JP2003280199A - Positive resist composition for electron beam, x-radiation or euv - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition for an electron beam, X- radiation or EUV (extreme-ultraviolet radiation) improved in resist pattern profile and variation of line width due to keeping in a vacuum chamber. <P>SOLUTION: The positive resist composition comprises (a) a resin which has a structural unit containing an acid-decomposable group having a structure represented by formula (I) and is decomposed by the action of an acid to increase solubility in an alkali developer and (b) a compound which generates and acid upon irradiation with an active radiation, wherein R1 and R2 may be the same or different and are each H or a 1-4C alkyl; W is a divalent organic group; and X is -S-, -N(R4)CO-, -Se-, -CO-, -COO-, -OCO-, -SO- or -SO<SB>2</SB>- (where R4 is H or a 1-4C alkyl). <P>COPYRIGHT: (C)2004,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.
Depending on the reaction
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 by radiation exposure
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. 10-87724,
Containing ketone, ester, sulfonyl, amide groups
If the resin introduced with a settal group is effective in reducing standing waves
It is disclosed as. Japanese Patent Laid-Open No. 10-306120
In this publication, an acetal group unit containing an ester group is used.
A resin having a base is disclosed. However, these
In the case of a resin having an acetal group of
When used, the effect of electron backscattering appears strongly and
The resist pattern is a reverse taper profile
It became. Furthermore, in the vacuum chamber of the electron beam irradiation device
Improvement of the line width variation due to the holding time has also been desired. [0005] 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 [0006] SUMMARY OF THE INVENTION The present inventor has found such a present situation.
As a result of diligent investigation, an acid-decomposable group having a specific structure
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 structure.
It is completed. (1) (a) represented by the following general formula (I)
It has a structural unit containing a group that decomposes by the action of acid.
A resin having increased solubility in an alkaline developer, and
(B) containing a compound that generates an acid upon irradiation with actinic radiation.
Positive electron beam, X-ray or EUV characterized by having
Resist composition. [0008] [Chemical 2] In the formula (I), R1 and R2 may be the same or different.
May be a hydrogen atom or an alkyl having 1 to 4 carbon atoms.
W represents a divalent organic group, X represents —S—, —
N (R4) CO-, -Se-, -CO-, -COO-,
-OCO-, -SO-, or -SO₂-Represents (here
R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R3 is a chain alkyl group which may have a substituent,
A cyclic alkyl group which may have a substituent, a substituent
A good aryl group or aralkyl optionally having a substituent
Represents a group. ) The preferred embodiments are described below. (2) The resin of (a) is further represented by the following general formula (II)
(1) above, characterized by having a structural unit
A resist composition for positive type electron beam, X-ray or EUV. [0011] [Chemical 3]In the formula (II), R21 is a hydrogen atom or methyl.
R22 represents a group that is not decomposed by the action of an acid.
R23 represents a hydrogen atom, a halogen atom, an alkyl group, an
Reel group, alkoxy group, acyl group or acyloxy group
Represents. n represents an integer of 1 to 3. (3) (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)
As described in (1) or (2) above, which is one type
A resist composition for positive type electron beam, X-ray or EUV. [0014] [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 alkylsulfurs having 1 to 12 carbon atoms
A part or all of the hydrogen atom is an phosphonic acid anion.
May be substituted with a nitrogen atom, or (b) branched or
Is a cyclic alkyl group having 8 or more carbon atoms and an alkoxy group
Having at least one group selected from the group of
A linear, branched or cyclic alkyl group having 4 to 7 carbon atoms and
And at least 2 groups selected from the group of alkoxy groups
1 to 3 linear or branched C 1 to C 3 carbon atoms
There are few groups selected from the group of a kill group and an alkoxy group.
Have at least 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. [0016] [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. [0018] [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 [0020] [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 [0022] [Chemical 8] In the formula (A-6), Y has a substituent.
Linear, branched, cyclic alkyl groups, which may be substituted
Good aralkyl group, [0024] [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 an optionally substituted straight chain,
Heteroalkylene group, optionally substituted heteroatom
A monocyclic or polycyclic alkylene group which may contain
Linear, branched alkenylene groups, substituted
A single ring optionally containing heteroatoms or
Polycyclic alkenylene group, optionally substituted aryl
Rene group and an optionally substituted aralkylene group are shown.
X is bonded to another imide sulfonate residue.
Also good. Ar₁-SO₂-SO₂-Ar₂        (A-7) In formula (A-7), Ar₁, Ar₂Are the same or different
Or a substituted or unsubstituted aryl group. (4) Furthermore, by irradiation with actinic radiation,
The following general formulas (B-1) and (B-
2), (B-3), (B-4) and (B-5)
Containing at least one of the following compounds:
The positive electron beam, X-ray or EUV described in (3) above
Resist composition. [0027] Embedded image In the formulas (B-1) and (B-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. Y^-(A) linear
, Branched, or cyclic C1-C12 alkylcal
A part or all of the hydrogen atom is an anion of boric acid.
May be substituted with a nitrogen atom, or (b) branched or
Is a cyclic alkyl group having 8 or more carbon atoms and an alkoxy group
Having at least one group selected from the group of
A linear, branched or cyclic alkyl group having 4 to 7 carbon atoms and
And at least 2 groups selected from the group of alkoxy groups
1 to 3 linear or branched C 1 to C 3 carbon atoms
There are few groups selected from the group of a kill group and an alkoxy group.
Have at least 3 or 1 to 5 halogen atoms
Or linear or branched carbon having 1 to 10 carbon atoms.
Benzenecarboxylic acid having a ter group, naphthalenecarbo
An anion of acid or anthracene carboxylic acid. [0029] Embedded image In the formula (B-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. Y^-Is as defined above. m, n,
p and q each represent an integer of 1 to 3. [0031] Embedded image In the formula (B-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, Y^-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 [0033] Embedded image In the formula (B-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, Y^-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 (5) Decomposes by the action of an acid to produce an alkali
It may further contain a compound that increases solubility in the developer.
Any one of (1) to (4) above,
Resist composition for positive electron beam, X-ray or EUV. (6) The acid content contained in the resist composition is
The above (1) to 500 ppm or less,
(5) Positive electron beam, X-ray or EU according to any one of
Resist composition for V. (7) By electron beam irradiation with a high acceleration voltage of 40 KeV or higher
Any of the above (1) to (6) used for pattern formation
Resist composition for positive electron beam, X-ray or EUV
Stuff. [0036] The present invention will be described in detail below. (A) containing a group represented by the above general formula (I)
It has a structural unit and decomposes by the action of an acid
Compound with general solubility in re-developer (I)
As the alkyl group for R1 and R2 in FIG.
Ethyl group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, sec-butyl group, t-butyl group
Examples thereof include an alkyl group having 1 to 4 carbon atoms. W
As the divalent organic group, it preferably has a substituent.
A linear, branched or cyclic alkylene group,
Arylene, heteroarylene, and aralkylene groups
And -S-, -CO-, -N (R4)-, -SO-,
-SO₂-, -COO-, -N (R4) SO₂-(Here
R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Or a divalent combination of two or more of these groups
The group can be mentioned. X is -S-, -N (R4).
CO-, -Se-, -CO-, -COO-, -OCO
-, -SO-, or -SO₂-(Where R4 is
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), preferably
Or -S-, -SO-, -SO₂-, -N (R4)-
Represents. Specific examples of the alkyl group of R4 in W and X
Examples thereof include those similar to the above R1. The above-mentioned linear alkyl which may have a substituent for R3
The kill group is preferably 1 to 20 carbon atoms, more preferably
Preferably it is a straight chain with 1 to 18 carbon atoms, but it is branched.
For example, methyl group, ethyl group, n-pro
Pill group, i-propyl group, n-butyl group, i-butyl
Group, t-butyl group, n-pentyl group, i-pentyl group,
t-pentyl group, n-hexyl group, i-hexyl group, t
-Hexyl group, n-heptyl group, i-heptyl group, t-
Heptyl group, n-octyl group, i-octyl group, t-octyl group
Cutyl group, n-nonyl group, i-nonyl group, t-nonyl
Group, n-decyl group, i-decyl group, t-decyl group, n-
Undecyl group, i-undecyl group, n-dodecyl group, i
-Dodecyl group, n-tridecyl group, i-tridecyl group,
n-tetradecyl group, i-tetradecyl group, n-penta
Decyl group, i-pentadecyl group, n-hexadecyl group,
i-hexadecyl group, n-heptadecyl group, i-hepta
Decyl group, n-octadecyl group, i-octadecyl group,
Examples include n-nonadecyl group and i-nonadecyl group.
it can. These substituents are represented by the substituents shown below.
May be substituted. The above cyclic alkyl optionally having a substituent for R3
The kill group is preferably 3 to 20 carbon atoms, more preferably
Preferably a ring with 3 to 18 carbon atoms and up to 20 carbon atoms
Even when it is formed, it may be a cyclic alkyl having a substituent,
For example, cyclopropyl group, cyclobutyl group, cyclope
Nyl, cyclohexyl, cycloheptyl, cycl
Looctyl, cyclononyl, cyclodecyl, cycl
Loundecyl, cyclododecyl, cyclotridecyl
Group, cyclotridecyl group, cyclotetradecyl group, cycl
Lopentadecyl group, cyclohexadecyl group, cyclohept
Tadecyl group, cyclooctadecyl group, cyclononadecyl
Group, 4-cyclohexylcyclohexyl group, 4-n-he
Xylcyclohexyl group, pentanylcyclohexyl
Group, hexyloxycyclohexyl group, pentanyloxy
Cicyclohexyl group and the like can be mentioned. Here
Substituted cyclic alkyl groups other than the above are used within the above range.
Can be used. These substituents are shown below.
It may be substituted with a substituent. Ali which may have a substituent of the above R3
As a group, it preferably has 6 to 30 carbon atoms, preferably
Has 6 to 25 carbon atoms, for example, a phenyl group, a tolyl group,
Xylyl group, ethylphenyl group, propylphenyl group,
Methoxyphenyl group, ethoxyphenyl group, propylo
Xylphenyl group, 4-cyclopentylphenyl group, 4-
Cyclohexylphenyl group, 4-cycloheptenyl phen
Nyl group, 4-cyclooctanylphenyl group, 2-cyclo
A pentylphenyl group, a 2-cyclohexylphenyl group,
2-cycloheptenylphenyl group, 2-cyclooctani
Ruphenyl group, 3-cyclopentylphenyl group, 3-
Chlohexylphenyl group, 3-cycloheptenyl phenyl
Group, 3-cyclooctanylphenyl group, 4-cyclope
Ntyloxyphenyl group, 4-cyclohexyloxy
Enyl group, 4-cycloheptenyloxyphenyl group, 4
-Cyclooctanyloxyphenyl group, 2-cyclopent
Tyloxyphenyl group, 2-cyclohexyloxyphene
Nyl group, 2-cycloheptenyloxyphenyl group, 2-
Cyclooctanyloxyphenyl group, 3-cyclopentyl
Ruoxyphenyl group, 3-cyclohexyloxypheny
Group, 3-cycloheptenyloxyphenyl group, 3-
Crooctanyloxyphenyl group, 4-n-pentylph
Enyl group, 4-n-hexylphenyl group, 4-n-hept
Tenenylphenyl group, 4-n-octanylphenyl group, 2
-N-pentylphenyl group, 2-n-hexylphenyl
Group, 2-n-heptenylphenyl group, 2-n-octani
Ruphenyl group, 3-n-pentylphenyl group, 3-n-
Hexylphenyl group, 3-n-heptenylphenyl group,
3-n-octanylphenyl group, 2,6-di-isopropyl
Pyrphenyl group, 2,3-di-isopropylphenyl
Group, 2,4-di-isopropylphenyl group, 3,4-di
-Isopropylphenyl group, 3,6-di-t-butyl
Enyl group, 2,3-di-t-butylphenyl group, 2,4
-Di-t-butylphenyl group, 3,4-di-t-butyl
Phenyl group, 2,6-di-n-butylphenyl group, 2,
3-di-n-butylphenyl group, 2,4-di-n-butyl
Ruphenyl group, 3,4-di-n-butylphenyl group,
2,6-di-i-butylphenyl group, 2,3-di-i-
Butylphenyl group, 2,4-di-i-butylphenyl
Group, 3,4-di-i-butylphenyl group, 2,6-di-
t-amylphenyl group, 2,3-di-t-amylpheny
Group, 2,4-di-t-amylphenyl group, 3,4-di
-T-amylphenyl group, 2,6-di-i-amylphe
Nyl group, 2,3-di-i-amylphenyl group, 2,4-
Di-i-amylphenyl group, 3,4-di-i-amylf
An phenyl group, a 2,6-di-n-pentylphenyl group, 2,
3-di-n-pentylphenyl group, 2,4-di-n-pe
Nthylphenyl group, 3,4-di-n-pentylphenyl
Group, 4-adamantylphenyl group, 2-adamantyl
Enyl, 4-isoboronylphenyl, 3-isoboro
Nylphenyl, 2-isoboronylphenyl, 4-thio
Clopentyloxyphenyl group, 4-cyclohexylo
Xiphenyl group, 4-cycloheptenyloxyphenyl
Group, 4-cyclooctanyloxyphenyl group, 2-cycl
Lopentyloxyphenyl group, 2-cyclohexyloxy
Cyphenyl group, 2-cycloheptenyloxyphenyl
Group, 2-cyclooctanyloxyphenyl group, 3-cycl
Lopentyloxyphenyl group, 3-cyclohexyloxy
Cyphenyl group, 3-cycloheptenyloxyphenyl
Group, 3-cyclooctanyloxyphenyl group, 4-n-
Pentyloxyphenyl group, 4-n-hexyloxyph
Enyl group, 4-n-heptenyloxyphenyl group, 4-
n-octanyloxyphenyl group, 2-n-pentylo
A xylphenyl group, a 2-n-hexyloxyphenyl group,
2-n-heptenyloxyphenyl group, 2-n-octa
Nyloxyphenyl group, 3-n-pentyloxypheny
Group, 3-n-hexyloxyphenyl group, 3-n-he
Ptenyloxyphenyl group, 3-n-octanyloxy
Phenyl group, 2,6-di-isopropyloxyphenyl
Group, 2,3-di-isopropyloxyphenyl group, 2,
4-di-isopropyloxyphenyl group, 3,4-di-
Isopropyloxyphenyl group, 2,6-di-t-butyl
Ruoxyphenyl group, 2,3-di-t-butyloxyph
An phenyl group, a 2,4-di-t-butyloxyphenyl group,
3,4-di-t-butyloxyphenyl group, 2,6-di
-N-butyloxyphenyl group, 2,3-di-n-butyl
Ruoxyphenyl group, 2,4-di-n-butyloxyph
An phenyl group, a 3,4-di-n-butyloxyphenyl group,
2,6-di-i-butyloxyphenyl group, 2,3-di
-I-Butyloxyphenyl group, 2,4-di-i-butyl
Ruoxyphenyl group, 3,4-di-i-butyloxyph
An phenyl group, a 2,6-di-t-amyloxyphenyl group,
2,3-di-t-amyloxyphenyl group, 2,4-di
-T-amyloxyphenyl group, 3,4-di-t-amino
Ruoxyphenyl group, 2,6-di-i-amyloxyph
An phenyl group, a 2,3-di-i-amyloxyphenyl group,
2,4-di-i-amyloxyphenyl group, 3,4-di
-I-amyloxyphenyl group, 2,6-di-n-pen
Tyloxyphenyl group, 2,3-di-n-pentyloxy
Cyphenyl group, 2,4-di-n-pentyloxypheny
Group, 3,4-di-n-pentyloxyphenyl group, 4
-Adamantyloxyphenyl group, 3-adamantyl
A xylphenyl group, a 2-adamantyloxyphenyl group,
4-isoboronyloxyphenyl group, 3-isoboronyl
Oxyphenyl group, 2-isoboronyloxyphenyl
Group, etc.
It may be substituted and is not limited to substituents other than the above examples. this
These substituents are substituted by the substituents shown below.
May be. Aralkyl group optionally having substituent for R3
Is preferably 7-30 carbon atoms, more preferably
Is a C 8-25, for example, phenylethyl group, tri
Ruphenylethyl group, xylylphenylethyl group, ethyl
Ruphenylethyl group, propylphenylethyl group, 4-
Cyclopentylphenylethyl group, 4-cyclohexyl
Phenylethyl group, 4-cycloheptenylphenyl ethyl
Group, 4-cyclooctanylphenylethyl group, 2-silane
Clopentylphenylethyl group, 2-cyclohexyl
Enylethyl group, 2-cycloheptenylphenylethyl
Group, 2-cyclooctanylphenylethyl group, 3-cycl
Lopentylphenylethyl group, 3-cyclohexylfe
Nylethyl group, 3-cycloheptenylphenylethyl
Group, 3-cyclooctanylphenylethyl group, 4-cycl
Lopentyloxyphenylethyl group, 4-cyclohexyl
Ruoxyphenylethyl group, 4-cycloheptenyloxy
Cyphenylethyl group, 4-cyclooctanyloxyphene
Nylethyl group, 2-cyclopentyloxyphenyl ethyl
Group, 2-cyclohexyloxyphenylethyl group, 2
-Cycloheptenyloxyphenylethyl group, 2-cycl
Looctanyloxyphenylethyl group, 3-cyclopent
Tyloxyphenylethyl group, 3-cyclohexyloxy
Cyphenylethyl group, 3-cycloheptenyloxyphene
Nylethyl group, 3-cyclooctanyloxyphenyl ester
Til group, 4-n-pentylphenylethyl group, 4-n-
Hexylphenylethyl group, 4-n-heptenylphenyl
Ruethyl group, 4-n-octanylphenylethyl group, 2
-N-pentylphenylethyl group, 2-n-hexylsulfate
Enylethyl group, 2-n-heptenylphenylethyl
Group, 2-n-octanylphenylethyl group, 3-n-pe
N-phenylphenyl group, 3-n-hexylphenyl ester
Til group, 3-n-heptenylphenylethyl group, 3-n
-Octanylphenylethyl group, 2,6-di-isopropyl
Pyrphenylethyl group, 2,3-di-isopropyl phen
Nylethyl group, 2,4-di-isopropylphenylethyl
Group, 3,4-di-isopropylphenylethyl group,
2,6-di-t-butylphenylethyl group, 2,3-di
-T-butylphenylethyl group, 2,4-di-t-butyl
Ruphenylethyl group, 3,4-di-t-butylphenyl
An ethyl group, a 2,6-di-n-butylphenylethyl group,
2,3-di-n-butylphenylethyl group, 2,4-di
-N-butylphenylethyl group, 3,4-di-n-butyl
Ruphenylethyl group, 2,6-di-i-butylphenyl
An ethyl group, a 2,3-di-i-butylphenylethyl group,
2,4-di-i-butylphenylethyl group, 3,4-di
-I-butylphenylethyl group, 2,6-di-t-amino
Ruphenylethyl group, 2,3-di-t-amylphenyl
An ethyl group, a 2,4-di-t-amylphenylethyl group,
3,4-di-t-amylphenylethyl group, 2,6-di
-I-amylphenylethyl group, 2,3-di-i-ami
Ruphenylethyl group, 2,4-di-i-amylphenyl
An ethyl group, a 3,4-di-i-amylphenylethyl group,
2,6-di-n-pentylphenylethyl group, 2,3-
Di-n-pentylphenylethyl group, 2,4-di-n-
Pentylphenylethyl group, 3,4-di-n-pentyl
Phenylethyl group, 4-adamantylphenylethyl
Group, 3-adamantylphenylethyl group, 2-adaman
Tylphenylethyl group, 4-isoboronylphenylethyl
Group, 3-isoboronylphenylethyl group, 2-isobo
Ronylphenylethyl group, 4-cyclopentyloxyf
Enylethyl group, 4-cyclohexyloxyphenyl ester
Til group, 4-cycloheptenyloxyphenylethyl
Group, 4-cyclooctanyloxyphenylethyl group, 2
-Cyclopentyloxyphenylethyl group, 2-cyclo
Hexyloxyphenylethyl group, 2-cyclohepteni
Ruoxyphenylethyl group, 2-cyclooctanyloxy
Cyphenylethyl group, 3-cyclopentyloxypheny
Ruethyl group, 3-cyclohexyloxyphenylethyl
Group, 3-cycloheptenyloxyphenylethyl group, 3
-Cyclooctanyloxyphenylethyl group, 4-n-
Pentyloxyphenylethyl group, 4-n-hexylo
Xiphenylethyl group, 4-n-heptenyloxyphene
Nylethyl group, 4-n-octanyloxyphenyl ethyl
Group, 2-n-pentyloxyphenylethyl group, 2-
n-hexyloxyphenylethyl group, 2-n-hepte
Nyloxyphenylethyl group, 2-n-octanyloxy
Cyphenylethyl group, 3-n-pentyloxyphenyl
An ethyl group, a 3-n-hexyloxyphenylethyl group,
3-n-heptenyloxyphenylethyl group, 3-n-
Octanyloxyphenylethyl group, 2,6-diiso
Propyloxyphenylethyl group, 2,3-di-isopropyl
Lopyloxyphenylethyl group, 2,4-di-isopropyl
Pyroxyphenylethyl group, 3,4-diisopropyl
Ruoxyphenylethyl group, 2,6-di-tert-butylo
Xiphenylethyl group, 2,3-di-t-butyloxy
Phenylethyl group, 2,4-di-t-butyloxyphene
Nylethyl group, 3,4-di-t-butyloxyphenyl
Ethyl group, 2,6-di-n-butyloxyphenyl ethyl
Group, 2,3-di-n-butyloxyphenylethyl
Group, 2,4-di-n-butyloxyphenylethyl group,
3,4-di-n-butyloxyphenylethyl group, 2,
6-di-i-butyloxyphenylethyl group, 2,3-
Di-i-butyloxyphenylethyl group, 2,4-di-
i-butyloxyphenylethyl group, 3,4-di-i-
Butyloxyphenylethyl group, 2,6-di-t-amino
Ruoxyphenylethyl group, 2,3-di-t-amylo
Xiphenylethyl group, 2,4-di-t-amyloxy
Phenylethyl group, 3,4-di-t-amyloxyphene
Nylethyl group, 2,6-di-i-amyloxyphenyl
Ethyl group, 2,3-di-i-amyloxyphenyl ethyl
Group, 2,4-di-i-amyloxyphenylethyl
A group, 3,4-di-i-amyloxyphenylethyl group,
2,6-di-n-pentyloxyphenylethyl group,
2,3-di-n-pentyloxyphenylethyl group,
2,4-di-n-pentyloxyphenylethyl group,
3,4-di-n-pentyloxyphenylethyl group, 4
-Adamantyloxyphenylethyl group, 3-adaman
Tyloxyphenylethyl group, 2-adamantyloxy
Phenylethyl group, 4-isoboronyloxyphenyl ester
Til group, 3-isoboronyloxyphenylethyl group, 2
-Isoboronyloxyphenylethyl group or above
Alkyl is placed on methyl, propyl, butyl, etc.
The thing etc. which changed are mentioned. These substituents are
It may be substituted by the substituent shown. 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,
Droxypropoxy group, n-butoxy group, isobutoxy
Group, sec-butoxy group, t-butoxy group, etc.
Si group, methoxycarbonyl group, ethoxycarbonyl group, etc.
Alkoxycarbonyl group, benzyl group, phenethyl
Groups, aralkyl groups such as cumyl groups, aralkyloxy groups,
Formyl group, acetyl group, butyryl group, benzoyl group,
Cyanamil group, acyl group such as valeryl group, butyryloxy
An acyloxy group such as
Xyl group, propenyloxy group, allyloxy group, buteni
An alkenyloxy group such as a ruoxy group, the above aryl
Group, aryloxy group such as phenoxy group, benzoylo
Mention of aryloxycarbonyl groups such as xy groups
it can. These substituents may further have a substituent.
Often, the number of carbon atoms in a substituted aryl group or substituted aralkyl group
If it is in the range. Specific examples of the group represented by the general formula (I) are as follows:
However, it is not limited to these. [0045] Embedded image[0046] Embedded image[0047] Embedded image[0048] Embedded image[0049] Embedded image[0050] Embedded image[0051] Embedded imageIn the present invention, the group represented by the general formula (I)
Having a structural unit containing
Resin with increased solubility in Lucari developer (hereinafter referred to as one
(Also referred to as a resin having a group represented by the general formula (I))
Compound having molecular weight distribution obtained by polymerizing monomer
In which an acid-decomposable group represented by the general formula (I) is introduced
Of a compound that becomes alkali-soluble by the action of an acid
That is. A resin having a group represented by the general formula (I);
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 (I).
The Among these, it has a group represented by the general formula (I) in the side chain
A resin is more preferable. Next, a group represented by the general formula (I)
As the base resin when is bound as a side chain,
-OH or -COOH, preferably -R⁰-COO
Alkali-soluble resin having H or -Ar-OH group
It is. For example, it does not contain an acid-decomposable group described later
Mention may be made of alkali-soluble resins. Where-
R⁰-Is a divalent or higher valent aliphatic group which may have a substituent or
Represents an aromatic hydrocarbon, -Ar- is monocyclic or polycyclic
Represents a divalent or higher-valent aromatic group which may have the following substituent. As a preferred base resin in the present invention,
Is an alkali-soluble resin having a phenolic hydroxyl group
is there. Has phenolic hydroxyl group used in the present invention
Alkali-soluble resins are o-, m- or p-hydroxy
Styrene (collectively these are called hydroxystyrene)
Or o-, m- or p-hydroxy-α-me
Tylstyrene (collectively referred to as hydroxy-α-methyl)
At least as many repeating units as
30% by mole, preferably 50% by mole or more
Coalescence or homopolymer thereof, or benzene of the unit
It is preferred that the core is a partially hydrogenated resin
P-hydroxystyrene homopolymer is more preferred
Yes. Hydro for preparing the copolymer by copolymerization
Other than xylstyrene and hydroxy-α-methylstyrene
Examples of the monomer include acrylic acid esters and methacrylates.
Luric acid esters, acrylamides, methacrylamides
, Acrylonitrile, methacrylonitrile, anhydrous male
Inic acid, styrene, α-methylstyrene, acetoxys
Tylene and alkoxystyrenes are preferred, styrene,
Acetoxystyrene and t-butoxystyrene are more preferred
That's right. In the present invention, one of such resins
Content of repeating unit having a group represented by formula (I)
As 5 mol% to 50 mol based on all repeating units.
%, More preferably 5 mol% to 30 mol%
is there. In the present invention, it is represented by the above general formula (I).
In addition to the group to be formed, other acid-decomposable groups may be contained. Contains the group represented by the above general formula (I)
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.
The Another method is to use the corresponding alcohol and vinyl.
By the method of acetal exchange using nil ether
Can also be synthesized. In this case, the substituent to be introduced
Is contained in alcohol, and vinyl ether is t-butyl.
Relatively unstable vinyl ethers such as vinyl ether
P-toluenesulfonic acid and viridinium
It is carried out in the presence of an acid such as sylate. Contains a group represented by the above general formula (I)
Is preferably 3000 to 80000,
More preferably, it is 7000-50000. Molecular weight
The range of the cloth (Mw / Mn) is 1.01 to 4.0,
Preferably it is 1.05-3.00. Like this
To obtain a polymer with a molecular weight distribution, anionic polymerization, radical
It is preferable to use a technique such as polymerization. In the general formula (II), R21 represents 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 acyl group
Represents a loxy group. n represents an integer of 1 to 3. R21 represents a hydrogen atom or a methyl group.
A group that does not decompose by the action of an acid in R22 (acid stabilizing group
Also known as hydrogen, halogen, alkyl
Group, cycloalkyl group, alkenyl group, aryl group,
Alkyloxy group (excluding -O-tertiary alkyl)
), Acyl group, cycloalkyloxy group, alkenyl
Oxy group, aryloxy group, alkylcarbonyloxy
Si group, alkylamidomethyloxy group, alkylamide
Group, arylamidomethyl group, arylamido group, etc.
I can get lost. The acid stabilizing group is preferably an acyl group, an
Alkylcarbonyloxy group, alkyloxy group, cyclo
Alkyloxy group, aryloxy group, alkylamide
An oxy group and an alkylamide group, more preferably
Sil group, alkylcarbonyloxy group, alkyloxy
Group, cycloalkyloxy group, aryloxy group
The 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 structural unit represented by the general formula (II) is converted into 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 In the present invention, the general formula (I
As content of the repeating unit having a group represented by I)
Is preferably 5 mol% to 50 mol% with respect to all repeating units.
More preferably, it is 5 mol% to 35 mol%. Such a structural unit 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. [0064] Embedded image[0065] Embedded imageIn the positive photoresist composition of the present invention,
In addition, the structural unit represented by the following general formula (III)
It is preferable to have. [0067] Embedded image In the formula (III), R21 and R23 represent the formula (II)
Means the same substituents as defined for R21 and R23 in
The In the present invention, the general formula (II) in such a resin is used.
As content of the repeating unit having a group represented by I)
Is 30 mol% to 90 mol% with respect to all repeating units
Preferably, more preferably from 35 mol% to 85 mol%
The In these general formula (II) or general formula (III)
The resin containing the structural unit indicated is a phenolic resin or
Reacts with the acid anhydride in the presence of a base to the monomer.
Or with the corresponding halide in the presence of a base
It can be obtained by reacting. In the present invention, it decomposes by the action of an acid,
Trees with groups that increase solubility in alkaline developers
Fat is represented by general formula (I), general formula (II) or general formula (III).
Other monomers as copolymerization components in addition to the structural units represented
Units may be included. The resin used in the present invention has an alkali dissolution rate.
Polyhydride in the synthesis stage to adjust and improve heat resistance
Add a roxy compound to make the polymer main chain polyfunctional aceta
A cross-linking site linked by a diol group may be introduced. Polyhydr
The addition amount of the roxy compound is based on the number of hydroxyl groups in the resin.
0.01 to 10 mol%, preferably 0.05 to 8 mo
1%, more preferably 0.1 to 5 mol%. Poly
Hydroxy compounds include phenolic hydroxyl groups
Examples having 2 to 6 alcoholic hydroxyl groups are preferred.
Preferably the number of hydroxyl groups is 2-4, more preferably
The number of hydroxyl groups is 2 or 3. Specific examples are shown below.
However, the present invention is not limited to these. [0072] Embedded image 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. Also
The resin contained in the positive photosensitive composition of the present invention is an alcohol.
In order to maintain good developability for potash developer,
Lucari soluble groups such as phenolic hydroxyl groups, carboxylic acids
Other polymerizable monomers suitable so that a sil group can be introduced
May be copolymerized. The above general formula synthesized by the above method
(I) Repeated structure of general formula (II) or general formula (III)
The molecular weight of the resin having a building unit is the weight average (Mw: poly
Styrene standard) 2,000 or more, preferably 3,000
0 to 200,000, more preferably 5,000
~ 70,000. Also, dispersity (Mw / Mn)
Is preferably 1.0 to 4.0, more preferably 1.0.
~ 3.5, particularly preferably 1.0-3.0, dispersion
The smaller the degree, the better the heat resistance and image formation (pattern profile
Il, defocus latitude, etc.). The above general formula (I), (II) or general formula (II
Positive photosensitive group of resin having repeating structural unit of I)
The content of the composition (excluding the coating solvent) is preferably 50
-99 wt%, more preferably 70-97 wt%
The General formula (I), general formula (II) or general formula
Specific examples of the resin having the repeating structural unit (III) are as follows.
As shown below, the present invention is not limited to these.
Yes. [0077] Embedded image[0078] Embedded image[0079] Embedded image[0080] Embedded image[0081] Embedded image[0082] Embedded image[0083] Embedded imageIn the present invention, the general formula (I),
Repeated structure represented by general formula (II) or general formula (III)
In addition to resins with structural units, resins with acid-decomposable groups
May be used. In the chemically amplified resist in the present invention,
Decomposed by other acids used in the alkaline developer
As a resin having a group that increases solubility in
In the main chain or side chain, or both the main chain and side chain
It is a resin having a group that can be decomposed by. Of these, decomposition with acid
A resin having a group capable of being formed on the side chain is more preferred. Decompose with acid
Preferred groups that may be used are -COOA⁰ , -OB
⁰ As a group further including these, -R⁰ -C
OOA⁰ Or -Ar-OB⁰ A group represented by
It is. Where A⁰ Is -C (R⁰¹) (R⁰²) (R⁰³),
-Si (R⁰¹) (R⁰²) (R⁰³) Or -C (R⁰⁴)
(R⁰⁵) -O-R⁰⁶Indicates a group. B⁰ Is -A⁰ Or -C
O-O-A⁰ Group (R⁰ , R⁰¹~ R⁰⁶And Ar is
Synonymous with the following). 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 -COOH, preferably -R⁰ -COOH or
It is an alkali-soluble resin having an -Ar-OH group. Example
For example, the alkali-soluble resin described later can be mentioned.
The 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). Ma
From the point of achieving a rectangular profile,
Alkali-soluble tree with high transmittance for sima laser light
Fat is preferred. Preferably, at 248 nm with a thickness of 1 μm
The transmittance is 20 to 90%. From this perspective,
Particularly preferred alkali-soluble resins are o-, m-, p-
Poly (hydroxystyrene) and copolymers thereof, water
Basic poly (hydroxystyrene), halogen or a
Rualkyl-substituted poly (hydroxystyrene), poly (hydro
Part of xylene), O-alkylation or O-a)
Silylated product, styrene-hydroxystyrene copolymer, α
-Methylstyrene-hydroxystyrene copolymer and water
It is an elemental novolac resin. It has a group that can be decomposed by an 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-degradable dissolution inhibitor used in the present invention
As a stopping compound, there are few groups that can be decomposed by acid in the structure.
There are at least two, and the distance between the acid-decomposable groups is the longest
In the position, at least the bonding atom excluding the acid-decomposable group is
It is a compound that passes through eight. Also used in the present invention
The acid-decomposable low molecular weight dissolution inhibiting compound is represented by the general formula (X).
It may contain at least one acid-decomposable group. 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, the acid-decomposable dissolution inhibiting compound has an acid content.
When it has 3 or more, preferably 4 or more decomposable groups,
Even those having two acid-decomposable groups,
When they are separated from each other by a certain distance
Dissolution inhibitory properties for soluble resins are significantly improved. Na
The distance between the acid-decomposable groups in the present invention is the acid-decomposable group.
Indicated by the number of via-bonded atoms, excluding. For example, the following
In the case of compounds (1) and (2), the distance between the acid-decomposable groups is
There are 4 bonding atoms, and in compound (3), 12 bonding atoms.
It is a piece. [0091] Embedded image 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. Where A⁰Is -C
(R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹) (R⁰²)
(R^{0 Three}) Or -C (R⁰⁴) (R⁰⁵) -O-R⁰⁶Group
Show. B⁰A⁰Or -CO-O-A⁰Indicates a group.
R⁰¹, R⁰², R⁰³, R⁰⁴And R⁰⁵Are the same
It may be different, hydrogen atom, alkyl group, cycloa
Represents an alkyl group, an alkenyl group or an aryl group, R
⁰⁶Represents an alkyl group or an aryl group. However, R⁰¹
~ R⁰³At least two of these are groups other than hydrogen atoms,
R⁰¹~ R⁰³And R⁰⁴~ R⁰⁶Two groups of
To form a ring. R⁰Has a substituent
Good divalent or higher aliphatic or aromatic hydrocarbon group
-Ar- has a monocyclic or polycyclic substituent.
Or a divalent or higher aromatic group. Here, the alkyl group includes a methyl group and an alkyl 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. Moreover, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro
Group, cyano group, the above alkyl group, methoxy group, ethoxy group
Si group, hydroxyethoxy group, propoxy group, hydroxy
Cypropoxy group, n-butoxy group, isobutoxy group, s
alkoxy groups such as ec-butoxy group and t-butoxy group,
Alkyl such as methoxycarbonyl group and ethoxycarbonyl group
Coxycarbonyl group, benzyl group, phenethyl group, kumi
Aralkyl groups such as ru groups, aralkyloxy groups, formyl
Group, acetyl group, butyryl group, benzoyl group, cyanami
Such as an acyl group such as an alkyl group, valeryl group, butyryloxy group, etc.
An acyloxy group, the above alkenyl group, a vinyloxy group,
Propenyloxy, allyloxy, butenyloxy
Alkenyloxy groups such as the above groups, the above aryl groups,
Aryloxy groups such as xy groups, benzoyloxy groups, etc.
An aryloxycarbonyl group can be mentioned. 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. 3-200254, 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]. [0099] Embedded image [0100] Embedded imageR¹⁰¹, R¹⁰², R¹⁰⁸, R¹³⁰: Same or different
May be a hydrogen atom, -R0-COO-C (R
⁰¹) (R ⁰²) (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 [0103] 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 [0105] 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
Tylene group or haloalkylene group, a to v, g1 to n1:
When plural, the groups in parentheses may be the same or different,
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 from 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. [0108] Embedded image[0109] Embedded image[0110] Embedded imageIn this case, the content of the dissolution inhibiting compound is not sensitive.
3 to 4 based on the total weight of the light composition (excluding the solvent)
5% by weight, preferably 5-30% by weight, more preferably
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 alk
Resoluble resins are novolak resin and o-polyhydroxy
Styrene, m-polyhydroxystyrene, p-polyhydride
Roxystyrene and their copolymers, alkyl-substituted polymers
Rehydroxystyrene, part of polyhydroxystyrene
O-alkylated or O-acylated product, styrene-
Hydroxystyrene copolymer, α-methylstyrene-H
Droxystyrene copolymer. The novolac resin is
In the presence of an acidic catalyst with a predetermined monomer as the main component,
It can be obtained by addition condensation with aldehydes. 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
Can be used alone or in combination of two or more
The Acid catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid,
An acid or the like can be used. 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 polyhydroxy other than the novolak resin
Weight average molecular weight of styrene, its derivatives and copolymers
Is 2000 or more, preferably 5000-20000
0, more preferably 10,000 to 100,000.
From the viewpoint of improving the heat resistance of the resist film
Is preferably 25000 or more. Where the weight average molecule
The amount is the gel permeation chromatography police
It is defined with a chilled value. This in the present invention
Use two or more of these alkali-soluble resins.
Also good. Of these alkali-soluble resins in the present invention.
The addition amount in the composition is preferably 5 to 30% by weight.
It is. The acid generator (b) used in the present invention is active.
It is a compound that generates an acid upon irradiation with actinic radiation. Main departure
Actinic radiation (electron) as acid generator (b) used in light
A compound that generates acid upon irradiation with a daughter beam, X-ray or EUV.
A resist film containing an acid generator (b) is active
Compound that generates acid when irradiated with radiation
You just have to. That is, the acid generator is directly irradiated.
Even for compounds that generate acid, the resin
Secondary electrons are emitted from the constituents, thereby generating acid.
It may be a compound. This used in the present invention
Such compounds can be decomposed by irradiation with actinic radiation.
It can be used as long as it generates an acid.
Photoinitiator for photosynthesis, photoinitiator for photoradical polymerization, light of pigments
Used for decolorizers, photochromic agents, or microresists
Known light (400-200 nm ultraviolet, far
Ultraviolet rays, particularly preferably g-line, h-line, i-line, KrF
Excimer laser light), ArF excimer laser light, X
Compound that generates acid by beam, molecular beam or ion beam
And a mixture of them and use as appropriate.
You can. 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 Further, 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
The light described in Patent No. 3,779,778, European Patent No. 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. The substituent preferably has 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, the acid generated after exposure (benZe having the above group).
Zen sulfonic acid, naphthalene sulfonic acid, or anthra
Sensulphonic acid) is reduced in diffusibility, and the sulfone
Solvent solubility of nium and iodonium compounds is improved.
In particular, from the viewpoint of reducing diffusivity,
From a straight-chain alkyl group or alkoxy group.
Is preferably a cyclic alkyl group or an alkoxy group.
When the number of the above groups is one, linear and branched or cyclic expansion
The difference in dispersity becomes more pronounced. [0124] C8 or more, preferably C8-2
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. 8 or more carbon atoms, preferably 8 to 20 carbon atoms
As an alkoxy group, branched or cyclic octyl
Oxy, nonyloxy, decyloxy, undec
Ruoxy group, dodecyloxy group, tridecyloxy group,
Examples include tetradecyloxy group and octadecyloxy group
It is done. As an alkyl group having 4 to 7 carbon atoms, a straight chain
, Branched or cyclic butyl group, pentyl group, hexyl
Group, heptyl group and the like. Al with 4 to 7 carbon atoms
The alkoxy group includes linear, branched or cyclic butoxy
Group, pentyloxy group, hexyloxy group, heptylo
And a xyl group. As the alkyl group having 1 to 3 carbon atoms,
Til group, ethyl group, n-propyl group, isopropyl group
Can be mentioned. As an alkoxy group having 1 to 3 carbon atoms,
Methoxy group, ethoxy group, n-propoxy group, isopropyl
A poxy group is mentioned. As halogen atom, fluorine
Mention atoms, chlorine atoms, bromine atoms, iodine atoms.
And preferably a fluorine atom. Linear, branched or
Examples of cyclic esters having 1 to 10 carbon atoms include methyl ester.
Steal group, ethyl ester group, n-propyl ester
Group, i-propyl ester group, n-butyl ester group,
i-butyl ester group, t-butyl ester group, n-he
Xyl ester group, i-hexyl ester group, t-hex
Silester group, n-heptyl ester group, i-heptyl
Ruester group, t-heptyl ester group, n-octyl
Ester group, i-octyl ester group, t-octyl ester
Steal, n-nonyl ester group, i-nonyl ester
Group, t-nonyl ester group, n-decanyl ester group,
i-decanyl ester group, t-decanyl ester, cycl
Ropropyl ester group, cyclobutyl ester group,
Lopentyl ester group, cyclohexyl ester group,
Chloheptyl ester group, cyclooctyl ester group,
Cyclononyl ester group, cyclodecanyl ester group, etc.
Is mentioned. 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, etc.
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. [0129] Embedded image[0130] Embedded image[0131] Embedded image [0132] Embedded image[0133] Embedded image[0134] Embedded image[0135] Embedded image[0136] Embedded image[0137] Embedded image[0138] Embedded image[0139] Embedded image[0140] Embedded image[0141] Embedded image [0142] Embedded image[0143] Embedded image[0144] Embedded image[0145] Embedded image[0146] Embedded image[0147] Embedded image[0148] Embedded image[0149] Embedded image[0150] Embedded image[0151] Embedded image[0152] Embedded image[0153] Embedded image[0154] Embedded image[0155] Embedded image[0156] Embedded image[0157] Embedded image In the specific examples, n is a straight chain, s is a secondary, t
Indicates tertiary, i indicates branching. General formula (A-
The compounds represented by 1) to (A-3) correspond, for example,
Cl^-Salt (in formulas (A-1) to (A-3)^-Cl^-
And a compound substituted with^-Y⁺A compound represented by the formula (X
^-Is synonymous with the case of general formulas (A-1) to (A-3).
Y⁺Is H⁺, Na⁺, K⁺, NH_Four ⁺, N (CH_Three)_Four ⁺ etc
Of the cation. ) And salt exchange in aqueous solution
Can be synthesized. 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. Further, when l, m, and n are each 2 or 3,
2 or 3 R₁₁~ R₁₃Or R ₁₄~ 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. [0162] Embedded image [0163] Embedded image[0164] Embedded image[0165] Embedded image[0166] Embedded image[0167] Embedded image[0168] Embedded image [0169] Embedded image[0170] Embedded image[0171] Embedded image[0172] Embedded image [0173] Embedded image In the specific examples, n is a straight chain, s is a secondary, t
Indicates tertiary, i indicates branching. General formula (A-
4) The compounds represented by (A-5) correspond, for example,
Cl^-Salt (general formula (A-4), (A-5)^-Cl^-
And a compound substituted with^-Y⁺A compound represented by the formula (X
^-Is the same as in the general formulas (A-4) and (A-5), Y⁺Is
H ⁺, Na⁺, K⁺, NH_Four ⁺, N (CH3)_Four ⁺Cations etc.
Indicates. ) And salt exchange in aqueous solution
it can. 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 group
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 Acyl groups include acetyl, propionyl, and
Nzoyl group and the like. As acylamino group
Acetylamino group, propionylamino group, benzoyl
An amino group etc. are mentioned. As a sulfonylamino group
Is methanesulfonylamino group, ethanesulfonylamino group
A sulfonylamino group having 1 to 4 carbon atoms such as a group, p-tolu
Substituted or unsubstituted benzene such as enesulfonylamino group
And benzenesulfonylamino group. An aryl group and
Examples include phenyl, tolyl, and naphthyl groups.
It is. As an alkoxycarbonyl group, methoxycarbo
Nyl group, ethoxycarbonyl group, ethoxyethoxycal
Bonyl group, octyloxycarbonyl group, dodecyloxy
Alkoxy groups having 2 to 20 carbon atoms such as a sicarbonyl group
A rubonyl group. 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. Aralkyl groups are substituted or unsubstituted
7 carbon atoms such as dil group, substituted or unsubstituted phenethyl group
There are ˜15 aralkyl groups. Aralkyl group
Preferred substituents are the same as those listed above.
can give. 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.
It may be formed. As another imide sulfonate
Is a compound represented by the general formula (A-6), wherein X or Y is
By the way, there is a monovalent group. As the alkylene group for X, 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 a 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. As the cyclic alkylene group, cyclopentylene is used.
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. Cited here
Alkoxy group, acyl group, nitro group, acylamino
Group, sulfonylamino group, aryl group, alkoxycal
Bonyl group is R₃₁~ R₅₁It is synonymous with what was mentioned in. Halo
Gen atoms include fluorine, chlorine, bromine, and iodine.
A boron atom can be mentioned. 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. 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 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. Cyclic alkenylene groups are cyclo
Carbon number such as pentenylene group, cyclohexenylene group, etc.
4-8 monocyclic cycloalkenylene groups, 7-oxabici
Chloro [2.2.1] heptenylene group, norbornenylene
C5-C15 polycyclic cycloalkenylene group such as a group
Is mentioned. As an aralkylene group, a tolylene group,
Xylylene group and the like.
Examples thereof include the substituents exemplified for the -len group. 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. [0185] Embedded image [0186] Embedded image[0187] Embedded image [0188] Embedded image[0189] Embedded image [0190] [Chemical Formula 86][0191] Embedded image [0192] Embedded image[0193] 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
And aryl groups include phenyl, tolyl, naphth
A til group etc. are mentioned. As a substituent of the aryl group
Is an alkyl group, cycloalkyl group, alkoxy group,
Sil group, formyl group, nitro group, acylamino group, sulfo group
Phonylamino group, halogen atom, aryl group, alkoxy
A cicarbonyl group may be mentioned. Alkyl mentioned here
Group, cycloalkyl group, alkoxy group, acyl group,
Mill group, nitro group, acylamino group, sulfonylamino
Group, aryl group, alkoxycarbonyl group₃₁~
R₅₁It is synonymous with what was mentioned in. As halogen atom
List fluorine atom, chlorine atom, bromine atom, iodine atom
be able to. 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. [0197] Embedded image[0198] 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 formula (A-1)
Among the acid generators represented by (A-7), the general formula (A-
Acid generators represented by 1) to (A-5) are preferred, and more
Preferably acids represented by general formulas (A-1) to (A-4)
It is a generator. This further improves resolution and sensitivity.
It becomes like this. 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. Furthermore, in the present invention, the above general formula (A
-1) to (A-7) and the acid generator
Combined use of acid generators represented by general formulas (B-1) to (B-5)
You may do it. The general formulas (B-1) to (B-
5) The structure on the cation side of the acid generator represented by
It is represented by the corresponding general formulas (A-1) to (A-5).
The structure is the same as that on the cation side. In addition, the corresponding
Nion (Y^-Is an anion of the above general formula (A-1)
(X^-) Anion of sulfonic acid (SO)_Three ^-)
This is the same as that replaced with the anion of rubonic acid. The amount of the acid generator that can be used in combination is the total acid.
1 to 80% by weight is preferable with respect to the generator, and 10 to 50%.
More preferred is weight percent. Specific examples of these compounds are shown below.
However, the present invention is not limited to this. [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[0214] Embedded image[0215] Embedded image[0216] Embedded image[0217] Embedded image[0218] Embedded image[0219] Embedded image [0220] Embedded image [0221] Embedded image[0222] Embedded image[0223] Embedded image[0224] Embedded image 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 presence that can be used in the present invention
Basic compounds are more basic than phenol
It is a compound. Of these, nitrogen-containing basic compounds are preferred. Good
As a favorable chemical environment, the following structures (A) to (E)
Can be mentioned. [0226] Embedded imageFurther preferable 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. Cyclic amine compounds include polycyclic structures
It is more preferable that Preferred cyclic amine compounds
As specific examples, compounds represented by the following general formula (F)
Is mentioned. [0228] Embedded image In the formula (F), Y and Z are each independently
A straight chain, which may contain a
Represents a cyclic alkylene group. Where heteroatoms
Examples thereof include a nitrogen atom, a sulfur atom, and an oxygen atom. A
The alkylene group preferably has 2 to 10 carbon atoms,
More preferably, it is 2-5. Placement of alkylene group
As the substituent, an alkyl group having 1 to 6 carbon atoms, aryl
Group, alkenyl group, halogen atom, halogen-substituted group
Examples include an alkyl group. Furthermore, it is represented by the general formula (F)
Specific examples of the compound include the compounds shown below.
The [0230] Embedded image Of these, 1,8-diazabicyclo
[5.4.0] Undec-7-ene, 1,5-diazabi
Cyclo [4.3.0] non-5-ene is particularly preferred. 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 2 parts by weight. 0.001 part by weight
If it is full, the above effect cannot be obtained. On the other hand, over 10 parts by weight
This tends to reduce sensitivity and developability in unexposed areas.
The In the chemically amplified positive resist composition of the present invention,
If necessary, further 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). These surface activities
Among these agents, fluorine or silicon surfactants are applied.
This is preferable in terms of fabric properties and reduction in development defects. The blending amount of the surfactant 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. This
These surfactants can be used alone or in combination of two or more.
They can be used together. 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 during the synthesis of the resin of the present invention
The effect of the content of (derived from the medium) was observed. That is,
The acid contained as an impurity in the resist composition of the present invention
When the content is more than 500 ppm, the effect of the present invention
Some excellent pattern profile shapes and vacuum channels
Less line width fluctuation in the holding time in the bar
The Therefore, in the resist composition of the present invention, the resist
The content of acid contained as an impurity in the strike composition is 50
It is necessary to suppress it to 0 ppm or less, preferably 2
00 ppm or less, more preferably 100 ppm or less
is there. Further, 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 benzophene.
Non, p, p'-tetramethyldiaminobenzopheno
P, p'-tetraethylethylaminobenzopheno
, 2-chlorothioxanthone, anthrone, 9-eth
Xyanthracene, anthracene, pyrene, perylene,
Phenothiazine, benzyl, acridine orange, ben
Zoflavine, cetoflavin-T, 9,10-diphenyl
Anthracene, 9-fluorenone, acetophenone, fu
Enanthrene, 2-nitrofluorene, 5-nitroacetate
Naphthene, benzoquinone, 2-chloro-4-nitroani
Phosphorus, N-acetyl-p-nitroaniline, p-nitro
Aniline, N-acetyl-4-nitro-1-naphthylua
Min, picramide, anthraquinone, 2-ethylant
Laquinone, 2-tert-butylanthraquinone, 1,2-
Benzanthraquinone, 3-methyl-1,3-diaza
1,9-benzanthrone, dibenzalacetone, 1,2
-Naphthoquinone, 3,3'-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene.
However, it is not limited to these. Feno that promotes solubility in developers
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 above chemically amplified positive resist composition is precision.
Substrates such as those used in the manufacture of integrated circuit elements (eg, silicon
Spinner, coater, etc.
After application by an appropriate application method, pass through a predetermined mask.
Good resist by exposure, baking and development
Pattern can be obtained. The chemically amplified positive resist composition of the present invention
Examples of the developer include sodium hydroxide and potassium hydroxide.
Sodium, sodium carbonate, sodium silicate, sodium phosphate
Thorium, sodium metasilicate, ammonia water, etc.
Machine alkalis, ethylamine, n-propylamine, etc.
Primary amines, diethylamine, di-n-butylamine
Secondary amines such as triethylamine, methyldiethyl
Tertiary amines such as amines, dimethylethanolamine,
Alcohol amines such as triethanolamine, form
Amides such as amide and acetamide, tetramethylan
Monium hydroxide, trimethyl (2-hydroxy ester)
Til) ammonium hydroxide, tetraethylammo
Nium hydroxide, tributylmethylammonium
Droxide, tetraethanolammonium hydroxy
Methyltriethanolammonium hydroxide,
Benzylmethyldiethanolammonium hydroxy
And benzyldimethylethanolammonium hydroxide
Sid, benzyltriethanolammonium hydroxy
Tetrapropylammonium hydroxide, tetra
Quaternary ammonia such as butylammonium hydroxide
Alkaline such as cyclic amines such as salt, pyrrole and piperidine
There is an aqueous solution of li. [0244] 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]
Benzenethiol 55.01 g (0.5 mol) 300
dissolved in ml N, N-dimethylformamide, then
Add 150 g of 2-chloroethyl vinyl ether,
25 g of sodium hydroxide was added to the mixture at 120 ° C. for 2 hours.
The mixture was heated and stirred for a while. The reaction solution was washed with water, and excess pressure was removed by distillation under reduced pressure.
Chloroethyl vinyl ether was removed. Obtained oy
The target product, phenylthio, is obtained by distillation under reduced pressure.
Ethyl vinyl ether (X-1) was obtained. [Synthesis Examples I-2 to 6] In the same manner as in Synthesis Example I-1,
Vinyl ether X-2, X-3, X-4, X-
5, X-6 was obtained. [0246] Embedded image[Synthesis Example II-1] p-acetoxystyrene
Dissolve 32.4 g (0.2 mol) in 120 ml butyl acetate.
Azobisisobutane at 80 ° C. under nitrogen flow and stirring
Place 0.033 g of Tyronitrile (AIBN) for 2.5 hours.
3 times and finally continue stirring for another 5 hours
Thus, a polymerization reaction was performed. The reaction liquid is hexane 1200m.
1 was deposited to precipitate a white resin. The resulting resin
After drying, it was dissolved in 150 ml of methanol. To this
Sodium chloride 7.7 g (0.19 mol) / water 50 ml
Add aqueous solution and heat to reflux for 3 hours to hydrolyze
I was allowed to understand. Then, add 200 ml of water to dilute, hydrochloric acid
And a white resin was precipitated. 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]
Distilled and purified p-tert-butoxystyrene monomer 3
5.25 g (0.2 mol) and styrene monomer 5.2
1 g (0.05 mol) of 100 ml of tetrahydrofuran
Dissolved in. Azobis at 80 ° C under nitrogen flow and stirring
Isobutyronitrile (AIBN) 0.033 g 2.5
Add 3 times every hour and finally continue stirring for another 5 hours
Thus, a polymerization reaction was performed. Hexane 12
The solution was poured into 00 ml to precipitate a white resin. Obtained
After drying the resin, dissolve it in 150 ml of tetrahydrofuran.
It was. Add 4N hydrochloric acid and heat to reflux for 6 hours.
After being hydrolyzed by this, it is re-precipitated in 5 L of ultrapure water.
The resin was filtered off, washed with water and dried. Tetrahydroph
Dissolve in 200 ml of run and stir vigorously in 5 L of ultrapure water
While dropping, reprecipitation was performed. Repeat this re-sink operation three times.
I returned. The resulting resin was placed in a vacuum dryer at 120 ° C., 12
Time dried and poly (p-hydroxystyrene / styrene)
N) A copolymer alkali-soluble resin R-2 was obtained. Obtained
The weight average molecular weight of the 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) dissolved in 120 ml butyl acetate
And azobisisobutyrate at 80 ° C. under nitrogen flow and stirring.
Ritonitrile (AIBN) 0.033g every 2.5 hours
3 times and finally stirring for another 5 hours
The polymerization reaction was performed. The reaction solution is 1200 ml of hexane.
The white resin was deposited. Dry the resulting resin
After drying, it was dissolved in 200 ml of methanol. This is hydroxylated
Sodium 7.7 g (0.19 mol) / water 50 ml water
Hydrolysis by adding solution and heating to reflux for 1 hour
I let you. Then, add 200 ml of water to dilute and add hydrochloric acid.
To neutralize a white resin. This resin is filtered off,
Washed with water and dried. Furthermore, 200 ml of tetrahydrofuran
Dissolved in 5 L of ultrapure water and stirred vigorously,
Re-precipitation was performed. This reprecipitation operation was repeated three times. Obtained
The dried resin is dried at 120 ° C. for 12 hours in a vacuum drier.
Li (p-hydroxystyrene / methyl methacrylate)
Polymer alkali-soluble resin R-3 was obtained. Obtained resin
The weight average molecular weight of was 10000. [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] Obtained in Synthesis Example II-4
Alkali-soluble resin R-4 20g propylene glycol
Monoethyl ether acetate (PGMEA) 80
ml is dissolved in a flask, distilled under reduced pressure, water and PG
MEA was distilled off azeotropically. Make sure that the water content is low enough.
After confirmation, vinyl ether X- obtained in Synthesis Example I-1
7.0 g of 1 and 50 mg of p-toluenesulfonic acid were added.
The mixture was stirred at room temperature for 1 hour. There pyridine 1.5
g and 1.5 g of acetic anhydride were added and stirred at room temperature for 1 hour.
Stir. Ethyl acetate was added to the reaction solution and further washed with water.
Then, PGM of ethyl acetate, water and azeotrope by vacuum distillation
EA is distilled off and the alkali having the substituent according to the present invention is acceptable.
Soluble resin B-1 was obtained. [Synthesis Examples III-2 to III-18]
Alkali soluble resin, acid anhydride and vinyl ether indicated
And substitution according to the present invention in the same manner as in Synthesis Example III-1.
Obtaining alkali-soluble resins B-2 to B-18 having a group
It was. [0253] [Table 1] [Synthesis Examples IV-1 to IV-2] Shown in Table 2 below
Alkali-soluble resin and ethyl vinyl resin represented by the following formula:
Resins C-1 and C-2 were obtained with ruether (Y-1). [0255] Embedded image [0256] [Table 2] As surfactant (F-1), mega fat
C08 (Dainippon Ink Co., Ltd.) was used. Surface activity
As a sex agent (F-2), Troisol S-366 (Troy
Chemical Co., Ltd.) was used. Examples 1-22 and Comparative Examples 1-2 [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. This resist solution
On a silicon wafer using a spin coater
Apply, 130 ° C, 60 seconds vacuum adsorption type hot play
To obtain a resist film having a film thickness of 0.3 μm. [0259] [Table 3]In addition, each photoacid generator used in the examples and
Organic base compounds are shown below. [0261] Embedded image An 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 resolution 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. In addition, the resist film obtained as described above was used.
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. The value is small
Better. Fluctuation rate = {1− | (B) − (A) | / (B)} × 100 [0266] [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 23 to 26 and Comparative Examples 3 to 4
As shown in Table 5, in general formula (I) and general formula (III)
It is decomposed by the action of an acid having the structural unit shown
Resins with increased solubility in Lucari developer, and / or
Are 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 1-22 with the exception 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. Solution in the same manner as in Examples 1-22.
Image power, resist pattern profile, vacuum chamber
The results of evaluating the line width variation due to the
Table 6 shows. [0269] [Table 5] In addition, the dissolution inhibiting compounds used in the examples are shown below.
Shown below. [0271] Embedded image[0272] [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. [0274] According to the present invention, a resist pattern processor is provided.
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    F-term (reference) 2H025 AA03 AB16 AC04 AC05 AC06                       AD03 BE00 BE10 BG00 CB16                       CB17 CB41 FA17                 4J100 AB02R AB04R AB07P AB07Q                       AB07R BA02H BA02Q BA02R                       BA03P BA05H BA05Q BA05R                       BA12H BA12Q BA15H BA15R                       BA20H BA20Q BA34H BA34Q                       BA35H BA35R BA51H BA51Q                       BA55Q BA58Q BA93H BA93Q                       BC43H BC43Q CA05 DA38                       DA39 HA19 HA61 HC33 HC70                       HC71 HC83 JA37

Claims (1)

What is claimed is: (a) a resin having a structural unit containing a group represented by the following general formula (I), 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 which generates an acid upon irradiation with actinic radiation. [Chemical 1] In formula (I), 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 X represents -S-, -N (R4) C.
O-, -Se-, -CO-, -COO-, -OCO-,
—SO— or —SO ₂ — (wherein R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), R3 represents a chain alkyl group which may have a substituent, or a substituent. The cyclic alkyl group which may have, the aryl group which may have a substituent, or the aralkyl group which may have a substituent is represented. )