenyl group, 3-cycloheptenyl
Oxyphenyl group, 3-cyclooctanyloxypheny
Group, 4-n-pentylphenyl group, 4-n-hexyl
Phenyl group, 4-n-heptenylphenyl group, 4-n-
Octanylphenyl group, 2-n-pentylphenyl group,
2-n-hexylphenyl group, 2-n-heptenyl phen
Nyl group, 2-n-octanylphenyl group, 3-n-pen
Tilphenyl group, 3-n-hexylphenyl group, 3-n
-Heptenylphenyl group, 3-n-octanylphenyl
Group, 2,6-di-isopropylphenyl group, 2,3-di
-Isopropylphenyl group, 2,4-di-isopropyl
Phenyl group, 3,4-di-isopropylphenyl group,
3,6-di-t-butylphenyl group, 2,3-di-t-
Butylphenyl group, 2,4-di-t-butylphenyl
Group, 3,4-di-t-butylphenyl group, 2,6-di-
n-butylphenyl group, 2,3-di-n-butylpheny
Group, 2,4-di-n-butylphenyl group, 3,4-di
-N-butylphenyl group, 2,6-di-i-butylphenol
Nyl group, 2,3-di-i-butylphenyl group, 2,4-
Di-i-butylphenyl group, 3,4-di-i-butylphenyl
Enyl group, 2,6-di-t-amylphenyl group, 2,3
-Di-t-amylphenyl group, 2,4-di-t-amyl
Phenyl group, 3,4-di-t-amylphenyl group, 2,
6-di-i-amylphenyl group, 2,3-di-i-ami
Ruphenyl group, 2,4-di-i-amylphenyl group,
3,4-di-i-amylphenyl group, 2,6-di-n-
Pentylphenyl group, 2,3-di-n-pentylpheny
Group, 2,4-di-n-pentylphenyl group, 3,4-
Di-n-pentylphenyl group, 4-adamantylpheny
Group, 2-adamantylphenyl group, 4-isoboronyl
Phenyl group, 3-isoboronylphenyl group, 2-isobo
Ronylphenyl group, 4-cyclopentyloxyphenyl
Group, 4-cyclohexyloxyphenyl group, 4-cyclo
Heptenyloxyphenyl group, 4-cyclooctanyl
Xiphenyl group, 2-cyclopentyloxyphenyl
Group, 2-cyclohexyloxyphenyl group, 2-cyclo
Heptenyloxyphenyl group, 2-cyclooctanoyl
Xiphenyl group, 3-cyclopentyloxyphenyl
Group, 3-cyclohexyloxyphenyl group, 3-cyclo
Heptenyloxyphenyl group, 3-cyclooctanyl
A xylphenyl group, a 4-n-pentyloxyphenyl group,
4-n-hexyloxyphenyl group, 4-n-hepteni
Ruoxyphenyl group, 4-n-octanyloxypheny
Group, 2-n-pentyloxyphenyl group, 2-n-he
Xyloxyphenyl group, 2-n-heptenyloxy
Enyl group, 2-n-octanyloxyphenyl group, 3-
n-pentyloxyphenyl group, 3-n-hexyloxy
Siphenyl group, 3-n-heptenyloxyphenyl group,
3-n-octanyloxyphenyl group, 2,6-di-i
Sopropyloxyphenyl group, 2,3-di-isopropyl
Ruoxyphenyl group, 2,4-diisopropyloxy
Phenyl group, 3,4-di-isopropyloxyphenyl
Group, 2,6-di-t-butyloxyphenyl group, 2,3
-Di-t-butyloxyphenyl group, 2,4-di-t-
Butyloxyphenyl group, 3,4-di-t-butyloxy
Cyphenyl group, 2,6-di-n-butyloxyphenyl
Group, 2,3-di-n-butyloxyphenyl group, 2,4
-Di-n-butyloxyphenyl group, 3,4-di-n-
Butyloxyphenyl group, 2,6-di-i-butyloxy
Cyphenyl group, 2,3-di-i-butyloxyphenyl
Group, 2,4-di-i-butyloxyphenyl group, 3,4
-Di-i-butyloxyphenyl group, 2,6-di-t-
Amyloxyphenyl group, 2,3-di-t-amyloxy
Cyphenyl group, 2,4-di-t-amyloxyphenyl
Group, 3,4-di-t-amyloxyphenyl group, 2,6
-Di-i-amyloxyphenyl group, 2,3-di-i-
Amyloxyphenyl group, 2,4-di-i-amyloxy
Cyphenyl group, 3,4-di-i-amyloxyphenyl
Group, 2,6-di-n-pentyloxyphenyl group, 2,
3-di-n-pentyloxyphenyl group, 2,4-di-
n-pentyloxyphenyl group, 3,4-di-n-pen
Tyloxyphenyl group, 4-adamantyloxypheny
Group, 3-adamantyloxyphenyl group, 2-adama
N-tyloxyphenyl group, 4-isoboronyloxyphene
Nyl group, 3-isoboronyloxyphenyl group, 2-iso
A boronyloxyphenyl group, and the like.
Substitutions other than the above examples may be further substituted within the range.
It is not limited to the group. R_ThreeCarbon number of 12-30, preferably carbon
As the aralkyl group of Formula 12 to 25, 4-cyclope
Nthylphenylethyl group, 4-cyclohexylphenyl
Ethyl group, 4-cycloheptenylphenylethyl group, 4
-Cyclooctanylphenylethyl group, 2-cyclopent
Tylphenylethyl group, 2-cyclohexylphenyl group
Til group, 2-cycloheptenylphenylethyl group, 2-
Cyclooctanylphenylethyl group, 3-cyclopentyl
Ruphenylethyl group, 3-cyclohexylphenylethyl
Group, 3-cycloheptenylphenylethyl group, 3-
Crooctanylphenylethyl group, 4-cyclopentyl
Oxyphenylethyl group, 4-cyclohexyloxy
Enylethyl group, 4-cycloheptenyloxyphenyl
Ethyl group, 4-cyclooctanyloxyphenyl ethyl
Group, 2-cyclopentyloxyphenylethyl group, 2-
Cyclohexyloxyphenylethyl group, 2-cyclohexyl
Ptenyloxyphenylethyl group, 2-cyclooctani
Ruoxyphenylethyl group, 3-cyclopentyloxy
Phenylethyl group, 3-cyclohexyloxyphenyl
Ethyl group, 3-cycloheptenyloxyphenyl ethyl
Group, 3-cyclooctanyloxyphenylethyl group, 4
-N-pentylphenylethyl group, 4-n-hexylsulfate
Enylethyl group, 4-n-heptenylphenylethyl
Group, 4-n-octanylphenylethyl group, 2-n-pe
N-phenylphenyl group, 2-n-hexylphenyl ester
Til group, 2-n-heptenylphenylethyl group, 2-n
-Octanylphenylethyl group, 3-n-pentylphene
Nylethyl group, 3-n-hexylphenylethyl group, 3
-N-heptenylphenylethyl group, 3-n-octani
Ruphenylethyl group, 2,6-di-isopropylpheny
Ruethyl group, 2,3-di-isopropylphenylethyl
Group, 2,4-di-isopropylphenylethyl group, 3,
4-di-isopropylphenylethyl group, 2,6-di-
t-butylphenylethyl group, 2,3-di-t-butyl
Phenylethyl group, 2,4-di-t-butylphenyl ester
A til group, a 3,4-di-t-butylphenylethyl group,
2,6-di-n-butylphenylethyl group, 2,3-di
-N-butylphenylethyl group, 2,4-di-n-butyl
Ruphenylethyl group, 3,4-di-n-butylphenyl
An ethyl group, a 2,6-di-i-butylphenylethyl group,
2,3-di-i-butylphenylethyl group, 2,4-di
-I-butylphenylethyl group, 3,4-di-i-butyl
Ruphenylethyl group, 2,6-di-t-amylphenyl
An ethyl group, a 2,3-di-t-amylphenylethyl group,
2,4-di-t-amylphenylethyl group, 3,4-di
-T-amylphenylethyl group, 2,6-di-i-ami
Ruphenylethyl group, 2,3-di-i-amylphenyl
An ethyl group, a 2,4-di-i-amylphenylethyl group,
3,4-di-i-amylphenylethyl group, 2,6-di
-N-pentylphenylethyl group, 2,3-di-n-pe
N-phenylphenyl group, 2,4-di-n-pentylph
Enylethyl group, 3,4-di-n-pentylphenyl ether
Til, 4-adamantylphenylethyl, 3-ada
Mantylphenylethyl group, 2-adamantylphenyl
Ethyl group, 4-isoboronylphenylethyl group, 3-i
Soboronylphenylethyl group, 2-isoboronylphenyl
Ruethyl group, 4-cyclopentyloxyphenylethyl
Group, 4-cyclohexyloxyphenylethyl group, 4-
Cycloheptenyloxyphenylethyl group, 4-cyclo
Octanyloxyphenylethyl group, 2-cyclopent
Ruoxyphenylethyl group, 2-cyclohexyloxy
Phenylethyl group, 2-cycloheptenyloxypheny
Ruethyl group, 2-cyclooctanyloxyphenyl ethyl
Group, 3-cyclopentyloxyphenylethyl group, 3
-Cyclohexyloxyphenylethyl group, 3-cyclo
Heptenyloxyphenylethyl group, 3-cycloocta
Nyloxyphenylethyl group, 4-n-pentyloxy
Phenylethyl group, 4-n-hexyloxyphenyl ester
A til group, a 4-n-heptenyloxyphenylethyl group,
4-n-octanyloxyphenylethyl group, 2-n-
Pentyloxyphenylethyl group, 2-n-hexylo
Xiphenylethyl group, 2-n-heptenyloxyphene
Nylethyl group, 2-n-octanyloxyphenyl ethyl
Group, 3-n-pentyloxyphenylethyl group, 3-
n-hexyloxyphenylethyl group, 3-n-hepte
Nyloxyphenylethyl group, 3-n-octanyloxy
Cyphenylethyl group, 2,6-diisopropyloxy
Phenylethyl group, 2,3-di-isopropyloxy
Enylethyl group, 2,4-di-isopropyloxyphene
Nylethyl group, 3,4-diisopropyloxypheny
Ruethyl group, 2,6-di-t-butyloxyphenyl ester
Til group, 2,3-di-t-butyloxyphenylethyl
Group, 2,4-di-t-butyloxyphenylethyl group,
3,4-di-t-butyloxyphenylethyl group, 2,
6-di-n-butyloxyphenylethyl group, 2,3-
Di-n-butyloxyphenylethyl group, 2,4-di-
n-butyloxyphenylethyl group, 3,4-di-n-
Butyloxyphenylethyl group, 2,6-di-i-butyl
Ruoxyphenylethyl group, 2,3-di-i-butylo
Xiphenylethyl group, 2,4-di-i-butyloxy
Phenylethyl group, 3,4-di-i-butyloxyphene
Nylethyl group, 2,6-di-t-amyloxyphenyl
Ethyl group, 2,3-di-t-amyloxyphenyl ethyl
Group, 2,4-di-t-amyloxyphenylethyl
Group, 3,4-di-t-amyloxyphenylethyl group,
2,6-di-i-amyloxyphenylethyl group, 2,
3-di-i-amyloxyphenylethyl group, 2,4-
Di-i-amyloxyphenylethyl group, 3,4-di-
i-Amyloxyphenylethyl group, 2,6-di-n-
Pentyloxyphenylethyl group, 2,3-di-n-pe
Nthyloxyphenylethyl group, 2,4-di-n-pen
Tyloxyphenylethyl group, 3,4-di-n-pent
Ruoxyphenylethyl group, 4-adamantyloxyph
Enylethyl group, 3-adamantyloxyphenyl ethyl
Group, 2-adamantyloxyphenylethyl group, 4-
Isoboronyloxyphenylethyl group, 3-isoboroni
Ruoxyphenylethyl group, 2-isoboronyloxy
An phenylethyl group, or the above alkyl is a methyl group,
For example, propyl group, butyl group, etc.
It is. As a further substituent of the above group, water
Acid groups, halogen atoms (fluorine, chlorine, bromine, iodine),
Nitro group, cyano group, the above alkyl group, methoxy group,
Ethoxy group, hydroxyethoxy group, propoxy group, H
Droxypropoxy group, n-butoxy group, isobutoxy group
Alkoxy such as group, sec-butoxy group, t-butoxy group
Si group, methoxycarbonyl group, ethoxycarbonyl group, etc.
Alkoxycarbonyl group, benzyl group and phenethyl group
・ Aralkyl groups such as cumyl groups, aralkyloxy groups,
Rumyl group, Acetyl group, Butyryl group, Benzoyl group, Si
Acyl groups such as anamil group and valeryl group, butyryloxy
Acyloxy groups such as groups, the above alkenyl groups, vinyloxy
Si group, propenyloxy group, allyloxy group, butenyl
An alkenyloxy group such as an oxy group, the above aryl group,
Aryloxy group such as phenoxy group, benzoyloxy
And aryloxycarbonyl groups such as
The R_ThreeAs a substituent of
11-25 aryl group or C12-25 aryl
Kill group. These substituents have further substituents
The number of carbon atoms of the substituted aryl group or the substituted aralkyl group is
It may be within this range. In the general formula (X), R₁,
R₂At least one of which is a straight or branched chain having 2 to 4 carbon atoms
The alkyl group is preferably. Specific examples of the group represented by the general formula (X) are as follows:
However, it is not limited to these. [0048] Embedded image [0049] Embedded image[0050] Embedded image[0051] Embedded imageGroup represented by the general formula (X) in the present invention
It decomposes by the action of acid and is
Resin with increased solubility (hereinafter represented by general formula (X)
Is also obtained by polymerizing monomers.
The compound having a molecular weight distribution is represented by the general formula (X)
It has a structure in which the acid-decomposable group shown is introduced.
It is a compound that becomes more alkali-soluble. A resin having a group represented by the general formula (X);
The main chain or side chain of the resin, or the main chain and side chain
Both are resins having a group represented by the general formula (X).
The Among these, it has a group represented by the general formula (X) in the side chain
A resin is more preferable. Next, the group represented by the general formula (X) is a side chain.
As a base resin in the case of bonding,
Or —COOH, preferably —R⁰-COOH
Is an alkali-soluble resin having an -Ar-OH group.
For example, an alkali containing no acid-decomposable group described later
A soluble resin can be mentioned. Where -R⁰− Is
Divalent or higher aliphatic or aromatic which may have a substituent
Represents a hydrocarbon, -Ar- is a monocyclic or polycyclic substituent
Represents a divalent or higher-valent aromatic group which may have As a preferred base resin in the present invention,
Is an alkali-soluble resin having a phenolic hydroxyl group
is there. The phenolic hydroxyl group used in the present invention is
The alkali-soluble resin having o-, m- or p-hydride
Loxystyrene (collectively these are hydroxystyrene)
Or o-, m- or p-hydroxy-α
-Methylstyrene (collectively these are hydroxy-α-
The number of repeating units corresponding to
At least 30 mol%, preferably 50 mol% or more
A copolymer or a homopolymer thereof, or
It is preferred that the core is a partially hydrogenated resin.
P-hydroxystyrene homopolymer is more preferred
That's right. To prepare the above copolymer by copolymerization
Hydroxystyrene and hydroxy-α-methylstyrene
As monomers other than Len, acrylic acid esters,
Methacrylic acid esters, acrylamides, methacrylates
Luamides, acrylonitrile, methacrylonitrile,
Maleic anhydride, styrene, α-methylstyrene, acetate
Toxistyrene and alkoxystyrene are preferred,
Tylene, acetoxystyrene, t-butoxystyrene
More preferred. In the present invention, one of the resins in such a resin is used.
A repeating unit having a group represented by the general formula (X) (structural unit
Content) is 3 mol with respect to all repeating units.
% To 50 mol% is preferred, more preferably 5 mol% to
30 mol%. In the present invention, a group represented by the general formula (X)
In the resin having a group represented by the general formula (X)
In addition, other acid-decomposable groups may be included. Contains a group represented by the above general formula (X)
Resin is synthesized by synthesizing the corresponding vinyl ether and tetrahydride.
Phenolic hydroxyl group dissolved in a suitable solvent such as lofuran
React with alkali-containing resin in a known manner
Can be obtained. The reaction is usually an acidic catalyst, preferably
Preferably, acidic ion exchange resin, hydrochloric acid, p-toluene
Like sulfonic acid or pyridinium tosylate
It is carried out in the presence of a salt. Corresponding vinyl ether
Is it an active ingredient like chloroethyl vinyl ether?
Can be synthesized by a method such as a nucleophilic substitution reaction,
It can also be synthesized using mercury or palladium catalysts.
The As another method, the corresponding alcohol is used.
For acetal exchange using ruthenium and vinyl ether
Therefore, it can be synthesized. In this case, I want to introduce
Substituents are attached to alcohol, and vinyl ether is t-butyl.
Relatively unstable vinyl agents such as til vinyl ether
Mixed with p-toluenesulfonic acid and pyridinium
It is carried out in the presence of an acid such as mutosylate. Contains a group represented by the above general formula (X)
The weight average molecular weight of the resin is preferably 2000-200000
300 to 100,000 is more preferable, 500
0 to 50000 is more preferable. The range of molecular weight distribution (Mw / Mn) is 1.
01-4.0, preferably 1.05-3.00
is there. To obtain a polymer having such a molecular weight distribution
Use anionic polymerization, radical polymerization, etc.
preferable. Such a group represented by the general formula (X) is included.
The specific structure of the resin having is exemplified below, the present invention is
It is not limited to these. [0066] Embedded image [0067] Embedded image[0068] Embedded image [0069] Embedded image[0070] Embedded image [0071] Embedded image [0072] Embedded image [0073] Embedded image [0074] Embedded image Resin used in the present invention (shown by general formula (X))
A resin containing a group represented by formula (I) and formula (II)
Decomposed by the action of an acid having the structural unit represented by I)
A resin having increased solubility in an alkaline developer, and
And / or the above general formula (I), general formula (II) and general formula
By the action of an acid having the structural unit represented by (III)
Trees that decompose and increase solubility in alkaline developers
Fat) for adjusting alkali dissolution rate and improving heat resistance
In the synthesis stage, polyhydroxy compounds are added to
A cross-linking site that connects the main chain of the limer with a polyfunctional acetal group
It may be introduced. The amount of polyhydroxy compound added is resin water.
0.01 to 10 mol%, preferably based on the number of acid groups
Is 0.05-8 mol%, more preferably 0.1-5 m
ol%. As polyhydroxy compounds, phenol
Having 2 to 6 rutile hydroxyl groups or alcoholic hydroxyl groups
Preferably, the number of hydroxyl groups is 2-4
More preferably, the number of hydroxyl groups is 2 or 3. Less than
Specific examples are shown below, but the present invention is not limited thereto.
is not. [0078] Embedded image (A) -2: General formula (I) and general formula
By the action of an acid having the structural unit represented by (III)
Resin that decomposes and increases solubility in alkaline developer
(Hereinafter also referred to as the resin (A) -1) and / or above
General formula (I), general formula (II) and general formula (III)
Having a structural unit that is decomposed by the action of an acid,
Resin with increased solubility in potash developer (hereinafter,
(Also referred to as (A) -2 resin) R21 represents a hydrogen atom or a
Represents a til group. Does not decompose by the action of acid in R22
Examples of groups (also referred to as acid stable groups) include hydrogen atoms, halogens
Atoms, alkyl groups, cycloalkyl groups, alkenyl groups,
Aryl group, alkyloxy group (provided that -O-tertiary
Except alkyl), acyl group, cycloalkyloxy group,
Alkenyloxy group, aryloxy group, alkylcal
Bonyloxy group, alkylamidomethyloxy group, al
Killamide group, arylamidomethyl group, arylamido
And the like. The acid stabilizing group is preferably
Sil group, alkylcarbonyloxy group, alkyloxy
Group, cycloalkyloxy group, aryloxy group, al
Kiramidooxy group and alkylamido group, more preferred
Preferably, acyl group, alkylcarbonyloxy group, al
Killoxy group, cycloalkyloxy group, aryloxy group
Si group. In the acid stable group of R22, an alkyl group and
A methyl group, an ethyl group, a propyl group, n-butyl
Group, such as sec-butyl group, t-butyl group, 1 to
4 are preferred, and the cycloalkyl group is
Ropropyl, cyclobutyl, cyclohexyl,
Those with 3 to 10 carbon atoms such as a damantyl group are preferred.
Alkenyl groups include vinyl, propenyl, and
Those having 2 to 4 carbon atoms such as a ryl group and a butenyl group are preferred.
As the alkenyl group, a vinyl group, a propenyl group,
Those having 2 to 4 carbon atoms such as allyl group and butenyl group are preferred.
Preferably, aryl groups include phenyl, xylyl,
Toluyl, cumenyl, naphthyl, anthracenyl
A group having 6 to 14 carbon atoms such as a group is preferred. Alkoki
Si groups include methoxy, ethoxy and hydroxy groups.
Toxi group, propoxy group, hydroxypropoxy group, n
-Butoxy group, isobutoxy group, sec-butoxy group, etc.
The C1-C4 alkoxy group of these is preferable. As a halogen atom in R23
Is preferably fluorine, chlorine, bromine or iodine, and an alkyl group
As methyl, ethyl, propyl, n-butyl, s
ec-butyl, t-butyl, hexyl, octyl, etc.
Such an aryl group having 1 to 8 carbon atoms is preferable.
Phenyl, xylyl, toluyl, cumenyl, naphth
Having 6 to 14 carbon atoms such as chill, anthracenyl, etc.
Is preferred. Examples of alkoxy groups include methoxy and ethoxy.
Si, hydroxyethoxy, propoxy, hydroxypro
Poxy, n-butoxy, isobutoxy, sec-butoxy
Preferred are those having 1 to 4 carbon atoms such as t-butoxy.
Preferably, acyl groups include formyl, acetyl, pro
1 to 7 carbon atoms such as panoyl, butanoyl, benzoyl
Those having an acyloxy group such as acetoxy,
Propnoyloxy, butanoyloxy, benzoylo
Those having 2 to 7 carbon atoms such as xy are preferred. The substituent W in the general formula (I)
It is general formula (X), and general formula (X) is as described above.
is there. Such a structure represented by the general formula (I)
Specific examples of the structure are illustrated below, but the present invention includes these examples.
It is not limited. [0085] Embedded image [0086] Embedded image[0087] Embedded image [0088] Embedded image[0089] Embedded image [0090] Embedded image The structural unit represented by the general formula (II) is used as a resin.
By containing, the resin decomposes by the action of acid
And control the solubility in alkaline developer.
The In addition, by introducing this structural unit, rectangularity
Excellent profile can be achieved. Furthermore, the general formula
Effective for adjusting the amount of the structural unit represented by (I)
The Such a structure represented by the general formula (II)
Specific examples of the polymerizable monomer at the position include the following.
However, it is not limited to these. [0093] Embedded image [0094] Embedded imageThese general formula (II) or general formula (III)
The resin containing the structural unit represented by is a phenol resin
Or the monomer is reacted with acid anhydride in the presence of a base.
Or the corresponding halide in the presence of a base
It can obtain by making it react. The general formula in the resin (A) -1 of the present invention
Repeating structural units represented by (I) and general formula (III)
Is a molar ratio (the structural unit represented by the general formula (I)
/ Structural unit represented by general formula (III)) 5 / 95-50
/ 50, preferably 10/90 to 30/70
The In the resin (A) -2 of the present invention,
Shown by general formula (I), general formula (II) and general formula (III)
The ratio of structural units to satisfy the following conditions
And are preferred. 0.10 <(I) / (I) + (II) + (III) <0.
25 0.01 <(II) / (I) + (II) + (III) <0.
15 (I)> (III) 0.5 <(I) / (I) + (II) <0.85 (In the formula, (I), (II), and (III) each represent a general formula
(I), a structure represented by general formula (II) and general formula (III)
Represents the mole fraction of building units. ) In the present invention, (A) -1 resin or (A) -2 tree
The fat is represented by general formula (I), general formula (II) or general formula (III).
In addition to the structural unit represented by
-Units may be included. General formula (I), general formula (II) or general formula
Repeating unit represented by (III) or other polymerizability
Each repeating structural unit from the monomer is one kind or two
A combination of more than one species may be present in the resin. In the positive resist composition of the present invention,
And (A) -1 resin or (A) -2 resin are simultaneously
It may be present, and another resin may be used in combination. In the present invention, (A) -1 resin and
When the resin (A) -2 is present at the same time,
The resin content is 20 to 90% by weight based on the entire resin.
Preferably, it is 40 to 70% by weight. In addition, the content of the resin (A) -2 is the resin
20 to 90% by weight with respect to the whole, preferably 3
0 to 50% by weight. Also included in the positive resist composition of the present invention.
The resin used has good developability for alkaline developers.
To maintain alkali-soluble groups such as phenol
Suitable so that a neutral hydroxyl group and a carboxyl group can be introduced.
Other polymerizable monomers may be copolymerized. Of the present invention synthesized by the above method.
The molecular weight of the resin (A) -1 or the resin (A) -2 is
2,000 or more by weight average (Mw: polystyrene standard),
Preferably it is 3,000-100,000, and more preferable
It is preferably 5,000 to 40,000. The dispersity (Mw / Mn) is preferably
1.0 to 4.0, more preferably 1.0 to 3.5,
Is preferably 1.0 to 3.0, and the degree of dispersion is small.
Heat resistance, image formability (pattern profile, differential
The focus latitude, etc.). The general formula (I), general formula (II) and
Tree having a repeating structural unit represented by the general formula (III)
Specific examples of fat (resin (A) -2) are shown below.
Akira is not limited to these. Incidentally, it is represented by the general formula (I) and the general formula (III).
Having repeating structural units (tree of (A) -1
As specific examples of fat, the above-described specific examples (A-1) to (A
-28), but the present invention is limited to these.
It is not a thing. [0107] Embedded image [0108] Embedded image[0109] Embedded image[0110] Embedded image[0111] Embedded image Tree having a group represented by the above general formula (X)
Fat (including (A) -1 resin or (A) -2 resin)
Content in positive resist composition (excluding coating solvent)
Is preferably 50 to 99% by weight, more preferably 70%.
~ 97 wt%. Further, in the present invention, other acid-decomposable groups
You may use together resin which has. Chemical enhancement in the present invention
Decomposed by other acids used in width resists,
Trees with groups that increase solubility in alkaline developers
As the fat, the main chain or side chain of the resin, or the main chain and
It is a resin having groups capable of decomposing with an acid on both side chains.
Of these, resins having side groups that can be decomposed by acid are more preferred.
Good. Preferred groups that can be decomposed with an acid are-
COOA⁰, -OB⁰And a group containing these, and
-R⁰-COOA⁰Or -Ar-O-B⁰Indicated by
Group to be used. Here, A⁰Is -C (R⁰¹) (R⁰²) (R
⁰³), -Si (R⁰¹) (R⁰²) (R^{0 Three}) Or -C
(R⁰⁴) (R⁰⁵) -O-R⁰⁶Indicates a group. B⁰Is -A⁰or
Is -CO-O-A⁰Group (R⁰, R⁰¹~ R⁰⁶And A
r is as defined below. The acid-decomposable group is preferably silyl ether.
Ether group, cumyl ester group, acetal group, tetra
Dropyranyl ether group, tetrahydropyranyl ester
Group, enol ether group, enol ester group, third
Grade alkyl ether groups, tertiary alkyl esters
Groups, tertiary alkyl carbonate groups, and the like. Even better
Preferably, tertiary alkyl ester group, tertiary alkyl
Carbonate group, cumyl ester group, acetal group, tetra
It is a trahydropyranyl ether group. Next, these acid-decomposable groups become side chains.
As the base resin,
Or a group containing —COOH, preferably —R⁰-CO
Alkali-soluble having OH group or -Ar-OH group
Resin. For example, alkali-soluble resins described later are listed.
I can make it. Alkali dissolution of these alkali-soluble resins
The speed is 0.261N tetramethylammonium hydride
170 (23 ° C.) measured with peroxide (TMAH)
A / sec or more is preferable. Particularly preferably 330A
Per second (A is angstrom). From the point of achieving a rectangular profile
High transmittance for deep ultraviolet light and excimer laser light
Lucari soluble resin is preferred. Preferably, 1 μm film thickness
The transmittance at 248 nm is 20 to 90%. From this point of view, particularly preferred alk
Re-soluble resins are o-, m-, p-poly (hydroxys
Styrene) and their copolymers, hydrogenated poly (hydroxy)
Styrene), halogen or alkyl-substituted poly (H
Droxystyrene), poly (hydroxystyrene)
Part, O-alkylated or O-acylated, styrene
-Hydroxystyrene copolymer, α-methylstyrene-
Hydroxystyrene copolymer and hydrogenated novolac resin
It is. It has a group that can be decomposed by the acid used in the present invention.
The resin to be used is an acid-decomposable group of an alkali-soluble resin.
Bonding of groups that can react with precursors or decompose with acids
Combined alkali-soluble resin monomers with various monomers
It can be obtained by copolymerization. The acid generator has a group that can be decomposed by an acid.
Along with resin, acid-decomposable low-molecular-weight dissolution inhibiting compounds described later
May be mixed. Acid-decomposable dissolution inhibiting compound used in the present invention
As a product, there must be at least groups that can be decomposed by acid in the structure.
2 and the distance between the acid-decomposable groups is the farthest away.
In this case, at least 8 bond atoms excluding the acid-decomposable group
It is a compound. In addition, the acid-decomposable small molecule used in the present invention
The dissolution inhibiting compound has an acid-decomposable group represented by the general formula (X).
You may contain at least 1 sort. In the present invention, preferably acid-decomposable dissolution
Blocking compounds contain fewer groups that can be decomposed with acid in their structure.
The position where the distance between the acid-decomposable groups is furthest away
And at least 10 bonding atoms excluding the acid-decomposable group.
, Preferably at least 11, more preferably less
There are at least 12 compounds or acid-decomposable groups
The position where the distance between the acid-decomposable groups is the most distant
And at least 9 bond atoms excluding the acid-decomposable group.
, Preferably at least 10, more preferably less
It is a compound that passes through at least 11. In addition, the above bonding atom
The upper limit is preferably 50, more preferably 30
The In the present invention, an acid-decomposable dissolution inhibiting compound
Has 3 or more, preferably 4 or more acid-decomposable groups
In the case where there are two acid-decomposable groups, the acid
If the degradable groups are separated from each other by a certain distance,
Dissolution prevention for alkali-soluble resins is significantly improved
The Incidentally, the distance between the acid-decomposable groups in the present invention.
Is represented by the number of via-bonded atoms excluding the acid-decomposable group. Example
For example, in the case of the following compounds (1) and (2), an acid-decomposable group
The distance between each is 4 bonded atoms, and in compound (3)
Is 12 bonded atoms. [0128] Embedded image Also, the acid-decomposable dissolution inhibiting compound of the present invention
Has a plurality of acid-decomposable groups on one benzene ring.
Preferably, one on one benzene ring
A compound composed of a skeleton having an acid-decomposable group of
The Furthermore, the molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is
3,000 or less, preferably 500 to 3,000
0, more preferably 1,000 to 2,500. In a preferred embodiment of the invention, the acid
Decomposable by the group, i.e. -COO-A⁰, -OB⁰Base
Examples of the group containing -R⁰-COO-A⁰Or -Ar-
OB⁰The group shown by these is mentioned. Here, A⁰Is -C (R⁰¹) (R⁰²) (R
⁰³), -Si (R⁰¹) (R⁰²) (R^{0 Three}Or -C
(R⁰⁴) (R⁰⁵) -O-R⁰⁶Indicates a group. B⁰A⁰Or
-CO-O-A⁰Indicates a group. R⁰¹, R⁰², R⁰³, R⁰⁴And R⁰⁵It
Each may be the same or different, hydrogen atom, alkyl
Group, cycloalkyl group, alkenyl group or aryl
Group R⁰⁶Represents an alkyl group or an aryl group
The However, R⁰¹~ R⁰³At least two of which are hydrogen atoms or less
Outside group and R⁰¹~ R⁰³And R⁰⁴~ R⁰⁶Of
Two groups may combine to form a ring. R⁰Is a substituent
Divalent or higher aliphatic or aromatic charcoal that may have
Represents a hydrogen fluoride group, -Ar- is a monocyclic or polycyclic substituent
The aromatic group more than bivalence which may have is shown. Here, the alkyl group includes a methyl group,
Til, propyl, n-butyl, sec-butyl
Group having 1 to 4 carbon atoms such as t-butyl group is preferred.
Cycloalkyl groups include cyclopropyl and cyclyl groups.
Such as butyl, cyclohexyl, and adamantyl groups
Those having 3 to 10 carbon atoms are preferred,
Of vinyl, propenyl, allyl, and butenyl groups
Are preferably those having 2 to 4 carbon atoms such as aryl groups.
Are phenyl, xylyl, toluyl, cumenyl
Group having 6 to 1 carbon atoms such as naphthyl group and anthracenyl group
Four are preferred. Further, examples of the substituent include a hydroxyl group and a halogen atom.
Child (fluorine, chlorine, bromine, iodine), nitro group, cyano
Group, the above alkyl group, methoxy group, ethoxy group, hydride
Roxyethoxy group, propoxy group, hydroxypropoxy group
Si group, n-butoxy group, isobutoxy group, sec-buto
Alkoxy groups such as xy group and t-butoxy group, methoxy group
Alkoxycarbonyl such as rubonyl group and ethoxycarbonyl group
Bonyl, benzyl, phenethyl, cumyl, etc.
Aralkyl group, aralkyloxy group, formyl group, acetyl
Group, butyryl group, benzoyl group, cyanamyl group,
Acyloxy such as acyl group such as ryl group and butyryloxy group
Group, the above alkenyl group, vinyloxy group, propenyl
Al, such as oxy group, allyloxy group, butenyloxy group
Such as kenyloxy group, the above aryl group, phenoxy group, etc.
Aryloxy groups such as aryloxy groups and benzoyloxy groups
Mention may be made of the xylcarbonyl group. Preferred as a group that can be decomposed by an acid
Is a silyl ether group, cumyl ester group, acetal
Group, tetrahydropyranyl ether group, enol ether
Group, enol ester group, tertiary alkyl ether
Group, tertiary alkyl ester group, tertiary alkyl group
-Bonate groups and the like. More preferably, the tertiary alkyl
Ruester group, tertiary alkyl carbonate group, cumyl
An ester group and a tetrahydropyranyl ether group. Preferred as an acid-decomposable dissolution inhibiting compound
JP-A-1-289946, JP-A-1-2899.
47, JP-A-2-2560, JP-A-3-12895
9, JP-A-3-158855, JP-A-3-1793
53, JP-A-3-191351, JP-A-3-200
No. 251, JP-A-3-200252, JP-A-3-20
No. 0253, Japanese Patent Laid-Open No. 3-200454, Japanese Patent Laid-Open No. 3-2
No. 00255, JP-A-3-259149, JP-A-3-259
279958, JP-A-3-279959, JP-A-4
-1650, JP-A-4-1651, JP-A-4-11
260, JP-A-4-12356, JP-A-4-123
No. 57, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-2307
No. 90, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-251
No. 57, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-1032
No. 15, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107
No. 885, Japanese Patent Application Nos. 4-107889 and 4-1521
Of polyhydroxy compounds described in specifications such as No. 95
Some or all of the phenolic OH groups are shown above.
Group, -R⁰-COO-A⁰Or B⁰Bonded by group and protected
Compound. More preferably, JP-A-1-289946.
No. 3, JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200262, JP-A-3-200
No. 255, JP-A-3-259149, JP-A-3-27
No. 9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
No. 7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application No. 4-1078889, No. 4-15219
Using the polyhydroxy compound described in the specification of No. 5
Can be mentioned. More specifically, the general formulas [I] to [XV]
I]. [0139] Embedded image [0140] Embedded imageR¹⁰¹, R¹⁰², R¹⁰⁸, R¹³⁰: Same or different
May be a hydrogen atom, -R0-COO-C (R
⁰¹) (R⁰²) (R⁰³) Or -CO-O-C (R⁰¹) (R
⁰²) (R⁰³) However, R⁰, R⁰¹, R⁰²And R⁰³Definition of
Is the same as above. R¹⁰⁰: -CO-, -COO-, -NHC
ONH-, -NHCOO-, -O-, -S-, -SO
-, -SO₂-, -SO_Three-Or [0143] Embedded image Here, G = 2 to 6 However, when G = 2,
R¹⁵⁰, R¹⁵¹At least one of them is an alkyl group, R¹⁵⁰, R¹⁵¹: Same or different, hydrogen source
Child, alkyl group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R¹⁵²-COOR¹⁵³Or
-R^{15 Four}-OH, R¹⁵², R¹⁵⁴: Alkylene group, R¹⁵³: Hydrogen atom, alkyl group, aryl group, or
Aralkyl group, R⁹⁹, R¹⁰³~ R¹⁰⁷, R¹⁰⁹, R¹¹¹~ R¹¹⁸, R¹³¹~ R
¹³⁴: May be the same or different, hydrogen atom, hydroxyl group, a
Alkyl group, alkoxy group, acyl group, acyloxy group, acyl group
Reel group, aryloxy group, aralkyl group, aralkyl
Ruoxy group, halogen atom, nitro group, carboxyl
Group, cyano group, or -N (R¹⁵⁵) (R¹⁵⁶) (R
¹⁵⁵, R¹⁵⁶: H, alkyl group, or aryl
Base) R¹¹⁰: Single bond, alkylene group, or [0145] Embedded image R¹⁵⁷, R¹⁵⁹: Same or different,
Single bond, alkylene group, -O-, -S-, -CO-,
Or a carboxyl group, R¹⁵⁸: Hydrogen atom, alkyl group, alkoxy group, acyl
Group, acyloxy group, aryl group, nitro group, hydroxyl group,
An ano group or carboxyl group, provided that the hydroxyl group has an acid content.
Decomposable groups (eg, t-butoxycarbonylmethyl, te
A trahydropyranyl group, a 1-ethoxy-1-ethyl group,
1-t-butoxy-1-ethyl group)
Yes. R¹¹⁹, R¹²⁰: Same or different,
Methylene group, lower alkyl substituted methylene group, halomethyl
Group or haloalkylene group, provided that in the present invention
The lower alkyl group refers to an alkyl group having 1 to 4 carbon atoms, A: Methylene group, lower alkyl-substituted methylene group, halogen
A tylene group or a haloalkylene group, a-v, g1-n1: When there are multiple groups, the groups in parentheses are the same or different
May be, a to q, s, t, v, g1 to i1, k1 to m1: 0 or 1 to 5
number, r, u: 0 or an integer from 1 to 4, j1, n1: 0 or an integer of 1 to 3, (a + b), (e + f + g), (k + l + m), (q + r + s), (g1 + h1 + i1 + j1) ≧ 2, (j1 + n1) ≦ 3, (r + u) ≦ 4, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1) ≦ 5, Represents. [0148] Embedded image[0149] Embedded image[0150] Embedded imageIn this case, the content of the dissolution inhibiting compound is
3 to 3 based on the total weight of the dyst composition (excluding solvent)
45% by weight, preferably 5-30% by weight, more preferably
Is 10 to 20% by weight. Furthermore, in order to adjust the alkali solubility,
Mixing alkali-soluble resins that do not have acid-decomposable groups
May be. As such an alkali-soluble resin,
For example, novolac resin, hydrogenated novolac resin, aceto
-Pyrogallol resin, o-polyhydroxystyrene,
m-polyhydroxystyrene, p-polyhydroxystyrene
Ren, hydrogenated polyhydroxystyrene, halogen or
Is alkyl-substituted polyhydroxystyrene, hydroxys
Tylene-N-substituted maleimide copolymers, o / p- and m
/ P-hydroxystyrene copolymer, polyhydroxys
Partially O-alkylated product of hydroxyl group of tylene (for example,
5-30 mol% O-methylated product) or O-
Acylates (eg, 5-30 mol% o-acetylated)
), Styrene-maleic anhydride copolymer, styrene
-Hydroxystyrene copolymer, α-methylstyrene-
Hydroxystyrene copolymer, carboxyl group-containing meta
Examples thereof include cryl-based resins and derivatives thereof.
It is not limited to these. Particularly preferred alkali-soluble resins are Novola.
Resin, o-polyhydroxystyrene, m-polyethylene
Droxystyrene, p-polyhydroxystyrene and this
These copolymers, alkyl-substituted polyhydroxystyrene
, Partial O-alkylation of polyhydroxystyrene,
Or O-acylated product, styrene-hydroxystyrene
Copolymer, α-methylstyrene-hydroxystyrene copolymer
It is a polymer. The novolak resin mainly contains a predetermined monomer.
As an ingredient, addition condensation with aldehydes in the presence of an acidic catalyst
It is obtained by combining. As the predetermined monomer, phenol, m
-Cresol, p-cresol, o-cresol, etc.
Resols, 2,5-xylenol, 3,5-xylenol
, 3,4-xylenol, 2,3-xylenol, etc.
Silenols, m-ethylphenol, p-ethylphenol
Nord, o-ethylphenol, pt-butylpheno
, P-octylphenol, 2,3,5-trimethyl
Alkylphenols such as phenol, p-methoxyph
Enol, m-methoxyphenol, 3,5-dimethyl
Siphenol, 2-methoxy-4-methylphenol,
m-ethoxyphenol, p-ethoxyphenol, m
-Propoxyphenol, p-propoxyphenol,
such as m-butoxyphenol, p-butoxyphenol, etc.
Alkoxyphenols, 2-methyl-4-isopropyl
Bisalkylphenols such as ruphenol, m-chloro
Lophenol, p-chlorophenol, o-chlorofe
Nord, dihydroxybiphenyl, bisphenol A,
Phenylphenol, resorcinol, naphthol, etc.
Hydroxy aroma compound alone or in combination
However, it is not limited to these
There is no. Examples of aldehydes include formal.
Dehydr, paraformaldehyde, acetaldehyde,
Lopionaldehyde, benzaldehyde, phenylacetate
Toaldehyde, α-phenylpropyl aldehyde, β-
Phenylpropylaldehyde, o-hydroxybenzua
Rudehydr, m-hydroxybenzaldehyde, p-hydride
Roxybenzaldehyde, o-chlorobenzaldehyde
, M-chlorobenzaldehyde, p-chlorobenza
Rudehydr, o-nitrobenzaldehyde, m-nitrobe
Aldehyde, p-nitrobenzaldehyde, o-me
Tilbenzaldehyde, m-methylbenzaldehyde,
p-methylbenzaldehyde, p-ethylbenzalde
Hydride, pn-butylbenzaldehyde, furfura
, Chloroacetaldehyde and their acetals
Bodies such as chloroacetaldehyde diethyl acetal
Etc., but in these, formua
Preferably, aldehyde is used. These aldehydes may be used alone or
Two or more types are used in combination. As an acidic catalyst
Use hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, etc.
it can. The weight average of the novolak resin thus obtained
The average molecular weight should be in the range of 1000-30000
preferable. If it is less than 1000, film loss after development of the unexposed area is reduced.
If it is large and exceeds 30000, the developing speed will decrease.
End up. Particularly preferred is the range of 2000 to 20000
is there. In addition, the above polyhydrides other than novolac resins.
Weight average of loxystyrene and its derivatives and copolymers
The molecular weight is 2000 or more, preferably 5000 to 200
000, more preferably 10,000 to 100,000
The In addition, the viewpoint of improving the heat resistance of the resist film
Is preferably 25000 or more. Here, the weight average molecular weight is gel permeation.
With the polystyrene equivalent value of
Defined. These alkali-soluble trees in the present invention
Two or more kinds of fats may be mixed and used. These alkali-soluble trees in the present invention
The amount added in the fat composition is preferably 5 to 30 layers.
%. The acid generator (b) used in the present invention is active.
It is a compound that generates an acid upon irradiation with actinic radiation. As the acid generator (b) used in the present invention
By irradiation of actinic radiation (electron beam, X-ray or EUV)
The compound generating an acid is a resin containing an acid generator (b).
When the dyst film is irradiated with actinic radiation,
As long as it is a compound that generates That is, the acid generator
Even compounds that generate acid directly upon irradiation are irradiated.
Causes secondary electrons to be emitted from components such as resin,
This may be a compound that generates an acid. In the present invention
Such compounds used include photocationic polymerization
Photoinitiators, photoinitiators of radical photopolymerization, photoextinguishing of pigments
Used for colorants, photochromic agents, or microresists
Known light (400-200 nm UV, deep purple
Outside line, particularly preferably g line, h line, i line, KrF exhaust
Shima laser light), ArF excimer laser light, X-ray,
Compounds that generate acid by molecular beam or ion beam, and
Select from the mixture and use as appropriate.
Can do. For example, diazonium salt, ammonium
Salt, phosphonium salt, iodonium salt, sulfonium
Onium salts such as salts, selenonium salts and arsonium salts,
Organic halogen compounds, organometallic / organic halides, o
-Iminos, an acid generator having a nitrobenzyl-type protecting group
Photolysis, such as sulfonate, generates sulfonic acid.
Compounds and disulfone compounds produced
The In addition, these acid generating groups, or
Use a compound with a compound introduced into the main chain or side chain of the polymer
Can be. Furthermore, V.N.R.Pillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
D.H.R.Barton etal, J. Chem. Soc., (C), 329 (1970), USA
Light described in Patent 3,779,778, European Patent 126,712, etc.
A compound capable of generating an acid can also be used. In the present invention, the acid generator (b) is used.
Actives represented by the above general formulas (A-1) to (A-7)
The compound that generates sulfonic acid when irradiated with actinic radiation
Preferably used. Hereinafter, the general formulas (A-1) to (A-
The compound represented by 7) will be described in detail. It is represented by the general formulas (A-1) to (A-3)
Acid generator R in the general formulas (A-1) to (A-3)₁~ R₆
And R₇~ R_TenAs the alkyl group, it has a substituent.
Methyl group, ethyl group, propyl group, n-butyl
1 carbon number such as a group, sec-butyl group, t-butyl group
There are ~ 4. As a cycloalkyl group
May have a substituent, cyclopropyl group, cyclo
3-8 carbon atoms such as pentyl and cyclohexyl groups
Can be mentioned. As an alkoxy group, methoxy
Group, ethoxy group, hydroxyethoxy group, propoxy
Group, n-butoxy group, isobutoxy group, sec-butoxy group
Those having 1 to 4 carbon atoms such as cis-group and t-butoxy group
Can be mentioned. Halogen atoms include fluorine and chlorine
An atom, a bromine atom, and an iodine atom can be mentioned. Ant
Examples of the group include phenyl group, tolyl group, methoxyphenol
Carbon which may have a substituent such as a nyl group or a naphthyl group
A thing of several 6-14 pieces is mentioned. [0170] The substituent is preferably 1 to 4 carbon atoms.
Alkoxy group, halogen atom (fluorine atom, chlorine atom
Child, iodine atom), aryl group having 6 to 10 carbon atoms, carbon
Several to six alkenyl groups, cyano groups, hydroxy groups,
Carboxy group, alkoxycarbonyl group, nitro group etc.
Can be mentioned. The general formula (A-1)-
Sulfonium represented by (A-3), iodinated
The compound is its counter anion, X^-(A) linear,
Branched or cyclic alkyl sulfone having 1 to 12 carbon atoms
An anion of acid, part or all of its hydrogen atoms are fluorine
Optionally substituted by atoms, or (b) branched or ring
Group of alkyl and alkoxy groups having 8 or more carbon atoms
Having at least one group selected from
, Branched or cyclic alkyl groups having 4 to 7 carbon atoms and
At least two groups selected from the group of alkoxy groups
A linear or branched alkyl having 1 to 3 carbon atoms
Less groups selected from the group consisting of
Have 3 or 1 to 5 halogen atoms
Or linear or branched carbon having 1 to 10 carbon atoms.
Benzene sulfonic acid with ter group, naphthalene sulfo
An anion of acid or anthracene sulfonic acid
The As a result, an acid generated after exposure (having the above group).
Benzene sulfonic acid, naphthalene sulfonic acid, or
Anthracene sulfonic acid) is less diffused, and
The solvent solubility of the sulfonium and iodonium compounds is improved.
I will go up. Especially from the viewpoint of reducing diffusibility.
Is a linear alkyl group or alkoxy group as the above group
A branched or cyclic alkyl group or alkoxy group
Is preferred. When there is a single group, straight-chain and branched or
The difference in diffusibility from the ring becomes more prominent. [0174] 8 or more carbon atoms, preferably 8 to 2 carbon atoms
Zero alkyl groups include branched or cyclic octyl
Group, nonyl group, decyl group, undecyl group, dodecyl group,
Tridecyl group, tetradecyl group, octadecyl group, etc.
I can get lost. [0175] C8 or more, preferably C8-2
Zero alkoxy groups include branched or cyclic octyl
Ruoxy, nonyloxy, decyloxy, unde
Siloxy group, dodecyloxy group, tridecyloxy
Group, tetradecyloxy group, octadecyloxy group, etc.
Can be mentioned. As the alkyl group having 4 to 7 carbon atoms,
Chain, branched or cyclic butyl, pentyl, hex
Group, heptyl group and the like. As the alkoxy group having 4 to 7 carbon atoms,
Linear, branched or cyclic butoxy group, pentyloxy
Group, hexyloxy group, heptyloxy group, etc.
The As the alkyl group having 1 to 3 carbon atoms,
Til group, ethyl group, n-propyl group, isopropyl group
Can be mentioned. As the alkoxy group having 1 to 3 carbon atoms,
Methoxy group, ethoxy group, n-propoxy group, isopropyl
A poxy group is mentioned. The halogen atom includes a fluorine atom and chlorine.
Atom, bromine atom, iodine atom can be mentioned and preferred
Or a fluorine atom. Linear, branched or cyclic carbon number 1-10
These esters include methyl ester groups, ethyl ester
Tell group, n-propyl ester group, i-propyl ester
Group, n-butyl ester group, i-butyl ester group,
t-butyl ester group, n-hexyl ester group, i-
Hexyl ester group, t-hexyl ester group, n-he
Butyl ester group, i-heptyl ester group, t-hept
Chill ester group, n-octyl ester group, i-octyl
Ruester group, t-octyl ester, n-nonyl ester
Tell group, i-nonyl ester group, t-nonyl ester
Group, n-decanyl ester group, i-decanyl ester
Group, t-decanyl ester, cyclopropyl ester
Group, cyclobutyl ester group, cyclopentyl ester
Group, cyclohexyl ester group, cycloheptyl ester
Group, cyclooctyl ester group, cyclononyl ester
Group, cyclodecanyl ester group and the like. Linear, branched or cyclic carbon number 1-12
Group in the anion of one alkyl sulfonic acid
Is preferably an alkyl group having 1 to 12 carbon atoms,
For example, methyl group, ethyl group, propyl group, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl
Group, pentyl group, neopentyl group, hexyl group, heptyl
And the like, alkyl group, octyl group, nonyl group, decyl group
Can do. In addition, X^-Alkyl sulfone represented by
In acid and aromatic sulfonic acid, in addition to the above specific substituents,
Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine
Atom), aryl group having 6 to 10 carbon atoms, cyano group,
Rufido group, hydroxy group, carboxy group, nitro group, etc.
May be contained as a substituent. Specific examples of these compounds (A-1) are shown below.
-1) to (A-1-66), (A-2-1) to (A-2)
-59), (A-3-1) to (A-3-35) are shown.
However, the present invention is not limited to this. [0185] Embedded image [0186] Embedded image[0187] Embedded image [0188] Embedded image[0189] Embedded image[0190] Embedded image[0191] Embedded image[0192] Embedded image[0193] Embedded image[0194] Embedded image[0195] Embedded image[0196] Embedded image[0197] Embedded image [0198] Embedded image[0199] Embedded image[0200] Embedded image[0201] Embedded image[0202] Embedded image[0203] Embedded image[0204] Embedded image[0205] Embedded image[0206] Embedded image[0207] Embedded image[0208] Embedded image[0209] Embedded image[0210] Embedded image[0211] Embedded image[0212] Embedded image[0213] Embedded image In the specific examples, n is a straight chain, s is a secondary, t
Indicates tertiary, i indicates branching. Represented by the general formulas (A-1) to (A-3).
The compounds are for example the corresponding Cl^-Salt (general formula (A-1)
~ (A-3) X^-Cl^-And a compound substituted with^-
Y⁺A compound represented by the formula (X^-Are general formulas (A-1) to (A
-3), which is synonymous with Y⁺Is H⁺, Na⁺, K⁺, N
H_Four ⁺, N (CH_Three)_Four ⁺ And the like cations. ) And water soluble
It can be synthesized by salt exchange in the liquid. Represented by the general formulas (A-4) and (A-5)
Acid generator In the general formulas (A-4) and (A-5), R₁₁~ R₁₃,
R₁₄~ R₁₆Alkyl group, cycloalkyl group,
Lucoxy group, halogen atom is R¹~ R^FiveSimilar to
Can be given as a specific example. R₆, X
^-Is as defined above. Also, when l, m, and n are each 2 or 3,
2 or 3 R₁₁~ R₁₃Or R₁₄~ R₁₆Each of
Two of them bonded together to form a carbocyclic, heterocyclic or aromatic ring
You may form the ring which consists of 5-8 elements containing. The compound represented by the general formula (A-4) is shown below.
Specific examples of products (A-4-1) to (A-4-28), general formula
Specific examples of the compound represented by (A-5) (A-5-1) to
(A-5-30) is shown but is not limited to this.
Absent. [0219] Embedded image [0220] Embedded image[0221] Embedded image[0222] Embedded image[0223] Embedded image[0224] Embedded image[0225] Embedded image [0226] Embedded image[0227] Embedded image[0228] Embedded image[0229] Embedded image [0230] [Chemical Formula 86] In the specific examples, n is a straight chain, s is a secondary, t
Indicates tertiary, i indicates branching. It is represented by general formulas (A-4) and (A-5).
The compounds are for example the corresponding Cl^-Salt (general formula (A-
4) X in (A-5)^-Cl^-And a compound substituted with
X^-Y⁺A compound represented by the formula (X^-Is the general formula (A-4),
Synonymous with (A-5), Y⁺Is H⁺, Na⁺, K⁺, NH
_Four ⁺, N (CH3)_Four ⁺And the like cations. ) And in aqueous solution
And can be synthesized by salt exchange. Acid generator represented by general formula (A-6) Y and R in the general formula (A-6)₃₁~ R₅₁Straight
Chain, branched, and cyclic alkyl groups include methyl and ethyl
Group, propyl group, isopropyl group, n-butyl group, sec-
Butyl group, t-butyl group, hexyl group, octyl group
Such straight-chain or branched alkyl groups having 1 to 20 carbon atoms and
Chloropropyl group, cyclopentyl group or cyclohexyl
And cyclic alkyl groups such as groups. Preferred alkyl groups
New substituents include alkoxy groups, acyl groups, and acyloxy groups.
Si group, chlorine atom, bromine atom, iodine atom, etc.
The In addition, the aralkyl group of Y is benzyl.
Group having 7 to 12 carbon atoms such as phenethyl group or phenethyl group
An aralkyl group may be mentioned. Preferred substitution of aralkyl groups
The group includes a lower alkyl group having 1 to 4 carbon atoms and 1 carbon atom.
-4 lower alkoxy group, nitro group, acetylamino
Group, halogen atom and the like. R₃₁~ R₅₁As an alkoxy group of
Si group, ethoxy group, propoxy group, isopropoxy group,
n-butoxy group, isobutoxy group, sec-butoxy group, t
-Of butoxy group, octyloxy group, dodecyloxy group
Such an alkoxy group having 1 to 20 carbon atoms or ethoxy group
And alkoxy groups having a substituent such as a toxi group.
The The acyl group includes an acetyl group and propioni.
Group, benzoyl group and the like. Acylamino group
As acetylamino group, propionylamino group,
And nzoylamino group. Sulfonylamino
The groups include methanesulfonylamino group, ethanesulfonyl
A sulfonylamino group having 1 to 4 carbon atoms such as a ruamino group,
substituted or absent such as p-toluenesulfonylamino group
Examples thereof include a substituted benzenesulfonylamino group. As the aryl group, a phenyl group and tolyl
Group, naphthyl group and the like. Alkoxycarboni
As the alkyl group, methoxycarbonyl group, ethoxycarbonyl group
Group, ethoxyethoxycarbonyl group, octyloxy
Carbon such as carbonyl group and dodecyloxycarbonyl group
Examples thereof include several to 20 alkoxycarbonyl groups. As an acyloxy group, an acetoxy group, a pro
Panoyloxy group, octanoyloxy group, benzoyl
There are acyloxy groups with 2 to 20 carbon atoms such as oxy groups.
I can get lost. An aralkyl group is a substituted or unsubstituted group.
Carbon number such as benzyl group, substituted or unsubstituted phenethyl group
There are 7 to 15 aralkyl groups. Aralkyl group
Preferred substituents for are the same as those listed above
Can be given. R₃₁~ R₅₁In R₃₁~ R₃₅, R₃₆
~ R₄₂And R₄₃~ R₅₁Are two of each group
Combined to form a 5- to 8-membered ring consisting of carbon and / or heteroatoms.
It may be formed. Examples of such 5- to 8-membered rings include
For example, cyclohexane, pyridine, furan or pyrrolidine
Can be given. X and Y are other imide sulfonates.
It may be bound to the residue of the compound and forms a dimer or trimer
It may be made. As another imide sulfonate,
A compound represented by the general formula (A-6), wherein X or Y
A monovalent group can be mentioned. The alkylene group for X is linear or branched
An alkylene group having 1 to 10 carbon atoms or a hetero atom
A monocyclic or polycyclic alkylene group which may contain
Can be mentioned. As the linear or branched alkylene group,
Len group, ethylene group, propylene group or octylene group
I can give it. As a preferred substituent of the alkylene group
Is an alkoxy group, acyl group, formyl group, nitro group,
Silamino group, sulfonylamino group, halogen atom, a
Examples thereof include a reel group and an alkoxycarbonyl group. here
Alkoxy group, acyl group, nitro group, acyl group
Mino group, sulfonylamino group, aryl group, alkoxy
The carbonyl group is R₃₁~ R₅₁It is synonymous with what was mentioned in.
Halogen atoms include fluorine, chlorine and bromine
Examples include a child and an iodine atom. The cyclic alkylene group is cyclopentylene.
Single group having 4 to 8 carbon atoms such as chlorobenzene group, cyclohexylene group, etc.
A ring cycloalkylene group, 7-oxabicyclo [2.2.
1] Polycyclic cyclohexane having 5 to 15 carbon atoms such as heptylene group
An alkylene group, and a cycloalkylene group is preferred.
Examples of the substituent include alkyl groups having 1 to 4 carbon atoms,
Coxy group, acyl group, formyl group, nitro group, acyl group
Mino group, sulfonylamino group, halogen atom, aryl
Group and alkoxycarbonyl group. The alkoxy groups, acyl groups, di
Toro group, acylamino group, sulfonylamino group, aryl
R group and alkoxycarbonyl group are R₃₁~ R₅₁Also mentioned in
Is synonymous with Halogen atoms include fluorine atoms and salts
Mention may be made of elemental atoms, bromine atoms and iodine atoms. The arylene group includes a phenylene group and naphth
Tylene group etc. are mentioned. Preferred substitution of arylene groups
Groups include alkyl groups, cycloalkyl groups, and alkoxy
Group, acyl group, formyl group, nitro group, acylamino
Group, sulfonylamino group, halogen atom, aryl group,
An alkoxycarbonyl group is mentioned. Alkyl groups and cycloalkyl mentioned here
Group, alkoxy group, acyl group, formyl group, nitro group,
Acylamino group, sulfonylamino group, aryl group,
Lucoxycarbonyl group is R₃₁~ R₅₁Synonymous with
It is. As halogen atoms, fluorine atoms, chlorine atoms,
A bromine atom and an iodine atom can be mentioned. The alkenylene group has 2 to 4 carbon atoms.
Alkenylene groups such as ethenylene group, butene
Nylene group and the like, preferred substitution of alkenylene group
Groups include alkyl groups, cycloalkyl groups, and alkoxy
Group, acyl group, formyl group, nitro group, acylamino
Group, sulfonylamino group, halogen atom, aryl group,
An alkoxycarbonyl group is mentioned. A
Alkyl group, cycloalkyl group, alkoxy group, acyl
Group, formyl group, nitro group, acylamino group, sulfoni
Ramino group, aryl group, alkoxycarbonyl group is R
₃₁~ R₅₁It is synonymous with what was mentioned in. As halogen atoms
Include fluorine, chlorine, bromine and iodine atoms.
I can make it. The cyclic alkenylene group is cyclopente.
4-8 carbon atoms such as a nylene group or a cyclohexenylene group
Monocyclic cycloalkenylene groups, 7-oxabicyclo
[2.2.1] heptenylene group, norbornenylene group
Which polycyclic cycloalkenylene group having 5 to 15 carbon atoms is
I can get lost. Examples of the aralkylene group include a tolylene group and a key.
Examples of the substituent include arylene.
The substituents mentioned for the len group can be mentioned. In the following, these are represented by the general formula (A-6).
Specific examples of compounds (A-6-1) to (A-6-49)
However, the present invention is not limited to this. [0252] Embedded image [0253] Embedded image[0254] Embedded image [0255] Embedded image[0256] Embedded image [0257] Embedded image[0258] Embedded image [0259] Embedded image[0260] Embedded imageThe compound represented by formula (A-6) is G.
F. Jaubert, Ber .. 28, 360 (1895), D.E.Ames, etc.
Written by J.Chem.Soc..3518 (1955) or M.A.Stol
berg et al., J. Am. Chem. Soc. 79, 2615 (1957)
N-hydroxyimide compound and sulfone synthesized accordingly
Acid chloride and basic conditions, for example, L. Bauer et al., J.
Org.Chem..24,1294 (1959)
Is possible. Acid generator represented by general formula (A-7) In general formula (A-7), Ar₁, Ar₂Is the same or different
A substituted or unsubstituted aryl group. Here, as the aryl group, phenyl
Group, tolyl group, naphthyl group and the like. Aryl
As the substituent of the group, an alkyl group, a cycloalkyl group,
Alkoxy, acyl, formyl, nitro, acyl
Ruamino group, sulfonylamino group, halogen atom, ant
Group and alkoxycarbonyl group. Alkyl groups and cycloalkyl mentioned here
Group, alkoxy group, acyl group, formyl group, nitro group,
Acylamino group, sulfonylamino group, aryl group,
Lucoxycarbonyl group is R₃₁~ R₅₁And those listed in
It is synonymous. Halogen atoms include fluorine and chlorine
Examples thereof include a child atom, a bromine atom and an iodine atom. Ingredients of acid generator represented by formula (A-7)
As examples, the following compounds (A-7-1) to (A-
7-14), but is limited to these.
There is no. [0266] Embedded image[0267] Embedded image Acid generator represented by the above general formula (A-7)
As a synthesis of Sea. Denser. Junior. Et
"Journal of Organic Chemistry"
(G.C.Denser, Jr. et al., `` Journal of Organic Chemi
stry ") 31, 3418-3419 (1966). Pi
-. By Hildeich “Journal of the Chemical
  Society (Journal of the C by T.P.Hilditch
he mi cal Society ”) 93, 1524-1527 (1908)
Method or Oh. By Hinsberg "Berichte der
  Deutsche Hemicie Gezelshaft (O. Hinsbe
rg, "Berichte der Deutschen Chemischen Gesellsc
haft ”) 49, 2593-2594 (1918)
Can be synthesized. That is, in sulfuric acid aqueous solution, sulfuric acid
Cobalt and sulfinic acid represented by the general formula (a)
More synthetic methods, using ethyl xanthate,
One synthesized from sulfonic acid chloride represented by formula (b)
The method represented by the general formula (a) under basic or basic conditions
Rufinic acid and sulfonic acid chloride represented by the general formula (b)
And the like. Ar₁ -SO₂H (a) Ar₂ -SO₂Cl (b) (Where Ar₁, Ar₂Is defined by the general formula (A-7)
It has the same meaning as ) In the present invention, the above general formulas (A-1) to (A-7)
Among the acid generators represented by general formulas (A-1) to (A-
The acid generator represented by 5) is preferred, more preferably one
An acid generator represented by general formulas (A-1) to (A-4)
The This will improve resolution and sensitivity.
The In the present invention, an acid generator (preferably one
Composition of general formulas (A-1) to (A-7))
The content in the product is 0.1-25 with respect to the solid content of the whole composition.
% By weight is preferred, more preferably 1-15% by weight,
Preferably, it is 2 to 10% by weight. Further, the acid generator (b) is irradiated with actinic radiation.
Compound a that generates fluorine-containing sulfonic acid upon irradiation
It is also preferable. [A] As the compound a, for example,
An iodonium salt represented by the following general formula (PAG3),
Or a sulfonium salt represented by the general formula (PAG4).
I can make it. [0272] Embedded image In the formula, Ar¹, Ar²Are each independently substituted
Or an unsubstituted aryl group is shown. R²⁰³, R²⁰⁴, R
²⁰⁵Each independently represents a substituted or unsubstituted alkyl
A group and an aryl group; Z^-Has at least one fluorine atom
A sulfonate anion. Also, R²⁰³, R²⁰⁴, R²⁰⁵Two of them
And Ar¹, Ar²Each via a single bond or substituent
May be combined. Ar¹, Ar², R²⁰³, R²⁰⁴, R²⁰⁵age
All the aryl groups preferably have 6 to 14 carbon atoms.
As the aryl group and alkyl group, the number of carbon atoms is preferably
1 to 8 alkyl groups. As a preferred substituent group, an aryl group
C1-C8 alkoxy group, C1-C8 a
Rualkyl group, C2-C9 alkoxycarbonyl group, charcoal
A prime number 2-9 alkylcarbonylamino group, a nitro group,
Carboxyl group, hydroxy group, halogen atom and
It is a nylthio group and has 1 to 8 carbon atoms for the alkyl group.
Alkoxy group, aryl group having 5 to 14 carbon atoms, carbon number
6-15 arylcarbonyl groups, carboxyl groups and
Mention may be made of halogen atoms. Z^-Preferred as sulfonate anion
Alternatively, the number of carbon atoms having at least one fluorine atom is 1
-20 aliphatic hydrocarbons and C5-C20 aromatic coals
Mention may be made of hydrogen fluoride. These have substituents
The substituent may be, for example, 1 to 10 carbon atoms.
A fluorine-substituted alkoxy group having 2 to 2 carbon atoms
11 fluorine-substituted alkoxycarbonyl
Group, phenylamino group, phenylcarbonyl group, halogen
An atom and a hydroxyl group can be mentioned. Aromatic hydrocarbons
In addition, an alkyl group having 1 to 15 carbon atoms is mentioned.
Can. Specific examples are given below, but the present invention is not limited to these.
Is not something [0280] Embedded image [0281] Embedded image[0282] Embedded image[0283] Embedded image[0284] Embedded image [0285] Embedded image[0286] Embedded image[0287] Embedded image[0288] Embedded image[0289] Embedded image[0290] Embedded imageWhen compound a is used, it is irradiated with actinic radiation.
Generates sulfonic acid that does not contain fluorine atoms.
Or carboxylic acid by irradiation with actinic radiation
Concomitant use with at least one of the compounds
Is preferred. [B] Preferably used in combination with compound a
Sulfo containing no fluorine atom by irradiation with actinic radiation
Examples of the compound that generates acid (compound b) include:
In the general formulas (PAG3) and (PAG4), Z
^-Is a sulfonate anion having no fluorine atom
Mention may be made of donium salts and sulfonium salts.
The Specific examples include the following compounds.
However, it is not limited to these. [0294] Embedded image[0295] Embedded image [0296] Embedded image[0297] Embedded image [0298] Embedded image [0299] Embedded image[0300] Embedded image [0301] Embedded imageFurther, it is represented by the following general formula (PAG5).
A disulfone derivative or an a represented by the general formula (PAG6)
Mention may be made of minosulfonate derivatives. [0303] Embedded image In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
An unsubstituted alkyl group and an aryl group are shown. A is substitution
Or an unsubstituted alkylene group, alkenylene group, aryle
Indicate group. Specific examples include the following compounds.
However, it is not limited to these. [0306] Embedded image [0307] Embedded image[0308] Embedded image [0309] Embedded image Further, it is represented by the following general formula (PAG7).
Mention may be made of diazodisulfone derivatives. [0311] Embedded image In the formula, R is linear, branched or cyclic alkyl.
Represents an aryl group which may be substituted. Specific examples include the following compounds.
However, it is not limited to these. [0314] Embedded image Compounds described in [a] and [b] above
Obtained by reacting aromatic compounds with periodate
Salt exchanged iodonium salt with the corresponding sulfonic acid
Can be synthesized. Further, arylmagnesium bromide and the like
Of aryl Grignard reagents and substituted or unsubstituted phenyl
The triarylsulfoxide obtained by reacting sulfoxide
For salt exchange of phonic halides with the corresponding sulfonic acids
Can be synthesized. In addition, substituted or unsubstituted phenylsulfur
Methanesulfonic acid / aromatic compound corresponding to foxide
Acid catalyst such as diphosphorus pentoxide or aluminum chloride
Condensation and salt exchange method, diaryliodonium
Salts and diaryl sulfides using catalysts such as copper acetate
It can be synthesized by methods such as condensation and salt exchange. [0317] After salt exchange, once led to halide salt
Convert to sulfonate using silver reagent such as silver oxide
Method or salt exchange by using ion exchange resin
it can. In addition, sulfonic acid or sulfur used for salt exchange
Use a commercially available fonate or use a commercially available sulfonate.
It can be obtained by hydrolysis of sulfonic acid halide.
Yes. Active release preferably used in combination with compound a
As a compound that generates carboxylic acid upon irradiation with rays
Are compounds c and fluorine which generate a fluorine-free carboxylic acid.
Mention may be made of compound d which generates a nitrogen-containing carboxylic acid.
it can. [C] Preferably used in combination with compound a
Generate fluorine-free carboxylic acid by irradiation with actinic radiation
As the compound c to be used, for example, the following general formula (AI) to
And a compound represented by (AV). [0320] Embedded image In the above formula, R₃₀₁~ R₃₃₇Each
Independently a hydrogen atom, a linear, branched or cyclic alkyl group,
Linear, branched or cyclic alkoxy group, hydroxy group,
Halogen atom or -S-R₀Represents a group. R₀Is straight chain,
A branched, cyclic alkyl group or aryl group is represented. Ra and Rb are each independently a hydrogen atom or nitrite.
B, a halogen atom, an optionally substituted al group
Represents a kill group or an alkoxy group. Rc and Rd are independent of each other
May have a halogen atom or a substituent, alkyl
Represents a group or an aryl group. Rc and Rd combine to give a fragrance
Ring, monocyclic or polycyclic hydrocarbons (within these rings)
May contain oxygen and nitrogen atoms)
Also good. Y₁, Y₂Represents a carbon atom and Y₁-Y₂Join
May be a single bond or a double bond. X above^-Is the following formula
The carboxylic acid compound represented by
Represent. X₁, X₂Are each independently represented by the following formula:
Carboxylic acid compound is an ester group at the carboxyl group
It represents what became. [0324] Embedded image[0325] Embedded imageIn the above formula, R₃₃₈Is straight from 1 to 30 carbon atoms.
A chain, branched or cyclic alkyl group (wherein
The chain of the kill group may contain oxygen and nitrogen atoms
1), linear, branched or cyclic having 1 to 20 carbon atoms
Alkenyl groups, straight-chain, branched or 1 to 20 carbon atoms
Is a cyclic alkynyl group, straight chain having 1 to 20 carbon atoms, branched
Or cyclic alkoxyl group, water of the alkyl group
At least some of the elementary atoms are halogen atoms and / or
A group substituted with a hydroxyl group, a hydrogen atom of the alkenyl group
At least part of which is a halogen atom and / or a hydroxyl group
A substituted group, or a C 6-20 substitution or
An unsubstituted aryl group is shown. Where substitution of aryl group
Groups include alkyl groups, nitro groups, hydroxyl groups, alkoxy
Group, acyl group, alkoxycarbonyl group, halogen atom
Can be mentioned. R₃₃₉Is a single bond or 1 to 2 carbon atoms
0 linear, branched or cyclic alkylene group (here
Including an oxygen atom and a nitrogen atom in the chain of the alkylene group.
May be straight-chain, branched or 1 to 20 carbon atoms.
Is a cyclic alkenylene group, a hydrogen atom of the alkylene group
At least a part of which is a halogen atom and / or a hydroxyl group
The number of hydrogen atoms of the alkenylene group
A group partially substituted with a halogen atom or carbon
Indicates an alkoxyalkylene group having 2 to 20 prime numbers
R to do₃₃₈, R₃₃₉May be the same as or different from each other. R₃₄₀Represents a hydroxyl group or a halogen atom
And there are multiple R₃₄₀May be the same or different
Yes. m, n, p and q are each independently an integer of 0 to 3
M + n ≦ 5 and p + q ≦ 5. z is 0 or 1
is there. In the general formulas (AI) to (AV),
R₃₀₁~ R₃₃₇, Ra, Rb, Rc, Rd, R₀In
As a linear or branched alkyl group, it may have a substituent.
Methyl group, ethyl group, propyl group, n-butyl group,
1 to 4 carbon atoms such as sec-butyl group and t-butyl group
Individuals are listed. Cyclic alkyl groups are substituted
May have a group, cyclopropyl group, cyclopentyl
Group having 3 to 8 carbon atoms such as cyclohexyl group
Can be mentioned. R₃₀₁~ R₃₃₇, Ra and Rb alkoxy groups
As methoxy group, ethoxy group, hydroxyethoxy
Si group, propoxy group, n-butoxy group, isobutoxy
Groups, sec-butoxy groups, carbons such as t-butoxy groups
The thing of several 1-4 is mentioned. R₃₀₁~ R₃₃₇, Ra, Rb, Rc, Rd
Halogen atoms include fluorine, chlorine and bromine
A child and an iodine atom can be mentioned. R₀As the aryl group of Rc, Rd,
Phenyl group, tolyl group, methoxyphenyl group, naphthyl
6 to 14 carbon atoms which may have a substituent such as a group
Can be mentioned. These substituents are preferably carbon atoms.
1-4 alkoxy groups, halogen atoms (fluorine atoms,
Chlorine atom, iodine atom), aryl having 6 to 10 carbon atoms
Group, alkenyl group having 2 to 6 carbon atoms, cyano group, hydro
Xoxy group, carboxy group, alkoxycarbonyl group, nitro
And the like. Aroma formed by combining Rc and Rd
Ring, monocyclic or polycyclic hydrocarbons (within these rings)
May contain oxygen and nitrogen atoms)
Benzene structure, naphthalene structure, cyclohexane structure,
Examples include norbornene structure and oxabicyclo structure
The General formulas (AI) to (A) used in the present invention
III) sulfonium and iodonium compounds represented by
Is its counter anion X^-As the above formulas (C1) to (C
At least one of the carboxylic acid compounds represented by 10)
The carboxyl group (—COOH) of the seed compound is an anion
(-COO^-) Is included. In the present invention, the general formula (AIV) to
The compound represented by (AV) has the substituent X₁, X₂As
Carboxyoxidized compounds represented by the above formulas (C1) to (C10)
A carboxyl group (-
COOH) is an ester group (—COO—) substituent
including. R₃₃₈Straight chain having 1 to 30 carbon atoms
Alkyl, branched or cyclic alkyl groups (wherein alkyl
The oxygen group or nitrogen atom may be included in the chain of the ru group)
As methyl, ethyl, propyl, butyl, pliers
Hexyl, cyclohexyl, dodecyl, 1-ethoxy
Examples include ciethyl and adamantyl. C1-C20 linear, branched or
Cyclic alkenyl groups include ethenyl, propenyl,
Examples include isopropenyl and cyclohexene. C1-C20 linear, branched or
Cyclic alkynyl groups include acetylene and propenyl.
And the like. C1-C20 linear, branched or
Cyclic alkoxy groups include methoxy, ethoxy,
Lopyloxy, butoxy, cyclohexyloxy, iso
Examples include butoxy and dodecyloxy. A substituted or unsubstituted aryl having 6 to 20 carbon atoms
Reel groups include phenyl, naphthyl, anthranyl
Etc. As the substituent for the aryl group, an alkyl group,
Nitro group, hydroxyl group, alkoxy group, acyl group, alkoxy
A cicarbonyl group and a halogen atom can be mentioned. R₃₃₉Straight chain having 1 to 20 carbon atoms
, Branched or cyclic alkylene groups (wherein
Oxygen and nitrogen atoms may be included in the chain of the xylene group
), As methylene, ethylene, propylene,
Tylene, isobutylene, ethoxyethylene, cyclohex
Silene etc. are mentioned. C 1-20 linear, branched or
Examples of cyclic alkenylene groups include vinylene and arylene
Is mentioned. Specific examples are shown, but the present invention is not limited to these.
Is not something [0346] Embedded image[0347] Embedded image[0348] Embedded image[0349] Embedded image[0350] Embedded imageThe photoacid generator, that is, the general formula (A
I), general formula (AII), general formula (AIII)
The compound is described in US Pat. No. 3,734,928.
Method, Macromolecules, vol. 10, 1307 (1977), Journ
al of Organic Chemistry, vol.55, 4222 (1990), J. Ra
methods described in diat. Curing, vol. 5 (1), 2 (1978)
And further exchanging the counter anion
Can be synthesized. Represented by general formula (AIV) or general formula (AV)
N-hydroxyimide compound and carvone
React acid chloride under basic conditions or nitro
Basic conditions of benzyl alcohol and carboxylic acid chloride
It can be obtained by the following reaction. [D] Next, it is preferable to use in combination with compound a.
Fluorine-containing carboxylic acid by irradiation with active actinic radiation
The generated compound d will be described. As the fluorine-containing carboxylic acid, for example,
Fluorine-substituted aliphatic carboxylic acids and aromatic carbos
Mention may be made of acid. As a fluorine-substituted aliphatic carboxylic acid
Is acetic acid, propionic acid, n-butyric acid, isobutyric acid, valery
Anionic acid, trimethylacetic acid, caproic acid, heptanoic acid,
Prillic acid, pelargonic acid, capric acid, lauric acid,
Listinic acid, palmitic acid, stearic acid, undecane
Of aliphatic carboxylic acids such as acid, dodecanoic acid and tridecanoic acid
Fluorine substitution products are mentioned. These are hydroxyl, alcohol
May have a xy group or a halogen atom as a substituent
Yes. In addition, oxygen atoms, sulfur atoms,
Linkage of rubonyl, carboxyl, sulfonyl, etc.
Those containing groups are preferred. Preferred fluorinated aliphatic carboxylics
Examples of the acid include those represented by the following general formula:
it can. [0357] L- (CH₂) P (CF₂) Q (CH₂) R-COOH In the general formula, L represents a hydrogen atom or a fluorine atom. p and
And r are each independently an integer of 0-15, q is an integer of 1-15.
Represents a number. In this general formula, an alkyl chain hydrogen atom or
Is a fluorine atom which may be substituted with a fluorine atom
An alkyl group (preferably having 1 to 5 carbon atoms), and a fluorine atom.
An optionally substituted alkoxy group (preferably having 1 carbon atom)
-5) or may be substituted with a hydroxyl group. The above fluorine-substituted aliphatic carboxylic acid and
Therefore, the carbon number is preferably 2 to 20, more preferably
Fluorine substitution of saturated aliphatic carboxylic acids that are 4-20
It is preferable that it is a thing. Make this carbon number 4 or more
The carboxylic acid-decomposable diffusibility generated is reduced,
Reduces line width change over time from exposure to post-heating
Yes. Among them, straight chain or branched saturation having 4 to 18 carbon atoms
A fluorine-substituted aliphatic carboxylic acid is preferred. In addition, the above fluorine-substituted aromatic carbon
The boronic acid has 7 to 20 carbon atoms, more preferably 7 carbon atoms.
To 15 and more preferably 7 to 11
A fluorine-substituted product of rubonic acid is preferable. concrete
Benzoic acid, substituted benzoic acid, naphthoic acid, substituted naphtho
Toeic acid, anthracene carboxylic acid, substituted anthraceneca
Rubonic acid (wherein the substituent is alkyl group, alcohol
Xyl group, hydroxyl group, halogen atom, aryl group, acyl
Group, acyloxy group, nitro group, alkylthio group, ant
Of aromatic carboxylic acid such as
Elemental substitution may be mentioned. Among them, benzoic acid, substituted benzoic acid
A fluorine-substituted product of perfume acid is preferable. Some of these aliphatic groups are substituted with fluorine atoms.
Or aromatic carboxylic acid is a skeleton other than carboxyl group
One or more of the hydrogen atoms present in
And bones other than carboxyl groups are particularly preferred.
All hydrogen atoms present in the case were replaced with fluorine atoms
Aliphatic or aromatic carboxylic acids (perfluoro-saturated
Aliphatic carboxylic acid or perfluoroaromatic carboxylic
Acid). This will make the sensitivity even better.
The Preferably, the fluorine atom as described above is used.
Anion of a substituted aliphatic or aromatic carboxylic acid
Onium salt compounds having as counter anions
(Sulfonium salts, iodonium salts, etc.), carboxylic acid esters
Imidocarboxylate compounds having a stealth group or
Examples thereof include nitrobenzyl ester compounds. More preferably, the following general formulas (I) to (II)
Examples thereof include compounds represented by I). This will make you feel
Degree of resolution, resolution, and exposure margin are further improved. This
The compound of general formula
X of (I) to (III)^-At least one foot
Saturated aliphatic or aromatic carbos substituted with elemental atoms
Generates acid and functions as a photoacid generator. [0363] Embedded image (In the above formula, R₁ ~ R₃₇Are each independently
Hydrogen atom, straight chain, branched or cyclic alkyl group, straight chain,
Branched or cyclic alkoxy group, hydroxy group, halogen
Atom or -SR₃₈Represents a group. Where R₃₈Straight
Represents a chain, branched, cyclic alkyl group or aryl group. X
^-Is aliphatic substituted with at least one fluorine atom
Alternatively, an anion of an aromatic carboxylic acid. ) X^-Is preferably a perfluoroaliphatic carboxylic acid
Or an anion of perfluoroaromatic carboxylic acid,
Particularly preferred is a fluorine-substituted alkyl group having 4 or more carbon atoms.
It is an anion of rubonic acid. In the general formulas (I) to (III), R₁~ R
₃₈As the straight chain or branched alkyl group, a substituent may be present.
Good, methyl group, ethyl group, propyl group, n-butyl
1 carbon number such as a group, sec-butyl group, t-butyl group
There are ~ 4. As the cyclic alkyl group,
Cyclopropyl group, cyclopen which may have a substituent
3 to 8 carbon atoms such as til group and cyclohexyl group
Can be mentioned. R₁~ R₃₇As the alkoxy group of
Xoxy group, ethoxy group, hydroxyethoxy group, propoxy
Si group, n-butoxy group, isobutoxy group, sec-buto
Having 1 to 4 carbon atoms such as a xoxy group or t-butoxy group
Is mentioned. R₁~ R₃₇As halogen atoms of
Names of atomic, chlorine, bromine and iodine atoms
it can. R₃₈As the aryl group, a phenyl group,
Carbon number such as tolyl group, methoxyphenyl group, naphthyl group
6-14 things are mentioned. Aryl groups are substituted
You may have. These substituents are preferably carbon atoms.
1-4 alkoxy groups, halogen atoms (fluorine atoms,
Chlorine atom, iodine atom), aryl having 6 to 10 carbon atoms
Group, alkenyl group having 2 to 6 carbon atoms, cyano group, hydro
Xoxy group, carboxy group, alkoxycarbonyl group, nitro
And the like. General formulas (I) to (II) used in the present invention
I) Iodonium compounds or sulfoniu represented by I)
Compound is its counter anion X^-As at least 1
Saturated aliphatic or aromatic substituted with two fluorine atoms
Having an anion of carboxylic acid. These anions
Removed the hydrogen atom of the carboxylic acid (—COOH).
Anion (-COO^-). Specific examples are shown below, but the present invention is not limited to these.
It is not limited to. Specific examples of the photoacid generator represented by formula (I)
Examples (I-1f) to (I to 36f): [0373] Embedded image[0374] Embedded image [0375] Embedded image[0376] Embedded image [0377] Embedded image Specific examples of the photoacid generator represented by the general formula (II)
Examples (II-1f) to (II to 67f): [0379] Embedded image [0380] Embedded image[0381] Embedded image[0382] Embedded image[0383] Embedded image[0384] Embedded image[0385] Embedded image[0386] Embedded image[0387] Embedded imageIngredients of photoacid generator represented by general formula (III)
Examples (III-1f) to (III to 4f): [0389] Embedded image Specific examples of other photoacid generators (IV-1f)
~ (V ~ 4f): [0390] Embedded image The compounds represented by the above general formula (I) are
Obtained by reacting aromatic compounds with iodate
Salt exchange of iodonium salt to the corresponding carboxylic acid
Can be synthesized. Represented by formulas (II) and (III)
Examples of the compound include arylmagnesium bromide
Of aryl Grignard reagents and substituted or unsubstituted phenyl
The triarylsulfoxide obtained by reacting sulfoxide
Those who exchange salt with carboxylic acid
Can be synthesized. In addition, substituted or unsubstituted phenylsulfur
Methanesulfonic acid / aromatic compound corresponding to foxide
Acid catalyst such as diphosphorus pentoxide or aluminum chloride
Condensation and salt exchange method, diaryliodonium
Salts and diaryl sulfides using catalysts such as copper acetate
It can be synthesized by methods such as condensation and salt exchange. After salt exchange, once led to halide salt
Convert to carboxylate using silver reagent such as silver oxide
Method or salt exchange by using ion exchange resin
it can. In addition, carboxylic acid or calcium used for salt exchange
Use a commercially available bonate or a commercially available bonate.
It can be obtained by hydrolysis of rubonic acid halide.
Yes. Fluorine-substituted cation as an anion moiety
Rubonic acid is a telomerization method (also called telomer method).
Or oligomerization method (oligomer)
Fluoroaliphatic compounds produced by
The thing using what was guide | induced from the thing is also preferable. these
Regarding the method for producing a fluoroaliphatic compound, for example,
"Synthesis and Function of Fluorine Compounds" (Supervision: Nobuo Ishikawa, Depart
Row: 117-11 of CMC Corporation, 1987)
8 pages, “Chemistry of Organic Fluorine Compo
unds II "(Monograph 187, Ed by Milos Hudlicky and
 Attila E. Pavlath, American Chemical Society 199
5), pages 747-752. Telome
The Liza method is a large chain transfer constant such as iodide.
Tetrafluoro with alkyl halide as telogen
Radical polymerization of fluorine-containing vinyl compounds such as ethylene
Is a method of synthesizing telomers (examples in Scheme-1
Indicated). In the telomer synthesis, the carbon chain length
A mixture of different compounds is obtained, which is mixed
The product may be used as it is, or may be used after purification. Weight ratio of the total amount of compound a and compounds b to d
Is usually 1/1 to 50/1, preferably 1/1 to 10 /
1, particularly preferably 2/1 to 5/1. The total amount of compound a and compounds b to d is the composition
0.5 to 20% by weight with respect to the total solid content, preferably
Is 0.75 to 15 wt%, more preferably 1 to 10 wt%
% Range. Compound a and compounds b to d are plural
It may contain seeds. The composition of the present invention contains an organic basic compound.
Can be used. This improves stability during storage.
And line width change due to PED is further reduced
Therefore, it is preferable. Preferred organics that can be used in the present invention
Basic compounds are compounds that are more basic than phenol.
It is a thing. Of these, nitrogen-containing basic compounds are preferred. As a preferred chemical environment, the following formula (A)
(E) The structure can be mentioned. [0401] Embedded imageFurther preferred compounds are nitrogen-containing cyclic compounds.
Product (also called cyclic amine compound) or different in one molecule
A nitrogenous base having two or more nitrogen atoms in a chemical environment
It is a sex compound. The cyclic amine compound has a polycyclic structure.
More preferably. Preferred tools for cyclic amine compounds
Examples of the compounds include compounds represented by the following general formula (F).
I can get lost. [0404] Embedded image In formula (F), Y and Z are each independently
A straight chain, which may contain a
Represents a cyclic alkylene group. Here, the hetero atom includes a nitrogen atom,
A sulfur atom and an oxygen atom are mentioned. As an alkylene group
Preferably has 2 to 10 carbon atoms, more preferably 2 to 2 carbon atoms.
There are five. As a substituent of the alkylene group, carbon
1-6 alkyl groups, aryl groups, alkenyl groups
Other examples include halogen atoms and halogen-substituted alkyl groups.
It is. In addition, the compound represented by formula (F)
Examples of the body include the compounds shown below. [0408] Embedded image Among the above, 1,8-diazabicyclo
[5.4.0] Undec-7-ene, 1,5-diazabi
Cyclo [4.3.0] non-5-ene is particularly preferred. [0410] Nitrogen atoms of different chemical environments in one molecule
Particularly preferred as a nitrogen-containing basic compound having two or more.
Or a substituted or unsubstituted amino group and a nitrogen atom.
Compounds containing both ring structures or alkylamino groups
It is a compound which has this. Preferred examples include substitution
Or unsubstituted guanidine, substituted or unsubstituted
Minopyridine, substituted or unsubstituted aminoalkylpi
Lysine, substituted or unsubstituted aminopyrrolidine, substituted
Or unsubstituted indazole, substituted or unsubstituted
Pyrazole, substituted or unsubstituted pyrazine, substituted
Or unsubstituted pyrimidine, substituted or unsubstituted pre
Substituted or unsubstituted imidazoline, substituted or
Unsubstituted pyrazoline, substituted or unsubstituted piperazi
Substituted, unsubstituted aminomorpholine, substituted
Or unsubstituted aminoalkylmorpholine.
It is. Preferred substituents are amino group, aminoalkyl
Group, alkylamino group, aminoaryl group, aryl group
Mino group, alkyl group, alkoxy group, acyl group, acylo
Xyl group, aryl group, aryloxy group, nitro group, water
An acid group and a cyano group. As particularly preferred compounds, guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetrame
Tilguanidine, 2-aminopyridine, 3-aminopyri
Gin, 4-aminopyridine, 2-dimethylaminopyridy
4-dimethylaminopyridine, 2-diethylamino
Pyridine, 2- (aminomethyl) pyridine, 2-amino
-3-methylpyridine, 2-amino-4-methylpyridy
, 2-amino-5-methylpyridine, 2-amino-6
-Methylpyridine, 3-aminoethylpyridine, 4-a
Minoethylpyridine, 3-aminopyrrolidine, piperazi
, N- (2-aminoethyl) piperazine, N- (2-
Aminoethyl) piperidine, 4-amino-2,2,6,6
-Tetramethylpiperidine, 4-piperidinopiperidi
, 2-iminopiperidine, 1- (2-aminoethyl)
Pyrrolidine, pyrazole, 3-amino-5-methylpyra
Sol, 5-amino-3-methyl-1-p-tolylpyra
Zole, pyrazine, 2- (aminomethyl) -5-methyl
Pyrazine, pyrimidine, 2,4-diaminopyrimidine,
4,6-dihydroxypyrimidine, 2-pyrazoline, 3
-Pyrazoline, N-aminomorpholine, N- (2-a
Minoethyl) morpholine, trimethylimidazole,
Triphenylimidazole, methyldiphenylimidazo
However, it is not limited to this. These nitrogen-containing basic compounds are used alone.
Or two or more are used together. Nitrogen-containing basic compounds
Is used in a positive resist composition (excluding the solvent) 10
Usually 0.001 to 10 parts by weight, preferably 0 parts by weight
Or 0.01 to 5 parts by weight. When the amount is less than 0.001 part by weight, the above effect can be obtained.
I can't. On the other hand, when the amount exceeds 10 parts by weight, the sensitivity is reduced and non-dew
There is a tendency for the developability of the light part to deteriorate. In the chemically amplified positive resist composition of the present invention,
If necessary, surfactants, dyes, pigments, plastics
That promotes solubility in photosensitizers, photosensitizers and developers.
Containing a compound having two or more enolic OH groups
Can. The positive resist composition of the present invention has an interface.
It is preferable to contain an activator. Specifically, polio
Xylethylene lauryl ether, polyoxyethylenes
Tearyl ether, polyoxyethylene cetyl ether
And polyoxyethylene oleyl ether
Siethylene alkyl ethers, polyoxyethylene ether
Cutylphenol ether, polyoxyethylene nonyl
Polyoxyethylene alkyla such as phenol ether
Ryl ethers, polyoxyethylene / polyoxypro
Pyrene block copolymers, sorbitan monolaurate
, Sorbitan monopalmitate, sorbitan monostete
Allate, sorbitan monooleate, sorbitan tri
Solvita such as oleate, sorbitan tristearate
Fatty acid esters, polyoxyethylene sorbitan
Nolaurate, polyoxyethylene sorbitan monopal
Mitate, polyoxyethylene sorbitan monosteare
, Polyoxyethylene sorbitan trioleate,
Polyoxyethylene sorbitan tristearate, etc.
Noni such as reoxyethylene sorbitan fatty acid esters
ON-based surfactant, F-top EF301, EF30
3, EF352 (made by Shin-Akita Kasei Co., Ltd.), Mega Fuck
F171, F173, F176, F189, R08 (large
Nippon Ink Co., Ltd.), Florad FC430, FC4
31 (manufactured by Sumitomo 3M), Asahi Guard AG7
10, Surflon S-382, SC101, SC10
2, SC103, SC104, SC105, SC106
Fluorosurfactants such as Asahi Glass Co., Organo
Siloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
Manufactured) and acrylic acid or methacrylic acid (co) polymerization
Polyflow No. 75, no. 95 (Kyoeisha Yushi Chemical Co., Ltd.)
Industry Co., Ltd.), Troisol S-366 (Troy Chemical)
For example). Among these surfactants, fluorine type
Silicone surfactants are easy to apply and reduce development defects
Is preferable. The amount of the surfactant added is in the composition of the present invention.
Usually 0.01% by weight to 2% based on the solid content of the whole composition
% By weight, preferably 0.01% to 1% by weight. These surfactants may be used alone or in combination.
Two or more kinds can be used in combination. In the resin of the present invention, JP-A-9-31.
Compared to conventional resin containing acetal group such as 9092
Acid contained as an impurity (this is mainly acid generation
Impurities in the agent, or touch used when synthesizing the resin of the present invention
The effect of the content of (derived from the medium) was observed. That is, impurities are contained in the resist composition of the present invention.
If the acid content is more than 500ppm
Excellent pattern profile shape which is the effect of the present invention
Less time for storage in vacuum and vacuum chambers
Line width variation is impaired. Accordingly, in the resist composition of the present invention,
Contains acid contained as an impurity in the resist composition
It is necessary to keep the amount below 500ppm, which is preferable
Or 200 ppm or less, more preferably 100 pp.
m or less. Furthermore, the following spectral sensitizers are used.
Add and use far ultraviolet rays where the acid generator used has no absorption
By sensitizing to the long wavelength region, the chemically amplified type of the present invention
Diresist can be sensitive to i or g line
The Specific examples of suitable spectral sensitizers include:
Nzophenone, p, p'-tetramethyldiaminobenzo
Phenone, p, p'-tetraethylethylaminobenzo
Phenone, 2-chlorothioxanthone, anthrone, 9
-Ethoxyanthracene, anthracene, pyrene, peri
Len, phenothiazine, benzyl, acridine orene
Di, benzoflavin, cetoflavin-T, 9,10-di
Phenylanthracene, 9-fluorenone, acetophene
Non, phenanthrene, 2-nitrofluorene, 5-ni
Troacenaphthene, benzoquinone, 2-chloro-4-ni
Troaniline, N-acetyl-p-nitroaniline, p
-Nitroaniline, N-acetyl-4-nitro-1-na
Phthylamine, picramide, anthraquinone, 2-ethyl
Luanthraquinone, 2-tert-butylanthraquinone,
1,2-benzanthraquinone, 3-methyl-1,3-di
Aza-1,9-benzanthrone, dibenzalaceto
1,2-naphthoquinone, 3,3'-carbonyl-bis
(5,7-dimethoxycarbonylcoumarin) and corone
However, the present invention is not limited to these. Phenolic to promote solubility in developer
Examples of the compound having two or more oleic OH groups include polyoxy
And droxy compounds, preferably polyhydroxy
Compounds include phenols, resorcin, phlorogluci
, Phloroglucid, 2,3,4-trihydroxybenzo
Phenone, 2,3,4,4'-tetrahydroxybenzof
Enon, α, α ', α' '-Tris (4-hydroxypheny
L) -1,3,5-Triisopropylbenzene, Tris
(4-hydroxyphenyl) methane, tris (4-hydride)
Loxyphenyl) ethane, 1,1'-bis (4-hydro)
Xylphenyl) cyclohexane. Chemically amplified positive resist composition of the present invention
Is dissolved in a solvent that dissolves each of the above components and coated on the support.
As a solvent that can be used
Is ethylene dichloride, cyclohexanone, cyclo
Pentanone, 2-heptanone, γ-butyrolactone,
Tyl ethyl ketone, ethylene glycol monomethyl ether
Tellurium, ethylene glycol monoethyl ether, 2-methyl
Toxiethyl acetate, ethylene glycol monoethyl
Ruether acetate, propylene glycol monomethyl
Luether, propylene glycol monomethyl ether
Acetate, toluene, ethyl acetate, methyl lactate, lactic acid
Ethyl, methyl methoxypropionate, ethoxypropionate
Ethyl onate, methyl pyruvate, ethyl pyruvate,
Propyl pyruvate, N, N-dimethylformamide,
Dimethyl sulfoxide, N-methylpyrrolidone, tetra
Hydrofuran or the like is preferable.
Are mixed and used. The chemical amplification type positive resist composition is a finely divided resin.
Substrates such as those used in the manufacture of densely integrated circuit elements (eg,
Spinner, coater on recon / silicon dioxide coating)
After application by an appropriate application method such as
Exposure, baking, and developing
A strike pattern can be obtained. Chemically amplified positive resist composition of the present invention
Examples of the developer include sodium hydroxide and hydroxide.
Potassium, sodium carbonate, sodium silicate, phosphoric acid
Sodium, sodium metasilicate, ammonia water, etc.
Inorganic alkalis, ethylamine, n-propylamine, etc.
Primary amines, diethylamine, di-n-butylamino
Secondary amines such as triethylamine, triethylamine, methyldiethyl
Tertiary amines such as ruamine, dimethylethanolamine
Alcohol amines such as ethanol and triethanolamine,
Amides such as rumamide and acetamide, tetramethyl
Ammonium hydroxide, trimethyl (2-hydroxy
Siethyl) ammonium hydroxide, tetraethyla
Ammonium hydroxide, tributylmethylammonium
Muhydroxide, tetraethanolammonium hydro
Koxide, methyltriethanolammonium hydroxy
Benzylmethyldiethanolammonium hydroxide
Sid, benzyldimethylethanolammonium hydro
Koxide, benzyltriethanolammonium hydroxide
Sid, tetrapropylammonium hydroxide, tet
Quaternary ammonia such as rabutylammonium hydroxide
Um salt, pyrrole, piperidine and other cyclic amines
There is an aqueous solution of potash. [0428] The present invention will be described more specifically below.
However, the present invention is not limited to these. Synthesis Example I-1 Synthesis of vinyl ether
83.1 g of p-cyclohexylphenol (0.5 mole)
Is dissolved in 300 ml of toluene and then 2-chloro
Add 150 g of roethyl vinyl ether and further hydroxylate
Sodium 25g, tetrabutylammonium bromide
Add 5g and 60g of triethylamine at 120 ℃
The mixture was heated and stirred for 5 hours. The reaction solution was washed with water and distilled off under reduced pressure.
Remove excess chlororetyl vinyl ether and toluene
It was. From the obtained oil, by distillation under reduced pressure,
Some p-cyclohexylphenoxyethyl vinyl ether
(X-1) was obtained. [Synthesis Examples I-2, 3, 4, 5, 6, 7,
8, 9] Vinyl as shown below in the same manner as in Synthesis Example I-1.
Ether X-2, X-3, X-4, X-5, X-6, X
-7, X-8, and X-9 were obtained. [0431] Embedded image [0432] Embedded image [Synthesis Example II-1] p-acetoxystyrene
Dissolve 32.4 g (0.2 mol) in 120 ml of butyl acetate.
And azobisisothene at 80 ° C. under nitrogen flow and stirring.
Butyronitrile (AIBN) 0.033g for 2.5 hours
Add 3 times, and finally continue stirring for another 5 hours
The polymerization reaction was carried out. The reaction mixture was hexane 1200.
The solution was poured into ml to precipitate a white resin. Obtained resin
After drying, it was dissolved in 150 ml of methanol. This water
Sodium oxide 7.7g (0.19mol) / water 50ml
Add an aqueous solution of
Decomposed. Then add 200ml of water to dilute, and salt
A white resin was precipitated by neutralization with an acid. Filter this resin
Washed with water and dried. Tetrahydrofuran 200
Dissolve in ml and drop into 5 L ultrapure water with vigorous stirring
Below, re-precipitation was performed. This reprecipitation operation was repeated three times. Gain
The resulting resin in a vacuum dryer at 120 ° C for 12 hours
Poly (p-hydroxystyrene) alkali-soluble tree
Fat R-1 was obtained. The weight average molecular weight of the obtained resin is 15
000. Synthesis Example II-2 Dehydration and steaming based on conventional methods
Distilled and purified p-tert-butoxystyrene monomer 3
5.25 g (0.2 mol) and styrene monomer
21 g (0.05 mol) of tetrahydrofuran 100 m
I. Azo at 80 ° C under nitrogen flow and stirring
0.033 g of bisisobutyronitrile (AIBN)
Add 3 times every 2.5 hours and finally stir for another 5 hours
The polymerization reaction was carried out by continuing. Hexadecimal reaction solution
The solution was added to 1200 ml to precipitate a white resin. Gain
The obtained resin was dried and then added to 150 ml of tetrahydrofuran.
Dissolved. Add 4N hydrochloric acid and heat to reflux for 6 hours.
And then re-precipitation in 5 L of ultrapure water
The resin was filtered off, washed with water and dried. Tetra
Dissolve in 200 ml of hydrofuran and intensify in 5 L of ultrapure water
The solution was dropped and re-precipitated with vigorous stirring. This re-sink operation
Repeated 3 times. The obtained resin was 120 in a vacuum dryer.
Dry at 12 ° C. for 12 hours, and poly (p-hydroxystyrene /
Styrene) copolymer alkali-soluble resin R-2 was obtained.
The weight average molecular weight of the obtained resin was 12,000. [Synthesis Example II-3] p-acetoxystyrene
32.4 g (0.2 mol) and methyl methacrylate
7.01 g (0.07 mol) to 120 ml butyl acetate
Dissolve the azobisin at 80 ° C under nitrogen flow and stirring.
Sobutyronitrile (AIBN) 0.033g 2.5 hours
Add three times at a time, and finally continue stirring for another 5 hours.
Then, a polymerization reaction was performed. The reaction solution was hexane 120.
The solution was added to 0 ml to precipitate a white resin. The resulting tree
The fat was dried and then dissolved in 200 ml of methanol. to this
Sodium hydroxide 7.7g (0.19mol) / water 50m
Add 1 g of aqueous solution and heat to reflux for 1 hour.
Water split. Then add 200ml of water to dilute,
Neutralization with hydrochloric acid precipitated a white resin. Filter this resin
Separated, washed with water and dried. Tetrahydrofuran 20
Dissolve in 0 ml and stir vigorously in 5 L of ultrapure water.
Dropping and reprecipitation were performed. This reprecipitation operation was repeated three times.
The obtained resin is dried in a vacuum dryer at 120 ° C. for 12 hours.
Poly (p-hydroxystyrene / methacrylic acid methyl)
I) A copolymer alkali-soluble resin R-3 was obtained. Obtained
The resin had a weight average molecular weight of 10,000. [Synthesis Example II-4] manufactured by Nippon Soda Co., Ltd.
Al (p-hydroxystyrene) (VP8000)
Potassium-soluble resin R-4 was designated. The weight average molecular weight is 980
0. [Synthesis Example III-1] Alkali-soluble resin R-4 2 obtained in Synthesis Example II-4
0g Tetrahydrofuran 80ml Vinyl ether X-1 obtained in Synthesis Example I-1 6.5
0g In a flask and p-toluenesulfonic acid 10 m
g was added and stirred at room temperature for 18 hours. Pyridine 50
After adding mg, the reaction solution was vigorously poured into 5 L of ultrapure water.
Dropping and reprecipitation were performed while stirring. Vacuum the resulting resin
Dry in a dryer at 70 ° C. for 12 hours, according to the present invention
An alkali-soluble resin B-1 having a substituent was obtained. [Synthesis Examples III-2 to III-10]
Using the indicated alkali-soluble resin and vinyl ether,
Similar to Example III-1 having substituents according to the present invention
Alkali-soluble resins B-2 to B-15 were obtained. [0439] [Table 1] [Synthesis Examples IV-1 to IV-4] Shown in Table 2 below
Alkali-soluble resin and ethyl vinyl resin represented by the following formula:
Ruether (Y-1), naphthyloxyethyl vinyl ester
Ether (Y-2), (benzyloxyethoxy) ethyl
Resin C-1 to C-3 using vinyl ether (Y-3)
Got. [0441] Embedded image [0442] [Table 2] [Synthesis Example V-1] <Triphenylsulfoni
Synthesis of umnonafluorobutanesulfonate (VII-4)
> 20g of triphenylsulfonium iodide in methanol
12.5 g of silver oxide is added to this solution.
The mixture was stirred at room temperature for 4 hours. The reaction solution is filtered to obtain a silver compound
After removing the nonafluorobutane sulfonate into this solution
Acid 14.9g was added and the solution was concentrated. Obtained
Add 300 ml of diisopropyl ether to the oily product
After stirring well, diisopropyl ether is decanted.
The operation of removing the toner was repeated twice. The oil obtained was
When dried, 18 g of the desired product was obtained. [Synthesis Example V-2] <Triphenylsulfoni
Um 4-dodecylbenzenesulfonate (PAG4-
Synthesis of 1)> Triphenylsulfonium iodide 10 g
Is dissolved in 500 ml of methanol, and silver oxide 4.
44 g was added and stirred at room temperature for 4 hours. Filter the reaction solution
After removing the silver compound, 4-dodecylbenzase is added to this solution.
4.67 g of sulfonic acid is added, and this solution is added.
Concentrated. Diisopropyl ether 3 was added to the obtained oil.
After adding 00 ml and stirring well, diisopropyl ether
The operation of removing ether by decanting was repeated twice. Obtained
The oily product was dried under reduced pressure to obtain 6 g of the desired product. [Synthesis Example V-3] <Triphenylsulfoni
Synthesis of umnonafluoropentanoate (II-4f)
Rephenylsulfonium iodide (20 g) in methanol 5
Dissolve in 00ml, add 12.5g of silver oxide to this
Stir for 4 days at room temperature. Filter the reaction solution to remove the silver compound.
After this, nonafluoropentanoic acid in this solution
14.9 g was added and the solution was concentrated. Oil obtained
Add 300 ml of diisopropyl ether
After stirring, diisopropylpropyl ether is removed by decantation.
The operation was repeated twice. Dry the resulting oil under reduced pressure
As a result, 18 g of the desired product was obtained. As surfactant (F-1), mega fat
C08 (Dainippon Ink Co., Ltd.) was used. As the surfactant (F-2), Troisol
S-366 (manufactured by Troy Chemical Co., Ltd.) was used. (Examples 1 to 12, Comparative Examples 1 to 6) [Preparation and Evaluation of Resist Composition] Each material shown in Table 3 below
PGMEA (propylene glycol monomethyl ether
Ruacetate) dissolved in 8g, 0.2μm filter
To prepare a resist solution. Surfactant
The amount used was 0.0035 g. Using this resist solution, use a spin coater.
And applied onto a silicon wafer at 130 ° C., 60 ° C.
Dry on a vacuum adsorption-type hot plate for 2 seconds to obtain a film thickness of 0.
A 3 μm resist film was obtained. [0450] [Table 3] Each photoacid generator used in the examples and
Organic base compounds are shown below. [0452] Embedded imageAn electron beam irradiation device (acceleration is applied to this resist film.
Irradiation was performed using a voltage of 50 KeV. 100 after irradiation
Heat on a hot plate for 60 seconds and immediately add 0.2
6N tetramethylammonium hydroxide (T
MAH) soaked in aqueous solution for 60 seconds, rinsed with water for 30 seconds
And dried. Silicon wafer thus obtained
-Observe the upper pattern with a scanning electron microscope
The performance of was evaluated. The results are shown in Table 4. The resolving power is 0.15 μm line and spec.
Limit solution for exposure dose to reproduce the mask pattern
Represents image power. The obtained resist pattern was measured with an optical microscope.
Or, it is observed by SEM, and reverse taper of resist pattern
The degree of was observed. Degree of inclination of reverse taper of pattern
Matches with very little (almost rectangular profile)
◎, less is ○, pattern reverse taper is clear
What was observed was set as x. Also, the resist film obtained as described above is
After leaving in an electron beam irradiation device for 240 minutes under high vacuum,
As above, exposure and development to form a resist pattern
It was. As described above, obtained by leaving under high vacuum for 240 minutes
Limit resolution line width (A) of the pattern and do not leave under high vacuum
Measure the critical resolution line width (B) of the pattern obtained
The rate of change was calculated as follows. Its value is small
Better. [0458] Fluctuation rate = {1- | (B)-(A) | / (B)} × 100 [0459] [Table 4] As is apparent from the results in Table 4, the present invention
The positive resist compositions of the respective examples are satisfactory.
However, the resist composition of each comparative example is
Line width changes due to resist pattern shape and holding time
I was dissatisfied with the movement. (Examples 13 to 24, Comparative Examples 7 to 10)
As shown in Table 5, general formula (I) and general formula (III)
Decomposed by the action of an acid having a structural unit represented by
A resin with increased solubility in an alkaline developer, and / or
Or the above general formula (I), general formula (II) and general formula (II)
Decomposed by the action of an acid having the structural unit represented by I)
And a resin with increased solubility in an alkaline developer,
Furthermore, it decomposes by the action of acid and dissolves in alkaline developer
Examples 1 to 12 except that a compound with increased properties was added
Similarly, a resist solution is prepared and 0.3 μm is similarly obtained.
A resist film was obtained. In the same manner as in Examples 1 to 12, the resolution and resolution
Dist pattern profile, pull in vacuum chamber
Table 6 shows the results of the evaluation of line width variation due to settling.
The [0463] [Table 5] In addition, the dissolution inhibiting compounds used in the examples are shown below.
Shown below. [0465] Embedded image[0466] [Table 6] As is apparent from the results in Table 6, the present invention
The positive resist composition of each of these examples is particularly a resist.
Pattern profile, leaving in vacuum chamber
The line width variation caused by
Although satisfactory results were obtained, the resist composition of each comparative example
In particular, resist pattern profiles, vacuum channels
Unsatisfied with line width fluctuations due to placement in the bar
It was. [0468] According to the present invention, a resist pattern processor is obtained.
Line width change due to file and placement in vacuum chamber
Provides chemically amplified positive resist compositions with improved dynamics
Is done.

Continued front page    (72) Inventor Koji Shirakawa             4,000 Kawajiri, Yoshida-cho, Kashihara-gun, Shizuoka Prefecture Fuji             Within Shin Film Co., Ltd. (72) Inventor Takahashi Table             4,000 Kawajiri, Yoshida-cho, Kashihara-gun, Shizuoka Prefecture Fuji             Within Shin Film Co., Ltd. (72) Inventor Satoshi Fujimori             4,000 Kawajiri, Yoshida-cho, Kashihara-gun, Shizuoka Prefecture Fuji             Within Shin Film Co., Ltd. F-term (reference) 2H025 AA03 AB16 AC04 AC05 AC06                       AD03 BE00 BE10 BG00 CB17                       CB41 FA17                 4J100 AB02R AB07P AB07Q AB07R                       BA02P BA02R BA03Q BA04P                       BA05R BA12P BA15P BA15R                       BA34R BC03P BC04P BC04R                       BC09P BC43P CA04 CA05                       FA03 FA19 JA38

Claims (1)

What is claimed is: (a) a resin having a structural unit containing a group represented by the following general formula (X), which is decomposed by the action of an acid to increase the solubility in an alkali developer And (b)
A resist composition for positive electron beam, X-ray or EUV, comprising a compound that generates an acid upon irradiation with actinic radiation. [Chemical 1] In formula (X), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, W represents a divalent organic group, and R ₃ represents total carbon. An alkyl group that may have a substituent of 11 to 20, an aryl group that may have a substituent of 11 to 30 carbon atoms, and an aralkyl that may have a substituent of 12 to 30 carbon atoms Represents a group.