JP2003162061A - Positive resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition which improves edge roughness of a pattern, remedies the problem of development defects and gives an excellent resist pattern profile. <P>SOLUTION: The positive resist composition comprises (A) a resin having an alicyclic hydrocarbon group and having a velocity of dissolution in an alkali developing solution increased by the action of an acid, (B) a compound which generates an acid upon irradiation with an active ray or radiation, and (C) a compound represented by a specified structure and containing a sulfonimide structure in its molecule. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lithographic printing plate and an IC.
The present invention relates to a positive resist composition used in semiconductor manufacturing processes such as the above, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. In particular, the positive resist composition of the present invention acts by high-energy radiation such as deep ultraviolet rays (including excimer lasers, etc.), electron beams, X-rays, or synchrotron radiation, and is suitably used for manufacturing semiconductor integrated circuits. It is a thing.

[0002]

2. Description of the Related Art Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed.
In recent years, with the high integration of integrated circuits, formation of ultrafine patterns in the submicron region or the quarter micron region has been required. Along with this, the exposure wavelength tends to be shortened, such as from g-line to i-line and further to KrF excimer laser light. At present, lithography using excimer laser light is an important processing technique in this field, and a chemically amplified resist is used as a resist suitable for such an excimer laser lithography process.

The chemically amplified resist composition produces an acid in the exposed area by irradiation with radiation such as far-ultraviolet light, and reacts with the developer in the exposed area and the non-irradiated area of active radiation by a reaction using the acid as a catalyst. It is a material that forms a pattern on a substrate by changing its solubility. The chemically amplified resist has the advantages that it has high sensitivity and resolution, and that it can form an image with a compound that generates an acid with a small amount of radiation (hereinafter referred to as a “photoacid generator”).

The above-mentioned positive chemically amplified resist is a three-component system comprising an alkali-soluble resin, a photo-acid generator, and a dissolution inhibiting compound having an acid-decomposable group, and an alkali-soluble resin A two-component system comprising a resin having a soluble group and a photo-acid generator, a resin having a group which is decomposed by reaction with an acid to be alkali-soluble, a low molecular weight dissolution inhibiting compound having an acid-decomposable group, and It can be roughly divided into hybrid systems composed of photoacid generators. In these two-component, three-component, and hybrid positive chemically amplified resists, an acid from a photo-acid generator is interposed by exposure, heat treatment is performed, and development is performed to obtain a resist pattern.

In lithography using a chemically amplified resist, sensitivity, resolution, profile,
Coatability, heat resistance, dry etching resistance, adhesion, substrate dependence, environmental stability (eg resist dimension stability due to fluctuations in leaving time), and depth of focus (eg pattern formation against defocus during irradiation of radiation) A photoresist excellent in various properties such as (property) is required, and many devices for improving performance by additives have been disclosed so far.

Due to its unique reaction mechanism, chemical amplification type positive resists have been attempted to prevent the diffusibility of the generated acid by improving the resist properties, especially environmental stability, by adding an acid scavenger. There is. For example, JP-A-5-12
No. 7369, No. 5-232706, No. 5-24966.
No. 2, No. 5-289322, No. 6-317902,
As disclosed in JP-A-7-92678 and JP-A-7-120929, those to which an organic amine is added have been proposed. However, addition of amine improves the resolution but decreases the sensitivity.

On the other hand, it has been attempted to add various compounds to the chemically amplified resist composition for the purpose of improving the sensitivity and improving the shape of the resist pattern. For example, JP-A-5-181279, JP-A-7-92679, and JP-A-9-6.
No. 001, No. 6-6002, No. 9-6003, US Pat. Nos. 5,955,240, 5,948,589, and European Patent No. 6,799,51 disclose addition of a carboxylic acid, and JP-A-4-134345. Issue 4
No. 217251, No. 7-181680, No. 8-211
597, U.S. Pat. Nos. 5,688,628 and 5,972,255.
JP-A-5-181263 and JP-A-7-181263 disclose that an aromatic polyhydroxy compound is added.
No. 92680 discloses the addition of sulfonamide compounds.

Further, a device for improving resist characteristics such as resolution, exposure latitude, adhesion, and substrate dependence is also disclosed. For example, JP-A-9-5987, US Pat. No. 5,770,343, and European Patent No. 749044 disclose methods for preventing pattern collapse by adding a formamide or acetamide compound.
Japanese Patent No. 44950 discloses that the substrate dependence is improved by adding a nitrogen-containing compound such as succinimide or phthalimide. JP-A-5-232706,
6-11835, 6-242606, 6-2
66100, 7-333851, 7-3338.
44, US Patent 5663035, European Patent 6777.
By adding a compound (photobase) whose basicity is lowered by exposure to No. 88, environmental stability (for example,
A method for improving resist dimensional stability due to variation in the leaving time), resolution, depth of focus, etc. is disclosed. Further, JP-A-9-297396 discloses a device for improving resolution and depth of focus by adding a specific low molecular weight acid-decomposable dissolution inhibiting compound to a two-component chemically amplified resist.

However, even with the above techniques, there are many insufficient points in the performance of line edge roughness in the photoresist composition for deep UV exposure, and improvement has been required. Here, the line edge roughness means that the edge of the resist line pattern and the substrate interface irregularly fluctuates in the direction perpendicular to the line direction due to the characteristics of the resist. It says that the edge looks uneven. The unevenness is transferred by the etching process using the resist as a mask, and the electrical characteristics are deteriorated, so that the yield is reduced. In particular, as the resist pattern size becomes smaller than the quarter micron, the demand for improvement of the line edge roughness is increasing, but the guideline for the improvement has not been disclosed so far. Further, there are problems with the profile and development defects.

[0010]

As described above, in the known technique of the conventional photoresist composition, roughness is observed at the edge of the pattern, a stable pattern cannot be obtained, and there is a problem of development defect. Therefore, further improvement has been desired. Therefore, it is an object of the present invention to provide a positive resist composition in which the edge roughness of a pattern is improved and the problem of development defects is also improved and an excellent resist pattern profile is obtained.

[0011]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to the constituent materials of a resist composition in a positive type chemical amplification system, and as a result, by combining a specific acid-decomposable resin and a specific sulfonimide type compound. The present invention has been accomplished by knowing that the object is achieved. That is, the above object is achieved by the following configurations.

(1) (A) a resin which has an aliphatic cyclic hydrocarbon group and whose dissolution rate in an alkali developing solution is increased by the action of an acid, (B) a compound which generates an acid upon irradiation with actinic rays or radiation, (C) A positive resist composition containing a compound having a sulfonimide structure in the molecule represented by the following general formula (1).

[0013]

[Chemical 6]

(In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group. R ₂ and R ₃ are each independently an alkyl group, Cycloalkyl group, aryl group,
Represents an aralkyl group or a heterocyclic group. )

(2) The resin of (A) has the following general formula (p
I) to at least one selected from the group of repeating units represented by the general formula (pVI) and having a partial structure containing an alicyclic hydrocarbon and the repeating unit represented by the following general formula (II).
The positive resist composition as described in (1) above, which contains a seed.

[0016]

[Chemical 7]

(Wherein R ₁₁ is a methyl group, an ethyl group, n
Represents a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently have 1 to 4 carbon atoms,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{12 to} R ₁₄ , or either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R
_{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ is Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ are each independently
It represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. Also, R ₂₃ and R
₂₄ may combine with each other to form a ring. )

[0018]

[Chemical 8]

In formula (II): R ₁₁ 'and R ₁₂ ' each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z'represents an atomic group for forming an alicyclic structure which contains two carbon atoms (C-C) bonded and may have a substituent.

(3) Z'in the general formula (II)
Represents an atomic group for forming a bridged alicyclic structure, which contains two carbon atoms (C-C) bonded to each other and may have a substituent (2) The positive resist composition as described in 1.

(4) The positive resist composition as described in (2) above, wherein the general formula (II) is the following general formula (II-A) or general formula (II-B).

[0022]

[Chemical 9]

In formulas (II-A) and (II-B): R ₁₃ 'to R
₁₆ 'each independently represents a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR _5, group decomposable by the action of an acid, -C (= O) -X- A'-R 17', or substituted It represents an alkyl group which may have a group or a cyclic hydrocarbon group. Here, R ₅ represents an alkyl group which may have a substituent, a cyclic hydrocarbon group or the following —Y group. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n represents 0 or 1.
R ₁₇ 'is —COOH, —COOR ₅ , —CN, hydroxyl group,
An alkoxy group which may have a substituent, -CO-NH
-R _6, represents a -CO-NH-SO ₂ -R ₆ or -Y group shown below. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -Y group;

[0024]

[Chemical 10]

(In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represents a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.)

(5) The above composition (1), which is a composition for exposure by far-ultraviolet light having a wavelength of 220 nm or less.
~ The positive resist composition as described in any of (4).

The preferred embodiments will be described below. (6) The positive resist composition as described in any of (1) to (5) above, which further comprises (D) a nitrogen-containing basic compound. (7) (E) The above (1) to (6), further containing a fluorine-based and / or silicon-based surfactant.
The positive resist composition as described in any one of 1.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The components used in the present invention will be described in detail below. [1] (A) A resin whose dissolution rate in an alkali developing solution is increased by the action of an acid (also referred to as “acid-decomposable resin”).

The acid-decomposable resin (A) of the present invention may be any resin as long as it has an aliphatic cyclic hydrocarbon group and the dissolution rate in an alkali developing solution is increased by the action of an acid. Containing at least one selected from the group of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pI) to general formula (pVI) and the repeating unit represented by the general formula (II). It is preferable that the resin is

In the general formulas (pI) to (pVI), R
The alkyl group in _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples thereof include sec-butyl group and t-butyl group. Further, the further substituent of the above alkyl group has 1 carbon atom
To 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group for R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6 to 30, and particularly preferably 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

In the present invention, the alicyclic moiety is preferably adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group. , A cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Represent Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

In the above resins, the general formulas (pI) to (pV)
The structure represented by I) can be used for protection of alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field. Specific examples thereof include a carboxylic acid group, a sulfonic acid group, a phenol group and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable. General formula (pI) in the above resin
The alkali-soluble group protected by the structure represented by (pVI) is preferably the following general formulas (pVII) to (pVII).
The group represented by XI) is mentioned.

[0038]

[Chemical 14]

Here, R _{11 to} R ₂₅ and Z are the same as defined above. In the above resin, the repeating unit having an alkali-soluble group protected by the structures represented by the general formulas (pI) to (pVI) is preferably a repeating unit represented by the following general formula (pA).

[0040]

[Chemical 15]

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, alone or in combination of two or more. Represents a combination of groups. Ra represents any group of the above formulas (pI) to (pVI).

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown below.

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

In the above general formula (II), R ₁₁ 'and R ₁₂ '
Are each independently a hydrogen atom, a cyano group, a halogen atom,
Alternatively, it represents an alkyl group which may have a substituent. Z '
Represents an atomic group for forming an alicyclic structure which contains two carbon atoms (C-C) bonded and may have a substituent.

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. Above R ₁₁ ', R ₁₂ ', R ₂₁ '~ R
The alkyl group in ₃₀ 'is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and further preferably Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
a sec-butyl group and a t-butyl group.

Examples of the further substituent in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like,
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, examples of the acyl group include formyl group, acetyl group and the like, and examples of the acyloxy group include Can include an acetoxy group and the like.

The above-mentioned atomic group for forming the alicyclic structure of Z'is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferable. Examples of the alicyclic hydrocarbon skeleton to be formed include those shown by the following structures.

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

Preferred skeletons of bridged alicyclic hydrocarbons include (5), (6), (7),
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47) is mentioned.

The skeleton of the alicyclic hydrocarbon may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the above general formula (II-A) or (II-B). Among the repeating units having the bridged alicyclic hydrocarbon, the repeating unit represented by the general formula (II-A) or (II-B) is more preferable.

The above general formula (II-A) or (II-B)
In the formula, R ₁₃ ′ to R ₁₆ ′ are each independently a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposable by the action of an acid, —C (═O) —XA ′. -R
₁₇ ', or an alkyl group which may have a substituent or a cyclic hydrocarbon group. R ₅ may have a substituent, an alkyl group, cyclic hydrocarbon group or said group -Y. X is an oxygen atom, a sulfur atom, -NH-, -NH
It represents SO ₂ — or —NHSO ₂ NH—. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n is 0
Or represents 1. R ₁₇ 'is —COOH, —COOR ₅ ,
-CN, a hydroxyl group, an optionally substituted alkoxy _{group, -CO-NH-R 6,} -CO-NH-SO 2 -R 6
Alternatively, it represents the above-Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -
In the Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and
b represents 1 or 2.

[0058] In the resin according to the present invention, the acid decomposable group is substituted the -C (= O) 'may be included in, Z in formula (II)'-X-A'- R 17 It may be included as a group. The structure of the acid-decomposable _{group, -C (= O) -X 1} -
It is represented by R ₀ . In the formula, R ₀ is a t-butyl group,
tertiary alkyl group such as t-amyl group, isobornyl group, 1
1-alkoxyethyl group such as ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxymethyl group, 1
-Alkoxymethyl group such as ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group, 2-methyl-2-adamantyl group, mevalonic Examples thereof include lactone residues. X ₁ has the same meaning as X above.

Examples of the halogen atom in R ₁₃ 'to R ₁₆ ' include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

The alkyl group in R ₅ , R ₆ , and R ₁₃ 'to R ₁₆ ' is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
Six linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

The cyclic hydrocarbon group for R ₅ , R ₆ , and R ₁₃ 'to R ₁₆ ' is, for example, a cyclic alkyl group or a bridged hydrocarbon, and is cyclopropyl group, cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
Examples thereof include an adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two members out of R ₁₃ ′ to R ₁₆ ′ is cyclopentene,
Examples thereof include rings having 5 to 12 carbon atoms such as cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R ₁₇ ′ include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

Further substituents on the above-mentioned alkyl group, cyclic hydrocarbon group and alkoxy group include hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group, acyloxy group, alkyl group, cyclic hydrocarbon group and the like. Can be mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, and examples of the acyl group include formyl group, acetyl group and the like, and acyloxy group. Examples thereof include acetoxy group and the like. Also,
Examples of the alkyl group and cyclic hydrocarbon group include those mentioned above.

The divalent linking group of A'is selected from the group consisting of alkylene group, substituted alkylene group, ether group, thioether group, carbonyl group, ester group, amide group, sulfonamide group, urethane group and urea group. These may be selected alone or in combination of two or more groups. Examples of the alkylene group and the substituted alkylene group for A ′ include groups represented by the following formula. - _{[C (R a) (R b} ) ] _r - wherein, R _a, R _b represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. As the substituent of the substituted alkyl group,
Examples thereof include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r represents an integer of 1 to 10.

In the resin according to the present invention, the group decomposable by the action of acid is one of the above general formulas (pI) to (pV
A repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I), a repeating unit represented by the general formula (II),
And at least one of the repeating units of the copolymerization component described below.
It may be contained in the repeating unit of the seed.

The above general formula (II-A) or general formula (II
The various substituents of R ₁₃ ′ to R ₁₆ ′ in —B) are an atomic group for forming the alicyclic structure in formula (II) or an atomic group for forming a bridged alicyclic structure. It also serves as a substituent of Z.

The above general formula (II-A) or general formula (II
As specific examples of the repeating unit represented by -B), the following [II
-1] to [II-175], but the present invention is not limited to these specific examples.

[0068]

[Chemical formula 24]

[0069]

[Chemical 25]

[0070]

[Chemical formula 26]

[0071]

[Chemical 27]

[0072]

[Chemical 28]

[0073]

[Chemical 29]

[0074]

[Chemical 30]

[0075]

[Chemical 31]

[0076]

[Chemical 32]

[0077]

[Chemical 33]

[0078]

[Chemical 34]

[0079]

[Chemical 35]

[0080]

[Chemical 36]

[0081]

[Chemical 37]

[0082]

[Chemical 38]

[0083]

[Chemical Formula 39]

[0084]

[Chemical 40]

[0085]

[Chemical 41]

[0086]

[Chemical 42]

The acid-decomposable resin of the present invention may further contain a repeating unit having a lactone structure represented by the following general formula (IV).

[0088]

[Chemical 43]

In formula (IV), R ₁ a represents a hydrogen atom or a methyl group. W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, or a combination of two or more groups selected from the group consisting of. Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, m + n
Is 2 or more and 6 or less.

Examples of the alkyl group having 1 to 4 carbon atoms represented by Ra _{1 to} Re ₁ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like. Can be mentioned.

In formula (IV), examples of the alkylene group for W ₁ include groups represented by the following formula. — [C (Rf) (Rg)] r ₁ — In the above formula, Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, and both may be the same or different. Good. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r ₁ is an integer of ₁ to 10.

Examples of the further substituent in the above alkyl group include a carboxyl group, an acyloxy group, a cyano group, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an acetylamide group, an alkoxycarbonyl group, An acyl group can be mentioned. Examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the substituent of the substituted alkoxy group include an alkoxy group and the like. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. An acetoxy group etc. are mentioned as an acyloxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

Specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (IV) are shown below, but the present invention is not limited thereto.

[0094]

[Chemical 44]

[0095]

[Chemical formula 45]

[0096]

[Chemical formula 46]

In the specific example of the above general formula (IV), from the viewpoint that the exposure margin becomes better (IV-17) to
(IV-36) is preferred. Further, as the structure of the general formula (IV), a structure having an acrylate structure is preferable from the viewpoint of good edge roughness.

Further, the following general formulas (V-1) to (V-4)
You may contain the repeating unit which has the group represented by either of these.

[0099]

[Chemical 47]

In the general formulas (V-1) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group or alkenyl group. Two of R _{1b to} R _5b may combine with each other to form a ring.

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include linear and branched alkyl groups, which may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
12 straight chain or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and even more preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t. -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
It is a decyl group. The cycloalkyl group for R _{1b to} R _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having a carbon number of 2 to 6, such as a vinyl group, a propenyl group, a butenyl group and a hexenyl group. Examples of the ring formed by combining two members out of R _{1b to} R _5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. The general formula (V-1)
R _{1b to} R _5b in to (V-4) may be bonded to any of the carbon atoms constituting the cyclic skeleton.

The preferred substituents that the alkyl group, cycloalkyl group and alkenyl group may have include alkoxy groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine). Atom), an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, a nitro group and the like.

The repeating unit having a group represented by any one of the general formulas (V-1) to (V-4) is represented by the above general formula (II-
A) or (II-B) in which at least one of R ₁₃ 'to R ₁₆ ' has a group represented by the above general formulas (V-1) to (V-4) (for example, -COOR ₅ R ₅ is a general formula (V-
1) to (V-4), or a repeating unit represented by the following general formula (AI).

[0104]

[Chemical 48]

In the general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group represented by R _b0 may have include those represented by the general formula (V-1) to
Examples of the preferable substituent that the alkyl group as R _1b in (V-4) may have include those exemplified above. Examples of the halogen atom of R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. A'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group combining these. B ₂ represents a group represented by any one of formulas (V-1) to (V-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0106]

[Chemical 49]

In the above formula, Rab and Rbb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group and an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

Specific examples of the repeating unit represented by formula (AI) are shown below, but the content of the present invention is not limited thereto.

[0109]

[Chemical 50]

[0110]

[Chemical 51]

[0111]

[Chemical 52]

[0112]

[Chemical 53]

[0113]

[Chemical 54]

[0114]

[Chemical 55]

[0115]

[Chemical 56]

The acid-decomposable resin of the present invention may further contain a repeating unit represented by the following general formula (VI).

[0117]

[Chemical 57]

In the general formula (VI), A ₆ is a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group or an ester group, alone or in combination of two or more groups. Represents R _6a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

In the general formula (VI), examples of the alkylene group for A ₆ include groups represented by the following formula. -[C (Rnf) (Rng)] r- In the above formula, Rnf and Rng are each a hydrogen atom, an alkyl group,
It represents a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, and more preferably selected from methyl group, ethyl group, propyl group and isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. r is an integer of 1-10. General formula (VI)
In the above, examples of the cycloalkylene group represented by A ₆ include those having 3 to 10 carbon atoms.
Examples thereof include a cyclohexylene group and a cyclooctylene group.

The bridged alicyclic ring containing Z ₆ may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 5 carbon atoms), an acyl group (eg, formyl group, benzoyl group), an acyloxy group ( Examples thereof include a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having a carbon number of 1 to 4), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (-CONHSO ₂ CH ₃ etc.). still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having a carbon number of 1 to 4) or the like.

In the general formula (VI), the oxygen atom of the ester group bonded to A ₆ may be bonded at any position of the carbon atoms constituting the bridged alicyclic ring structure containing Z _6. Good.

Specific examples of the repeating unit represented by formula (VI) are shown below, but the invention is not limited thereto.

[0123]

[Chemical 58]

[0124]

[Chemical 59]

Further, it may contain a repeating unit having a group represented by the following general formula (VII).

[0126]

[Chemical 60]

In formula (VII), R ₂ c to R ₄ c each independently represent a hydrogen atom or a hydroxyl group. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

The group represented by the general formula (VII) is preferably a dihydroxy body or a monohydroxy body, more preferably a dihydroxy body.

Examples of the repeating unit having a group represented by the general formula (VII) include the general formula (II-A) or (II-
At least one of R ₁₃ 'to R ₁₆ ' in B) has a group represented by the above general formula (VII) (for example, -COO).
R ₅ of R ₅ represents a group represented by general formulas (V-1) to (V-4), or a repeating unit represented by the following general formula (AII).

[0130]

[Chemical formula 61]

In formula (AII), R ₁ c represents a hydrogen atom or a methyl group. R ₂ c to R ₄ c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

Specific examples of the repeating unit having the structure represented by formula (AII) are shown below, but the invention is not limited thereto.

[0133]

[Chemical formula 62]

Further, it may contain a repeating unit having a group represented by the following general formula (VIII).

[0135]

[Chemical formula 63]

In the general formula (VIII): Z ₂ is —O— or —
Represents N (R ₄₁ ) −. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R 4
Represents 2. R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group for R ₄₁ and R ₄₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the haloalkyl group for R ₄₁ and R ₄₂ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group and a trichloromethyl group. Examples of the cycloalkyl group for R ₄₂ include a cyclopentyl group, a cyclohexyl group and a cyclooctyl group.

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group as R ₄₂ or the camphor residue may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom and an iodine atom), an alkoxy group (preferably having a carbon number of 1 to 1).
4, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, for example, formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group), an aryl group (preferably having a carbon number of 6 to 14, for example, a phenyl group), and the like.

Specific examples of the repeating unit represented by the general formula (VIII) include the following [I'-1] to [I'-7], but the present invention is not limited to these specific examples. Not a thing.

[0140]

[Chemical 64]

[0141]

[Chemical 65]

The acid-decomposable resin as the component (A) has, in addition to the repeating structural units described above, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary characteristics of resist. Various repeating structural units can be contained for the purpose of adjusting resolution, heat resistance, sensitivity and the like.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers. Thereby, the performance required for the acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film-forming property (glass transition point),
Fine adjustments such as (3) alkali developability, (4) film slippage (hydrophilicity / hydrophobicity, selection of alkali-soluble groups), (5) adhesion of the unexposed area to the substrate, and (6) dry etching resistance are possible. . Examples of such monomers include acrylic acid esters, methacrylic acid esters, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic Acid-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate,
Trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate,
Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.

Methacrylic acid esters (preferably alkyl methacrylate having an alkyl group having 1 to 10 carbon atoms): methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, penta Erythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.

Acrylamides: Acrylamide, N-
Alkyl acrylamide (Alkyl group has 1 carbon
10 to, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group and the like. ), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group,
(Eg, cyclohexyl group), N-hydroxyethyl-
N-methyl acrylamide, N-2-acetamidoethyl-N-acetyl acrylamide and the like.

Methacrylamides: Methacrylamides,
N-alkylmethacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-
Butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkylmethacrylamide (alkyl groups include ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-
Methylmethacrylamide, etc.

Allyl compounds: Allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol. etc.

Vinyl ethers: alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1
-Methyl-2,2-dimethylpropyl vinyl ether,
2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether,
Dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl. Acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Dialkyl itaconates: dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate and the like.

Others Crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleironitrile and the like.

In addition, any addition-polymerizable unsaturated compound copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may be copolymerized.

In the acid-decomposable resin, the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution and heat resistance, which are generally required performances of a resist. It is appropriately set in order to adjust the sex, sensitivity and the like.

Preferred examples of the acid-decomposable resin of the present invention include the following. (1) Those containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI) (side chain type) (2) represented by the general formula (II) Containing a repeating unit (main chain type) However, examples of (2) further include the following. (3) Those having a repeating unit represented by the general formula (II), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type)

In the acid-decomposable resin, the compounds represented by the general formulas (pI) to (pV)
The content of the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by I) is 30 to 30 in all repeating structural units.
70 mol% is preferable, 35-65 mol% is more preferable, and 40-60 mol% is still more preferable. The content of the repeating unit represented by the general formula (II) in the acid-decomposable resin is preferably 10 to 60 mol% in all the repeating structural units, more preferably 15 to 55 mol%, and further preferably 20 to 50 mol%. Mol%.

The content of the repeating unit represented by the general formula (IV) in the acid-decomposable resin is 1 to 6 in all repeating structural units.
0 mol% is preferable, more preferably 5 to 50 mol%,
More preferably, it is 10 to 40 mol%. In the acid-decomposable resin, the content of the repeating unit having a group represented by any one of formulas (V-1) to (V-1) is preferably 1 to 60 mol% in all repeating structural units, and more preferably Preferably 5
It is 50 mol%, more preferably 10 to 40 mol%.

The content of the repeating unit represented by the general formula (VI) in the acid-decomposable resin is 1 to 6 in all repeating structural units.
0 mol% is preferable, more preferably 5 to 50 mol%,
More preferably, it is 10 to 40 mol%. The content of the repeating unit having a group represented by the following general formula (VII) in the acid-decomposable resin is 5 to 40 mol% in all repeating structural units.
Is preferable, and more preferably 10 to 35 mol%.
The content of the repeating unit represented by the general formula (VIII) in the acid-decomposable resin is 15 to 55 mol% in all repeating structural units.
Is preferable, and more preferably 19 to 51 mol%.

Further, the content of the repeating structural unit in the resin based on the monomer of the above-mentioned additional copolymerization component can be appropriately set according to the desired performance of the resist. 99 moles based on the total total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by formulas (pI) to (pVI) and the repeating unit represented by the general formula (II). % Or less, more preferably 90 mol% or less, still more preferably 80 mol% or less.

The acid-decomposable resin used in the present invention can be synthesized by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer species is charged in a batch or in the middle of the reaction into a reaction vessel, and if necessary, a reaction solvent, for example, tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether or methyl ethyl ketone, Ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and further homogenized by dissolving in a solvent dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate described later, nitrogen, argon, etc. If necessary, heating is performed in an inert gas atmosphere, and polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.).
If desired, an initiator is added or added in portions, and after completion of the reaction, the reaction mixture is put into a solvent to recover the desired polymer by a method such as powder or solid recovery. Reaction concentration is 20% by weight
It is at least 30% by weight, preferably at least 40% by weight. Reaction temperature is 10 ° C to 150
C., preferably 30 to 120.degree. C., more preferably 50 to 100.degree.

The weight average molecular weight of the resin according to the present invention is G
The polystyrene conversion value by the PC method is preferably 1,000 to 200,000. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, which is not preferable, and when it exceeds 200,000, developability is deteriorated and film forming property is deteriorated due to extremely high viscosity. It produces less favorable results.

In the positive photoresist composition for deep UV exposure of the present invention, the compounding amount of all the resins according to the present invention in the whole composition is 40 to 99.
It is preferably 99% by weight, more preferably 50 to 99.9.
It is 7% by weight.

[2] (B) Compound that Generates Acid upon Irradiation with Actinic Rays or Radiation (Photoacid Generator) The photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. Is. The photo-acid generator used in the present invention is used in photo-initiator for photo-cationic polymerization, photo-initiator for photo-radical polymerization, photo-decoloring agent for dyes, photo-discoloring agent, micro resist, etc. Known light (ultraviolet ray of 400 to 200 nm, deep ultraviolet ray, particularly preferably g line, h line, i line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X ray,
A compound that generates an acid by a molecular beam or an ion beam and a mixture thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and other onium salts,
Organic halogen compounds, organic metal / organic halides, o
Examples thereof include a photoacid generator having a nitrobenzyl-type protecting group, a compound represented by iminosulfonate and the like, which photolyzes to generate a sulfonic acid, a disulfone compound, a diazoketosulfone, a diazodisulfone compound.
Further, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer can be used.

Further, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like which generate an acid by light can also be used.

Among the compounds which decompose when exposed to actinic rays or radiation to generate an acid, those which are particularly effectively used will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
1) an oxazole derivative or a general formula (PAG
An S-triazine derivative represented by 2).

[0167]

[Chemical formula 66]

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —C (Y) ₃
Indicate. Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0169]

[Chemical formula 67]

(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4).

[0171]

[Chemical 68]

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ ,
R ^205's each independently represent a substituted or unsubstituted alkyl group or aryl group.

Z ⁻ represents a counter anion, for example, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Condensed polynuclear aromatic sulfonate anion such as perfluoroalkane sulfonate anion such as O ₄ ⁻ and CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anion, naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, sulfonate group Examples thereof include dyes contained therein, but are not limited thereto.

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Specific examples include, but are not limited to, the compounds shown below.

[0176]

[Chemical 69]

[0177]

[Chemical 70]

[0178]

[Chemical 71]

[0179]

[Chemical 72]

[0180]

[Chemical formula 73]

[0181]

[Chemical 74]

[0182]

[Chemical 75]

[0183]

[Chemical 76]

[0184]

[Chemical 77]

In the above, Ph represents a phenyl group.
The onium salts represented by the general formulas (PAG3) and (PAG4) are known and can be synthesized by the method described in, for example, U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331. .

(3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

[0187]

[Chemical 78]

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0190]

[Chemical 79]

[0191]

[Chemical 80]

[0192]

[Chemical 81]

[0193]

[Chemical formula 82]

[0194]

[Chemical 83]

(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0196]

[Chemical 84]

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0198]

[Chemical 85]

[0199]

[Chemical 86]

The addition amount of these photo-acid generators is usually 0.001 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably, based on the solid content in the composition. Is used in the range of 0.5 to 10% by weight. If the addition amount of the photo-acid generator is less than 0.001% by weight, the sensitivity tends to be low, and if the addition amount is more than 30% by weight, the light absorption of the resist becomes too high, resulting in deterioration of the profile and process. (Especially bake) Margin tends to be narrow.

[3] (C) Compound represented by the general formula (1) and containing a sulfonimide structure in the molecule (also referred to as component (C) or compound of (C)) In the general formula (1), R ₁ is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (preferably having 1 to 12 carbon atoms), a cycloalkyl group (preferably having 4 to 18 carbon atoms), an aryl group ( Preferably, it has 6 to 20 carbon atoms, an aralkyl group (preferably, 7 to 20 carbon atoms) or a heterocyclic group (particularly, an aromatic group containing a hetero atom is preferable, and a heterocyclic group having 4 to 10 carbon atoms is preferable, In particular, an aromatic group containing a hetero atom having 4 to 10 carbon atoms is preferable). R ₂ and R ₃ are each independently
Alkyl group (preferably having 1 to 12 carbon atoms), cycloalkyl group (preferably having 4 to 18 carbon atoms), aryl group (preferably having 6 to 20 carbon atoms), aralkyl group (preferably having 7 to 20 carbon atoms) or hetero. Represents a cyclic group (in particular, an aromatic group containing a hetero atom is preferable, a heterocyclic group containing 4 to 10 carbon atoms is preferable, and an aromatic group containing a hetero atom having 4 to 10 carbon atoms is particularly preferable). All of these groups include those having a substituent. The substituent has 1 carbon atom
To C4 alkyl group, C1 to C4 alkoxy group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), C6 to C10 aryl group, C2 to C6 alkenyl group, cyano Group, hydroxy group, carboxy group,
Alkoxycarbonyl group having 2 to 5 carbon atoms, 2 to 5 carbon atoms
And an alkylcarbonyloxy group, a nitro group and the like.

R ₁ , R ₂ and R ₃ are preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent and a cycloalkyl having 4 to 15 carbon atoms which may have a substituent. A group, an aryl group having 6 to 18 carbon atoms which may have a substituent, an aralkyl group having 7 to 15 carbon atoms which may have a substituent, and a hetero atom which may have a substituent. It is an aromatic group having 4 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent, and an aromatic group having 5 to 12 carbon atoms which may have a substituent. A cycloalkyl group (cyclohexyl group, cyclooctyl group, etc.), an aryl group having 6 to 15 carbon atoms which may have a substituent, an aralkyl group having 7 to 15 carbon atoms which may have a substituent,
4 to 4 carbon atoms containing a hetero atom which may have a substituent
It is an aromatic group of 6 and particularly preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent (methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group). Etc.), an aryl group having 6 to 14 carbon atoms which may have a substituent (phenyl group, naphthyl group, anthryl group), an aralkyl group having 7 to 12 carbon atoms which may have a substituent (benzyl Group, a phenethyl group, etc.) and a hetero atom-containing aromatic group having 5 to 6 carbon atoms (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thiophenyl group, etc.). In addition to these, R ₁ is also preferably a hydrogen atom or a halogen atom.

Further, R ₁ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, n-propyl group, t-butyl group, n-hexyl group, etc.), a cycloalkyl group having 6 to 12 carbon atoms which may have a substituent (cyclohexyl group, cyclooctyl group etc.), and a C6 to 10 carbon atom which may have a substituent. Aryl group (phenyl group, naphthyl group, p-toluyl group, etc.), or aromatic group having 4 to 6 carbon atoms containing a hetero atom (nitrogen atom, sulfur atom, etc.) which may have a substituent (2- A pyridyl group, a 3-pyridyl group,
4-pyridyl group, 2-thiophenyl group, etc.) and R ₂
And R ₃ are each independently an optionally substituted alkyl group having 1 to 12 carbon atoms (methyl group, ethyl group, n-butyl group, n-octyl group, n-dodecyl group, tri Fluoromethyl group, nonafluorobutyl group, perfluorooctyl group, etc., aryl group having 6 to 10 carbon atoms which may have a substituent (phenyl group, naphthyl group, fluorine-substituted phenyl group, trifluoromethyl group substituted) A phenyl group, an alkoxyphenyl group, etc.) or an optionally substituted aralkyl group having 7 to 15 carbon atoms (benzyl group, phenethyl group, etc.).

Specific examples of the compound having a sulfonimide structure in the molecule of the component (C) are shown below, but of course the invention is not limited thereto.

[0205]

[Chemical 87]

[0206]

[Chemical 88]

[0207]

[Chemical 89]

The content of the component (C) is suitably 0.01 to 20% by weight, preferably 0.02 to 15% by weight, particularly preferably 0.03 to 10% by weight.
As the compound as the component (C), one type may be used, or two or more types may be mixed and used.

[4] (D) Nitrogen-containing basic compound Next, the (D) nitrogen-containing basic compound which can be preferably used in the positive resist composition of the present invention will be explained. As the nitrogen-containing basic compound (D), an organic amine,
A basic ammonium salt, a basic sulfonium salt, or the like is used as long as it does not deteriorate sublimation or resist performance. Among these nitrogen-containing basic compounds, organic amines are preferable in terms of excellent image performance. For example, JP-A-63-149640, JP-A-5-249662, JP-A-5-127369
No. 5-289322, No. 5-249683, No. 5-28
9340, JP 5-232706, JP 5-257282, JP
6-242605, JP-A-6-242606, JP-A-6-266100, JP-A-6-266110, JP-A-6-317902, JP-A-7-120929
No. 7, JP-A-7-146558, JP-A No. 7-319163, JP-A 7-50
8840, JP 7-333844, JP 7-219217, JP
7-92678, JP 7-28247, JP 8-22120, JP 8-110638, JP 8-123030, JP 9-274312,
JP-A-9-166871, JP-A-9-292708, JP-A-9-325496
No., special table 7-508840, USP5525453, USP5629134,
Basic compounds described in USP 5667938 and the like can be used.

The nitrogen-containing basic compound is preferably 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1, 4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4 '
-Diaminodiphenyl ether, pyridinium p-toluenesulfonate, 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine and the like. Among these, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2]. Organic amines such as octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4′-diaminodiphenyl ether, triethylamine and tributylamine are preferable.

The content of the nitrogen-containing basic compound (D) is usually 0.001 to 10 parts by weight, preferably 0.001 to 100 parts by weight with respect to 100 parts by weight of the positive resist composition (solid content).
5 parts by weight, more preferably 0.001 to 0.5 parts by weight. If it is less than 0.001 part by weight, the effect of adding the component (D) cannot be sufficiently obtained. On the other hand, if the amount exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the non-exposed areas tends to be significantly deteriorated.
The basic compound (D) can be used alone or in combination of two or more.

[5] (E) Fluorine-based and / or Silicon-based Surfactant The positive resist composition of the present invention comprises (E) a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicone. It is preferable to contain any one of a system surfactant and a surfactant containing both a fluorine atom and a silicon atom, or two or more kinds. When the positive resist composition of the present invention contains the (E) surfactant,
When an exposure light source of 50 nm or less, particularly 220 nm or less is used, it is possible to provide a resist pattern with good sensitivity and resolution and with less adhesiveness and less development defects. Examples of these (E) surfactants include those disclosed in JP-A-62-36.
663, JP 61-226746, JP 61-226745, JP 62-17095.
No. 0, JP-A-63-34540, JP-A-7-
230165, JP 8-62834A, JP 9-54432A, JP 9-5988A, JP 2002-277862A, US Pat. No. 5
No. 405720, No. 5360692, No. 5529881, No. 5296330,
The surfactants described in Nos. 5436098, 5576143, 5294511 and 5824451 can be mentioned, and the following commercially available surfactants can be used as they are. Examples of commercially available surfactants that can be used include Ftop EF30
1, EF303, (New Akita Kasei Co., Ltd.), Florard FC
430, 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F176, F189, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-38.
2, SC101, 102, 103, 104, 105, 1
06 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), and other fluorine-based surfactants or silicon-based surfactants. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Can also be used as a silicon-based surfactant.

As the surfactant, in addition to the known ones as described above, fluoroaliphatic compounds produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) are used. A surfactant using a polymer having a fluoroaliphatic group derived from the compound can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991. As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable, and the polymer is irregularly distributed. Or a block copolymer may be used. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having a different chain length of alkylene within the same chain length, such as a block linking body) or a poly (block connecting body of oxyethylene and oxypropylene) group may be used. Further, the copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer, but also a monomer having two or more different fluoroaliphatic groups. Alternatively, a ternary or more copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates) may be used. For example, commercially available surfactants include Megafac F178, F-470, F-47.
3, F-475, F-476, and F-472 (manufactured by Dainippon Ink and Chemicals, Inc.). further,
Copolymer of acrylate (or methacrylate) having C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) having C ₆ F ₁₃ group and (poly (oxyethylene)) ) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (copolymer of or methacrylate), acrylate having a C ₈ F _{1 7} group (or methacrylate) (poly (oxyalkylene)) acrylate (or methacrylate ), A copolymer of acrylate (or methacrylate) having a C ₈ F ₁₇ group, (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) , And so on It

The amount of the (E) surfactant used is preferably 0.0001 to 2% by weight, more preferably 0.001 to 2% by weight, based on the total amount of the positive resist composition (excluding the solvent).
2% by weight, particularly preferably 0.001 to 1% by weight.

The positive resist composition of the present invention, if necessary, has a molecular weight of 2000 or less, has a group capable of decomposing by the action of an acid, and has a low molecular weight whose alkali solubility is increased by the action of an acid. An acid decomposable compound can be included.
For example Proc.SPIE, 2724, 355 (1996), JP-A-8-15865,
USP5310619, USP-5372912, J. Photopolym. Sci., Te
ch., Vol.10, No.3,511 (1997)), which contains an acid decomposable group, cholic acid derivative, dehydrocholic acid derivative, deoxycholic acid derivative, lithocholic acid derivative, ursocholic acid derivative, abietin An alicyclic compound such as an acid derivative and an aromatic compound such as a naphthalene derivative having an acid-decomposable group can be used as the low-molecular acid-decomposable compound. Furthermore, the low molecular weight acid-decomposable dissolution-inhibiting compound described in JP-A-6-51519 can also be used in an addition range at a level that does not deteriorate the transmittance at 220 nm.
A 2-naphthoquinonediazite compound can also be used.

When the low molecular weight acid-decomposable dissolution inhibiting compound is used in the resist composition of the present invention, its content is usually 0.5 to 50 parts by weight based on 100 parts by weight (solid content) of the resist composition. Used in the range of 0.1 part, preferably 0.
5 to 40 parts by weight, more preferably 0.5 to 30 parts by weight,
It is particularly preferably used in the range of 0.5 to 20.0 parts by weight. Addition of these low-molecular-weight acid-decomposable dissolution-inhibiting compounds not only further improves the development defects but also improves dry etching resistance.

In the positive resist composition of the present invention, if necessary, a compound that accelerates dissolution in a developing solution, an antihalation agent, a plasticizer, a surfactant, a photosensitizer, an adhesion aid, and a crosslinking agent. , A photobase generator and the like can be contained.

Examples of the dissolution accelerating compound for a developing solution which can be used in the present invention include, for example, compounds containing two or more phenolic hydroxyl groups described in JP-A-3-206458, 1-
Naphthol such as naphthol or carboxyl group 1
Molecular weight of 100 or more compounds, carboxylic acid anhydrides, sulfonamide compounds, sulfonylimide compounds, etc.
Examples thereof include low molecular weight compounds of 0 or less. The compounding amount of these dissolution accelerating compounds is the total weight of the composition.
It is preferably 30% by weight or less, more preferably 20% by weight or less, based on (solid content).

As a suitable antihalation agent, a compound which efficiently absorbs irradiation radiation is preferable, and substituted benzenes such as fluorene, 9-fluorenone and benzophenone; anthracene, anthracene-9-methanol, anthracene-9-carboxyl. Examples thereof include polycyclic aromatic compounds such as ethyl, phenanthrene, perylene and azylene. Among them, polycyclic aromatic compounds are particularly preferable. These antihalation agents reduce the reflected light from the substrate and reduce the influence of multiple reflection in the resist film, thereby exhibiting the effect of improving standing waves.

A nonionic surfactant may be used in combination for the purpose of improving the coatability of the resist composition of the present invention and improving the developability. As nonionic surfactants that can be used in combination, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene sorbitan mono Examples thereof include stearate and sorbitan monolaurate.

Further, a photosensitizer can be added to improve the acid generation rate by exposure. Suitable photosensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, pyrene, phenothiazine, benzyl, benzoflavin, acetophenone, phenanthrene, benzoquinone, anthraquinone, 1 , 2
-Naphthoquinone and the like can be mentioned, but the invention is not limited thereto. These photosensitizers can also be used as the antihalation agent.

The resist composition of the present invention usually has a pore size of, for example,
It is prepared as a solution by filtering with a filter of about m to 0.2 μm. Examples of the solvent used here include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, 3 -Methyl methoxypropionate, ethyl 3-ethoxypropionate,
β-Methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N-methylpyrrolidone, N, N-dimethylformamide, γ- Examples include butyrolactone and N, N-dimethylacetamide.
These solvents may be used alone or in combination.
Among these solvents, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, in particular, from the viewpoints of solubility in the composition, coatability on a substrate, storage stability, and the like. , 3
It is preferable that at least one solvent selected from -methyl methoxypropionate, ethyl 3-ethoxypropionate, and 2-heptanone is contained in an amount of 70% by weight or more in all the solvents. Further, the water content contained in the solvent affects the resist performance, so that it is preferably as small as possible.

Further, the resist composition of the present invention contains metal impurities such as metals and impurity components such as chlorine ions in an amount of 10 or less.
It is preferable to reduce it to 0 ppb or less. The presence of a large amount of these impurities is not preferable because it may cause a malfunction, a defect, and a decrease in yield in manufacturing a semiconductor device.

After applying the resist composition of the present invention onto a substrate by a suitable coating method such as a spinner or coater, prebaking (heating before exposure) is performed, and 220 n is passed through a predetermined mask.
A good resist pattern can be obtained by exposing with exposure light having a wavelength of m or less, performing PEB (post-exposure bake), and developing. The substrate used here may be a substrate normally used in a semiconductor device or other manufacturing apparatus, and examples thereof include a silicon substrate, a glass substrate, and a nonmagnetic ceramic substrate. Further, if necessary, additional layers such as a silicon oxide layer, a wiring metal layer, an interlayer insulating film, a magnetic film, an antireflection film layer, etc. may be present on these substrates, and various wirings may be present. , Circuits, etc. may be built in. Furthermore, these substrates may be subjected to a hydrophobic treatment according to a conventional method in order to enhance the adhesiveness of the resist film. Suitable hydrophobizing agents include, for example, 1,1,1,3,3,3-hexamethyldisilazane (HMDS) and the like.

The film thickness of the resist coated on the substrate is preferably in the range of about 0.1 to 10 μm, and in the case of ArF exposure, about 0.1 to 1.5 μm is recommended. The resist film applied on the substrate is about 3 at a temperature of about 60 to 160 ° C.
It is preferable to pre-bake for 0 to 300 seconds. If the prebaking temperature is low and the time is short, the amount of residual solvent in the resist film is relatively large, which causes adverse effects such as deterioration of adhesion. On the other hand, if the prebaking temperature is high and the time is long, adverse effects such as decomposition of constituent components such as the binder and photoacid generator of the resist composition may occur, which is not preferable.

As a device for exposing the resist film after pre-baking, a commercially available ultraviolet light exposure device, X-ray exposure device, electron beam exposure device, KrF excimer exposure device, ArF excimer exposure device, F ₂ excimer exposure device, etc. are used. Particularly in the present invention, an apparatus using an ArF excimer laser as an exposure light source is preferable. The post-exposure bake is performed for the purpose of causing elimination of a protecting group using an acid as a catalyst, for eliminating standing waves, and for diffusing an acid generator and the like into the film. This post-exposure bake can be performed in the same manner as the above-mentioned pre-bake. For example, the baking temperature is about 60-160 ° C, preferably about 90-150 ° C.

As the developing solution for the resist composition of the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate and ammonia water,
Primary amines such as ethylamine and n-propylamine,
Secondary amines such as diethylamine and di-n-butylamine, and tertiary amines such as triethylamine and methyldiethylamine.
Amines, dimethylethanolamine, alcohol amines such as triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethyl Quaternary ammonium salts such as ammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo- [5.
4.0] -7-Undecene, 1,5-diazabicyclo-
An aqueous alkaline solution of cyclic amines such as [4.3.0] -5-nonane can be used.

Further, an appropriate amount of hydrophilic organic solvent such as alcohols and ketones, nonionic or anionic surfactant, cationic surfactant or defoaming agent may be added to the above alkaline aqueous solution. Can be used. These additives are alkaline for the purpose of improving the adhesion with the substrate, reducing the amount of developer used, and reducing defects caused by bubbles during development, in addition to the purpose of improving the performance of the resist. It is added to the aqueous solution.

[0229]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Synthesis Example (1) Synthesis of Resin (1) (Side Chain Type) 2-Ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45 and dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5 to give a solid. 100 mL of a solution having a concentration of 20% was prepared. 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After completion of the dropping, the reaction solution was heated for 4 hours, V-65 was added again at 1 mol% and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature and distilled water / ISO propyl alcohol = 1/1 mixed solvent 3 L
The resin (1), which is a white powder that was crystallized and precipitated in the above, was recovered. Polymer composition ratio determined from C ¹³ NMR is 46/54
Met. Further, the weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 10700.

Resins (2) to (18) were synthesized in the same manner as in Synthesis Example (1) above. Below, the above resin (2)
The composition ratio and molecular weight of (18) are shown. (Repeating unit 1,
2, 3 and 4 are the order from the left of the structural formula. )

[0232]

[Table 1]

The structures of the above resins (1) to (18) are shown below.

[0234]

[Chemical 90]

[0235]

[Chemical Formula 91]

[0236]

[Chemical Formula 92]

[0237]

[Chemical formula 93]

[0238]

[Chemical 94]

Synthesis Example (2) Synthesis of Resin (19) (Main Chain Type) Norbornenecarboxylic acid t-butyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (solid content 60).
(% By weight) was charged in a separable flask and placed under a nitrogen stream 6
Heated at 0 ° C. When the reaction temperature became stable, 2 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. Heated for 12 hours. The obtained reaction mixture was diluted twice with tetrahydrofuran and then added to a mixed solution of hexane / isopropyl alcohol = 1/1 to precipitate a white powder. The precipitated powder was filtered out and dried to obtain the target Resin (19). When the molecular weight analysis of the obtained resin (19) by GPC was attempted, it was 8300 (weight average) in terms of polystyrene. Further, it was confirmed from the NMR spectrum that the molar ratio of norbornenecarboxylic acid t-butyl ester / norbornenecarboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.

Resins (20) to (30) were synthesized in the same manner as in Synthesis Example (2). The following resin (2
The composition ratios and molecular weights of 0) to (30) are shown. (Alicyclic olefin units 1, 2, and 3 are in order from the left in the structural formula.)

[0241]

[Table 2]

Further, the following resins (19) to (30)
Shows the structure of.

[0243]

[Chemical 95]

[0244]

[Chemical 96]

Synthesis Example (3) Synthesis of Resin (31) (Hybrid Type) Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were reacted at a molar ratio of 35/35/20/10. It was charged in a container and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature became stable, 1 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran and then poured into hexane in an amount 5 times the volume of the reaction mixture to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved in methyl ethyl ketone, reprecipitated in a mixed solvent of 5 volumes of hexane / t-butyl methyl ether = 1/1, and the precipitated white powder was collected by filtration, dried, and purposed. A resin (31) which is a product was obtained. When the molecular weight analysis of the obtained resin (31) by GPC was tried, it was 1 in terms of polystyrene.
It was 2100 (weight average). Further, from the NMR spectrum, the composition of the resin (1) was as follows: norbornene / maleic anhydride / t-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention in a molar ratio of 32 /
It was 39/19/10.

Resins (32) to (44) were synthesized in the same manner as in Synthesis Example (3). The following resin (3
The composition ratios and molecular weights of 2) to (44) are shown.

[0247]

[Table 3]

Further, the following resins (31) to (44)
Shows the structure of.

[0249]

[Chemical 97]

[0250]

[Chemical 98]

[0251]

[Chemical 99]

[0252]

[Chemical 100]

Synthesis Example (4) Synthesis of Resin (45) (Hybrid Type) Norbornenecarboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate, norbornene lactone acrylate in a molar ratio of 20/20.
/ 35/25 was charged into a reaction vessel and dissolved in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 to give a solid content of 6
A 0% solution was prepared. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature became stable, 3 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 12 hours, the reaction mixture was poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was redissolved in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 and put into 5 times the amount of hexane / methyl tBu ether to precipitate a white powder, which was taken out by filtration. This operation was repeated again and dried to obtain the target Resin (45). When the molecular weight analysis (RI analysis) of the obtained resin (45) by GPC was tried, it was 11 in terms of polystyrene.
600 (weight average), the amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (45) was 18/23/34/25 in terms of molar ratio of norbornene / maleic anhydride / 2-methyl-2-adamantyl acrylate / norbornene lactone acrylate of the present invention.

Resins (46) to (69) were synthesized in the same manner as in Synthesis Example (4). The following resin (4
The composition ratios and molecular weights of 6) to (69) are shown.

[0255]

[Table 4]

Further, the following resins (45) to (69) will be described below.
Shows the structure of.

[0257]

[Chemical 101]

[0258]

[Chemical 102]

[0259]

[Chemical 103]

[0260]

[Chemical 104]

[0261]

[Chemical 105]

Examples 1 to 75 and Comparative Examples 1 to 4 (Preparation and Evaluation of Positive Resist Composition) 1.25 g of each resin shown in Tables 5 to 7 synthesized in the above synthesis example
(However, 1.4 g in Comparative Examples) Photoacid generator, component (C) of the present invention (compound containing sulfonimide structure in the molecule) 100 mg, organic basic compound (amine) 3 mg if necessary, interface if necessary Activators (10 mg) were blended as shown in Tables 5 to 7, dissolved in propylene glycol monomethyl ether acetate at a solid content of 14% by weight, and then filtered through a 0.1 μm microfilter to give Examples 1 to 1. 75 and Comparative Examples 1 to 1
A positive resist composition of No. 4 was prepared.

[0263]

[Table 5]

[0264]

[Table 6]

[0265]

[Table 7]

As the surfactant, W1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.)
(Fluorine type) W2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)
(Fluorine and silicone type) W3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W4: Polyoxyethylene nonylphenyl ether W5: Troisol S-366 (Troy Chemical Co., Ltd.)
Manufactured).

As the amine, 1 represents 1,5-diazabicyclo [4.3.0] -5-nonene (DBN),
2 is bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) sebacate 3 is tri-n-butylamine 4
Is triphenylimidazole 5 is antipyrine 6
Represents 2,6-diisopropylaniline.

(Evaluation Test) First, Brewer Sci
ARC-25 manufactured by ence Co., Ltd. is applied on a silicon wafer by a spin coater to a thickness of 30 nm and dried, and then the positive photoresist composition solution obtained is applied on the silicon wafer using a spin coater. 15 and Comparative Example 1
Was dried at 130.degree. C., and at 140.degree. C. for 90 seconds to form a positive type photoresist film of about 0.4 .mu.m, which was exposed to ArF excimer laser (193 nm). The heat treatment after exposure is 120 in Examples 1 to 15 and Comparative Example 1.
℃, otherwise 140 ℃ for 90 seconds, develop with 2.38% tetramethylammonium hydroxide aqueous solution,
Rinse with distilled water to obtain a resist pattern profile. For these, edge roughness, profile, and development defect were evaluated as follows. The evaluation results are shown in Tables 8 to 10.

[Edge roughness]: The edge roughness is measured by measuring the edge roughness of an isolated pattern using a length-measuring scanning electron microscope (SEM).
The line pattern edge is detected at a plurality of positions, and the variance (3σ) of variations in the detected positions is used as an index of the edge roughness, and the smaller the value, the more preferable.

[Profile]: 0.
The cross-sectional shape of the 0.15 μm line pattern obtained by the minimum exposure that reproduces the 15 μm line pattern was observed with a scanning electron microscope. The rectangular one is ○,
The taper shape is shown by x. A slightly tapered shape is indicated by Δ.

[Development Defects]: With respect to the resist pattern obtained as described above, the number of development defects was measured with a KLA-2112 machine manufactured by KLA-Tencor Co., Ltd., and the obtained primary data value was used as the number of development defects. And

[0272]

[Table 8]

[0273]

[Table 9]

[0274]

[Table 10]

As is clear from the results of Tables 8 to 10, it can be seen that the positive resist composition of the present invention has excellent performances in edge roughness and profile, and the problem of development defects is improved.

[0276]

INDUSTRIAL APPLICABILITY The positive resist composition of the present invention is suitable for far-ultraviolet light, in particular, ArF excimer laser light having a wavelength of 193 nm, has excellent performances in edge roughness and profile, and improves development defect problems. ing. Therefore, it is preferably used for lithography using deep ultraviolet rays such as ArF excimer laser exposure.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA03 AA04 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB08 CB10 CB14 CB41 CC20 FA17 4J100 AL08P AR21P BA04P BA05P BA06P BA10P BA14P BA16P BA20P BA35P BA52P BA58P BB01P BC02P BC04P BC07P BC12P CA01 CA03 DA01 JA38

Claims (5)

[Claims] 1. A resin having (A) an aliphatic cyclic hydrocarbon group and having a dissolution rate in an alkali developing solution increased by the action of an acid, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, C) A positive resist composition containing a compound having a sulfonimide structure in the molecule represented by the following general formula (1). [Chemical 1] (In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group. R ₂ and R ₃ are each independently an alkyl group, a cycloalkyl group. , Represents an aryl group, an aralkyl group or a heterocyclic group.) 2. The resin of (A) has the following general formula (pI):
A repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pVI) and at least one selected from the group of repeating units represented by the following general formula (II). The positive resist composition according to claim 1. [Chemical 2] (In the formula, R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an alicyclic hydrocarbon group together with a carbon atom. Represents an atomic group necessary to form R _12.
To R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R _{12 to} R ₁₄ or R _15; ,
One of R ₁₆ represents an alicyclic hydrocarbon group. R ₁₇ ~ R ₂₁
Each independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group,
However, at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ has 1 to 1 carbon atoms.
Represents four linear or branched alkyl groups or alicyclic hydrocarbon groups. R _{22 to} R ₂₅ each independently have 1 to 1 carbon atoms.
It represents four linear or branched alkyl groups or alicyclic hydrocarbon groups, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may combine with each other to form a ring. ) [Chemical 3] In formula (II): R ₁₁ 'and R ₁₂ ' are each independently a hydrogen atom,
It represents a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z'represents an atomic group for forming an alicyclic structure which contains two carbon atoms (C-C) bonded and may have a substituent. 3. Z'in the general formula (II) contains two carbon atoms (C-C) bonded to each other to form a bridged alicyclic structure which may have a substituent. The positive resist composition according to claim 2, wherein the positive resist composition represents 4. The general formula (II) is represented by the following general formula (II-
The positive resist composition according to claim 2, which is represented by the formula (A) or the general formula (II-B). [Chemical 4] In formulas (II-A) and (II-B): R ₁₃ ′ to R ₁₆ ′ are each independently a hydrogen atom, a halogen atom, a cyano group, or —COO.
H, -COOR ₅ , a group that decomposes by the action of an acid, -C
(= O) represents the -X-A'-R ₁₇ ', or may have a substituent alkyl or cyclic hydrocarbon group. Here, R ₅ is an alkyl group which may have a substituent,
It represents a cyclic hydrocarbon group or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NHS
Representing the O ₂ NH-. A'represents a single bond or a divalent linking group. It is also possible to form at least two members to the ring of R _l3 '~R _16'. n represents 0 or 1. R ₁₇ '
Is —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group which may have a substituent, —CO—NH—R
₆ represents a -CO-NH-SO ₂ -R ₆ or -Y group shown below. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. -Y group; (In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represents a hydrogen atom or an alkyl group which may have a substituent.
Represents 1 or 2. ) 5. The positive resist composition according to claim 1, which is a composition for exposure by far ultraviolet light having a wavelength of 220 nm or less.