JP2003122010A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition excellent in edge roughness and sensitivity. SOLUTION: The positive resist composition is characterized in containing a resin which has a specified aliphatic cyclic hydrocarbon group and which increases the solubility rate with an alkali developer liquid by the effect of an acid, a compound which generates an acid by radiation of active rays or radiation, and a compound which accelerates the solubility rate of the film with an alkali developer liquid.

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, there is an increasing demand for improvement of the line edge roughness, but so far, no technology that can sufficiently satisfy the line edge roughness has been disclosed, let alone the line edge roughness. In addition, no technique has been found that can satisfy other characteristics such as sensitivity.

[0010]

As described above, the known techniques of the conventional photoresist composition have problems that the edges of the pattern have roughness and the sensitivity is poor. Therefore, further improvement is desired. Was there. Therefore, an object of the present invention is to provide a positive resist composition having improved pattern edge roughness and excellent sensitivity.

[0011]

Means for Solving the Problems As a result of earnest studies on the constituent materials of a resist composition in a positive-type chemical amplification system, the present inventors have accelerated the dissolution rate of a specific acid-decomposable resin and film in an alkali developing solution. The inventors of the present invention have found that the above object can be achieved by combining the above compounds, and have reached the present invention. That is, the above object is achieved by the following configurations.

(1) (A) A resin having an aliphatic cyclic hydrocarbon group, the dissolution rate of which in an alkali developing solution is increased by the action of an acid, which is represented by the following general formula (pI) to general formula (pVI). A resin containing at least one selected from the group of repeating units having a partial structure containing an alicyclic hydrocarbon shown below and a group of repeating units represented by the following general formula (II)

[0013]

[Chemical 5]

(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. )

[0015]

[Chemical 6]

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.
A positive resist composition comprising (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a compound that accelerates the dissolution rate of a film in an alkali developing solution.

(2) 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 (1) The positive resist composition as described in 1.

(3) The positive resist composition as described in (1) above, wherein the general formula (II) is the following general formula (II-A) or general formula (II-B).

[0019]

[Chemical 7]

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;

[0021]

[Chemical 8]

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

(4) The compound (C) is a compound selected from the group consisting of carboxylic acids, alcohols, sulfonamides, nitriles, malonic acid derivatives, and malonic acid esters, and the above (1) to (1) The positive resist composition as described in any one of (3). (5) The positive resist composition as described in any one of (1) to (4) above, which further contains a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group. object.

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

The preferred embodiments will be described below. (7) The positive resist composition as described in any of (1) to (6) above, which further comprises (D) a nitrogen-containing basic compound. (8) (E) The above (1), which further contains a fluorine-based and / or silicon-based surfactant.
The positive resist composition as described in any of (7).

[0026]

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 is a resin having an aliphatic cyclic hydrocarbon group and having a dissolution rate in an alkali developing solution increased by the action of an acid, and having the general formula (pI) to A repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pVI) and the general formula (I
It is a resin containing at least one selected from the group of repeating units represented by I).

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.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

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.

[0036]

[Chemical 12]

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).

[0038]

[Chemical 13]

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.

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

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 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, and particularly, a bridged structure. 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.

[0051]

[Chemical 20]

[0052]

[Chemical 21]

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.

[0056] 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 for 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, a bridged hydrocarbon group, a cyclopropyl group, a 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 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 an 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 the 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.

[0066]

[Chemical formula 22]

[0067]

[Chemical formula 23]

[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]

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).

[0086]

[Chemical 41]

In the general 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 the general 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 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 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.

The above alkyl group may be substituted,
Examples of the substituent 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, and an acyl group. 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.

[0092]

[Chemical 42]

[0093]

[Chemical 43]

[0094]

[Chemical 44]

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.

[0097]

[Chemical formula 45]

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.

Preferred substituents which the above alkyl group, cycloalkyl group and alkenyl group may have are an alkoxy group having 1 to 4 carbon atoms, a halogen atom (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).

[0102]

[Chemical formula 46]

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.

[0104]

[Chemical 47]

In the above formula, Rab and Rbb represent a hydrogen atom, an alkyl group, 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 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.

[0107]

[Chemical 48]

[0108]

[Chemical 49]

[0109]

[Chemical 50]

[0110]

[Chemical 51]

[0111]

[Chemical 52]

[0112]

[Chemical 53]

[0113]

[Chemical 54]

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

[0115]

[Chemical 55]

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, or a combination of two or more groups selected from the group consisting of 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 ( For example, propyl carbonyloxy group, benzoyloxy group), an alkyl group (preferably having from 1 to 4 carbon atoms), a carboxyl group, a hydroxyl group and 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.

[0121]

[Chemical 56]

[0122]

[Chemical 57]

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

[0124]

[Chemical 58]

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.

As the repeating unit having a group represented by the general formula (VII), the above 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).

[0128]

[Chemical 59]

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.

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

[0131]

[Chemical 60]

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

[0133]

[Chemical formula 61]

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.
Represents ₄₂ . 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 above general formula (VIII) include the following [I′-1] to [I′-7], but the present invention is limited to these specific examples. Not a thing.

[0138]

[Chemical formula 62]

[0139]

[Chemical formula 63]

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 a repeating structural unit 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 an alkyl group having 1 to 10 carbon atoms): methyl acrylate, ethyl acrylate, propyl acrylate,
Amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, 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), 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, an addition-polymerizable unsaturated compound which can be copolymerized with the monomers corresponding to the above 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.

A preferred embodiment of the acid-decomposable resin of the present invention is a repeating unit (side chain type) having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI). And those having a maleic anhydride derivative and a (meth) acrylate structure in addition to the repeating unit (main chain type) represented by the general formula (II) (hybrid type)
Is mentioned.

In the acid-decomposable resin, one of 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%.

When the acid-decomposable resin contains the repeating unit represented by the general formula (IV), the content thereof is preferably 1 to 60 mol% in all the repeating structural units, more preferably 5
˜50 mol%, and more preferably 10 to 40 mol%. When the acid-decomposable resin contains a repeating unit having a group represented by any one of formulas (V-1) to (V-1), the content is 1 to 60 mol% in all repeating structural units.
Is more preferable, 5 to 50 mol% is more preferable, and 10 to 40 mol% is still more preferable.

When the acid-decomposable resin contains the repeating unit represented by the general formula (VI), the content thereof is preferably 1 to 60 mol% in all the repeating structural units, more preferably 5
˜50 mol%, and more preferably 10 to 40 mol%. In the acid-decomposable resin, the content of a repeating unit having a group represented by the following general formula (VII) is preferably 5 to 40 mol% in all repeating structural units, more preferably 10 to 35 mol. %. When the repeating unit represented by the general formula (VIII) is contained in the acid-decomposable resin, the content thereof is preferably 15 to 55 mol% in all the repeating structural units, more preferably 19 to 51 mol%.

The content of the repeating structural unit based on the monomer of the additional copolymerization component contained in the resin can be appropriately set according to the desired performance of the resist. To the total total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pVI) and the repeating unit represented by the general formula (II). On the other hand, it is preferably 99 mol% 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 of the present invention, the blending amount of all the resins according to the present invention in the whole composition is preferably 40 to 99.99% by weight, more preferably 50% by weight based on the total solid content of the resist. -99.97% by weight.

[2] (B) Compound that Generates Acid upon Irradiation with Actinic Rays or Radiation (hereinafter may be referred to as photoacid generator) In the composition of the present invention, actinic ray or It contains a compound (photoacid generator) that generates an acid upon irradiation with radiation. As such a photoacid generator, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization,
It is possible to appropriately select and use a known compound or a mixture thereof, which is a photo-decoloring agent for dyes, a photo-discoloring agent, or a micro-resist which generates an acid upon irradiation with actinic rays or radiation. .

For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium 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, and a disulfone compound.

Also, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer upon irradiation with actinic rays or radiation, such as US Pat. No. 3,849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824.
No. 62-69263, 63-1460.
38, JP-A-63-163452, JP-A-62-
The compounds described in JP-A-153853 and JP-A-63-146029 can be used.

Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

Among the compounds which decompose to generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are described below.

(1) An iodonium salt represented by the following general formula (PAG1) or a sulfonium salt represented by the following general formula (PAG2).

[0167]

[Chemical 64]

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferable substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Of these, an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof are preferable. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for an aryl group,
The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Perfluoroalkane sulfonate anions such as CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anions, condensed polynuclear aromatic sulfonate anions such as naphthalene-1-sulfonate anions, anthraquinone sulfonate anions, sulfonate group-containing dyes, etc. Examples thereof include, but are not limited to:

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

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

[0173]

[Chemical 65]

[0174]

[Chemical formula 66]

[0175]

[Chemical formula 67]

[0176]

[Chemical 68]

[0177]

[Chemical 69]

[0178]

[Chemical 70]

[0179]

[Chemical 71]

[0180]

[Chemical 72]

[0181]

[Chemical formula 73]

[0182]

[Chemical 74]

[0183]

[Chemical 75]

The onium salts represented by the general formulas (PAG1) and (PAG2) are known, for example, US Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331. Can be synthesized by the method described in No.

(2) A disulfone derivative represented by the following general formula (PAG3) or an iminosulfonate derivative represented by the general formula (PAG4).

[0186]

[Chemical 76]

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

[0188]

[Chemical 77]

[0189]

[Chemical 78]

[0190]

[Chemical 79]

[0191]

[Chemical 80]

[0192]

[Chemical 81]

(3) A diazodisulfone derivative represented by the following general formula (PAG5).

[0194]

[Chemical formula 82]

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

[0196]

[Chemical 83]

In addition to the above compounds, compounds represented by the following general formula (I) are also effectively used as the acid generator of the component (B) of the present invention.

[0198]

[Chemical 84] In formula (I), R _{1 to} R ₅ represent a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an alkyloxycarbonyl group or an aryl group, and at least two or more of R _{1 to} R ₅ are It may combine with each other to form a ring structure. R
₆ and R ₇ represent a hydrogen atom, an alkyl group, a cyano group or an aryl group. Y ₁ and Y ₂ represent an alkyl group, an aryl group, an aralkyl group or an aromatic group containing a hetero atom, and Y ₁ and Y ₂ may be bonded to each other to form a ring. Y
₃ represents a single bond or a divalent linking group. X ⁻ represents a non-nucleophilic anion. Provided that at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are combined to form a ring, or at least one of R ₁ to R ₅ and at least one of R ₆ or R ₇ are combined. To form a ring. In addition, R ₁
To R ₇ or any of Y ₁ or Y ₂ via a linking group to form a structure of formula (I)
You may have one or more.

The alkyl group represented by R _{1 to} R ₇ is a substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 5 carbon atoms. Examples of the unsubstituted alkyl group include methyl group and ethyl group. Group, propyl group, n-butyl group,
Examples thereof include sec-butyl group and t-butyl group. The alkoxy group of R _{1 to} R _{5 and} the alkoxy group in the alkyloxycarbonyl group are substituted or unsubstituted alkoxy groups, preferably alkoxy groups having 1 to 5 carbon atoms, and examples of the unsubstituted alkoxy group include , A methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. The aryl group represented by R _{1 to} R ₇ , Y ₁ and Y ₂ is a substituted or unsubstituted aryl group, preferably an aryl group having 6 to 14 carbon atoms, and examples of the unsubstituted aryl group include phenyl. Group, tolyl group,
Examples thereof include a naphthyl group. Examples of the halogen atom of R _{1 to} R ₅ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted alkyl group, preferably having 1 to 30 carbon atoms.
Is an alkyl group. As the unsubstituted alkyl group, for example, a linear or branched alkyl group such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cyclopropyl group, Examples thereof include cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group and boronyl group.

The aralkyl group of Y ₁ and Y ₂ is a substituted or unsubstituted aralkyl group, preferably having 7 to 7 carbon atoms.
Examples of the aralkyl group of 12 and the unsubstituted aralkyl group include a benzyl group, a phenethyl group, and a cumyl group.

The aromatic group containing a hetero atom means a group having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom in an aromatic group such as an aryl group having 6 to 14 carbon atoms. The aromatic group containing a hetero atom of Y ₁ and Y ₂ is an aromatic group containing a substituted or unsubstituted hetero atom, and examples of the unsubstituted group include furan, thiophene, pyrrole, pyridine and indole. And a heterocyclic aromatic hydrocarbon group.

Y ₁ and Y ₂ are combined to form S ⁺ in the formula (I).
Together, they may form a ring. In this case, the group formed by combining Y ₁ and Y ₂ has, for example, 4 to 1 carbon atoms.
And an alkylene group of 0, preferably a butylene group, a pentylene group and a hexylene group, particularly preferably a butylene group and a pentylene group. Further, a hetero atom may be contained in the ring formed together with S ⁺ in the formula (I) by combining with Y ₁ and Y ₂ .

Each of the above-mentioned alkyl group, alkoxy group, alkoxycarbonyl group, aryl group and aralkyl group is, for example, nitro group, halogen atom, carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably having carbon number). 1-5) etc. may be substituted. Further, the aryl group and aralkyl group may be substituted with an alkyl group (preferably having 1 to 5 carbon atoms). Moreover, a halogen atom is preferable as a substituent of the alkyl group.

Y ₃ represents a single bond or a divalent linking group, and as the divalent linking group, an optionally substituted alkylene group, alkenylene group, —O—, —S—, —CO—,
-CONR- (R is hydrogen, an alkyl group, an acyl group.), And a linking group which may include two or more of these are preferable.

Examples of the non-nucleophilic anion of X ⁻ include sulfonate anion and carboxylate anion. The non-nucleophilic anion is an anion having an extremely low ability to cause a nucleophilic reaction, and is an anion capable of suppressing decomposition over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist. Examples of the sulfonate anion include an alkyl sulfonate anion, an aryl sulfonate anion, and a camphor sulfonate anion. Examples of the carboxylic acid anion include an alkylcarboxylic acid anion, an arylcarboxylic acid anion, and an aralkylcarboxylic acid anion.

The alkyl group in the alkylsulfonate anion is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , Pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group Group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like. The aryl group in the aryl sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, for example, a phenyl group, a tolyl group, a naphthyl group and the like.

The alkyl group and aryl group in the alkyl sulfonate anion and aryl sulfonate anion may have a substituent. As a substituent,
For example, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group and the like can be mentioned.

Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, iodine atom and the like. As the alkyl group, for example, an alkyl group preferably having 1 to 15 carbon atoms, for example, a methyl group, an ethyl group,
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples thereof include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group. As the alkoxy group, for example, preferably an alkoxy group having 1 to 5 carbon atoms,
For example, methoxy group, ethoxy group, propoxy group, butoxy group and the like can be mentioned. The alkylthio group is, for example, preferably an alkylthio group having 1 to 15 carbon atoms, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, pentylthio group,
Neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group,
Tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group,
Examples thereof include nonadecylthio group and eicosylthio group. The alkyl group, alkoxy group and alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

Examples of the alkyl group in the alkylcarboxylic acid anion include those similar to the alkyl group in the alkylsulfonic acid anion. Examples of the aryl group in the arylcarboxylic acid anion include the same as the aryl group in the arylsulfonic acid anion. The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylmethyl group and the like.

The alkyl group, aryl group and aralkyl group in the above alkylcarboxylic acid anion, arylcarboxylic acid anion and aralkylcarboxylic acid anion may have a substituent, and examples of the substituent include:
The same halogen atom, alkyl group, alkoxy group, alkylthio group and the like as in the aryl sulfonate anion can be mentioned.

Other non-nucleophilic anions include, for example, fluorinated phosphorus, fluorinated boron and fluorinated antimony.

In the formula (I) of the present invention, at least one of R ₁ to R ₅ and at least one of Y ₁ or Y ₂ are combined to form a ring, or a ring of R ₁ to R ₅ At least one and at least one of R _{6 and} R ₇ are combined to form a ring. By forming a ring, the compound represented by the formula (I) has a fixed three-dimensional structure and improves optical resolution. Any _one of R ₁ to R ₇ or Y ₁
Or at any position of Y ₂ is bonded via a linking group,
It may have two or more structures of formula (I).

Further, the compound of formula (I) is preferably of the following general formula (IA) or (IB).

[0215]

[Chemical 85]

In the formula (IA), R _{1 to} R ₄ , R ₇ , Y ₁ and Y ₂
And X ⁻ are the same as those in the above formula (I), and Y
Represents a single bond or a divalent linking group. In formula (IB), R
_{1 to} R ₄ , R ₆ , R ₇ , Y ₁ and X ⁻ are the same as those in the above formula (I), and Y represents a single bond or a divalent linking group.

Y represents a single bond or a divalent linking group, and 2
As the valent linking group, an optionally substituted alkylene group, alkenylene group, -O-, -S-, -CO-, -C
ONR- (R is hydrogen, an alkyl group, or an acyl group), and a linking group which may include two or more of these are preferable. In formula (IA), Y is preferably an alkylene group, an alkylene group containing an oxygen atom, or an alkylene group containing a sulfur atom, and specifically, a methylene group, an ethylene group, a propylene group, —CH ₂ —O—, —CH. ₂ -S- are preferred, and most preferably an ethylene group, -CH ₂ -O-,
A connecting group forming a 6-membered ring such as —CH ₂ —S—. By forming a 6-membered ring, the carbonyl plane and C-
The S + sigma bond becomes closer to vertical, and the photolysis efficiency is improved by the orbital interaction.

The compound of formula (IA) has the corresponding α-
A method of reacting a halo cyclic ketone with a sulfide compound,
Alternatively, it can be obtained by converting the corresponding cyclic ketone into a silyl enol ether and then reacting it with a sulfoxide. The compound represented by the formula (IB) can be obtained by reacting an arylalkyl sulfide with an α- or β-halogenated halide.

The specific examples of the compounds represented by the above formula (I) are shown below, but the invention is not limited thereto.

[0220]

[Chemical 86]

[0221]

[Chemical 87]

[0222]

[Chemical 88]

[0223]

[Chemical 89]

[0224]

[Chemical 90]

[0225]

[Chemical Formula 91]

[0226]

[Chemical Formula 92]

[0227]

[Chemical formula 93]

[0228]

[Chemical 94]

Specific examples of the acid generator represented by the above general formula (I) include (IA-1) to (IA-30) and (I).
B-1) to (IB-12) are more preferable.

The compounds of the above formula (I) can be used alone or in combination of two or more.

The content of the compound as the component (B) in the positive photosensitive composition of the present invention is based on the solid content of the composition.
0.1 to 20% by weight is preferable, and 0.5 is more preferable.
10 to 10% by weight, more preferably 1 to 7% by weight.

Among the compounds (B) which generate an acid upon irradiation with actinic rays or radiation used in the present invention, particularly preferable examples are shown below.

[0233]

[Chemical 95]

[0234]

[Chemical 96]

[0235]

[Chemical 97]

[0236]

[Chemical 98]

[3] A compound that accelerates the dissolution rate of the film (C) in an alkali developing solution (hereinafter may be referred to as a dissolution accelerator). The compound (C) used in the present invention is added to the resist film. At this time, as long as it has an effect of promoting the dissolution rate of the film in an alkali developing solution, it is not particularly limited, but from carboxylic acid, alcohol, sulfonamide, nitrile, malonic acid derivative, malonic acid ester. It is preferable that the compound is selected from the group consisting of:

The dissolution rate was determined by preparing a resist film (coating a resist solution on a silicon wafer and drying by heating (usually 110 to 130 ° C./60 seconds to 90 seconds)).
It can be determined by permeating into an alkaline developer and measuring its dissolution rate. The dissolution rate can be measured using various devices capable of measuring the dissolution rate. The preferable acceleration rate of the dissolution rate is 1.01 to 3.0 times as high as that of the resist before addition of the component (C), and 1.01 to 2.0 times as much as the dissolution rate. More preferably.

(C) -1: Carboxylic acid As the carboxylic acid, any compound having a general carboxyl group may be used, but one having no aromatic ring such as a benzene ring in the molecular skeleton is particularly preferable. Specific examples are shown below, but the present invention is not limited thereto.

[0240]

[Chemical 99]

[0241]

[Chemical 100]

[0242]

[Chemical 101]

[0243]

[Chemical 102]

(C) -2: As the alcohol alcohol, a compound having a general hydroxyl group may be used, but one having no aromatic ring such as a benzene ring in the molecule is particularly preferable. Specific examples are given below,
The present invention is not limited to these.

[0245]

[Chemical 103]

[0246]

[Chemical 104]

[0247]

[Chemical 105]

(C) -3: Sulfonamide As a sulfonamide, a sulfonamide group (-
Any compound having SO ₂ —NH ₂ ) may be used, but a compound having no aromatic ring such as a benzene ring in the molecule is particularly preferable. Specific examples are shown below, but the present invention is not limited thereto.

[0249]

[Chemical formula 106]

(C) -4: Nitrile The nitrile may be a compound having a cyano group in general, but a compound having no aromatic ring such as a benzene ring in the molecule is particularly preferable. Specific examples are shown below, but the present invention is not limited thereto.

[0251]

[Chemical formula 107]

[0252]

[Chemical 108]

[0253]

[Chemical 109]

(C) -5: Malonic acid derivative and malonic acid ester compound As the malonic acid derivative and malonic acid ester compound,
There is no particular limitation as long as it is a general dicarboxylic acid methane derivative. Specific examples are shown below, but the present invention is not limited thereto.

[0255]

[Chemical 110]

[0256]

[Chemical 111]

In the present invention, as the component (C), 2
Two or more compounds may be contained, and two kinds of these compounds may be selected from the same classification or two kinds may be selected from different classifications. That is, for example, two kinds of carboxylic acid or one kind of carboxylic acid and one kind of alcohol are selected. Of course, three or more kinds may be mixed and used, and any compound other than the above specific examples may be used as long as it is a compound that accelerates the dissolution rate of the film in the alkali developing solution.

In the present invention, the amount of the dissolution accelerator (C) added is usually 0.1 based on the solid content in the composition.
Used in the range of up to 20.0% by weight, preferably 0.5
˜15.0% by weight, more preferably 1.0 to 10.0% by weight. If the addition amount of the dissolution accelerator (C) of the present invention is too small, the line edge roughness may not be sufficiently improved, and if the addition amount is too large, the pattern profile may be deteriorated or the film of the unexposed portion may be deteriorated. This is not preferable because it tends to decrease.

[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, JP-A-5-289322
JP-A-5-249683 and JP-A-5-28934.
No. 0, JP-A-5-232706, and JP-A-5-2572.
82, JP-A-6-242605, and JP-A-6-242.
No. 606, JP-A-6-266100, JP-A-6-26
6110, JP-A-6-317902, JP-A-7-
120929, JP-A-7-146558, JP-A-7
-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217, JP-A-7-92678, JP-A-7-28247, JP-A-8-22120, JP-A-8-. 110638, JP-A-8-123030, JP-A-9-274312, JP-A-9-166871, JP-A-9-292708,
JP-A-9-325496, JP-A-7-508840
No. 5,525,453, US 5,629,913
The basic compounds described in No. 4, US Pat. No. 5,667,938 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 based on 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 (E) Fluorine-based and / or Silicon-based Surfactant that can be preferably used in the positive resist composition of the present invention explain. The resist composition of the present invention may contain any one of a fluorine-based surfactant, a silicon-based surfactant and a surfactant containing a fluorine atom and a silicon atom, or two or more of them. Examples of these surfactants include those disclosed in JP-A-62-36663.
No. 61-226746, 61-226.
745, JP-A-62-170950, JP-A-63-
34540, JP-A-7-230165, JP-A-8-
62834, JP-A-9-54432, and JP-A-9-5.
988, US Pat. Nos. 5,405,720 and 5,360,69.
No. 2, No. 5529881, No. 5296330, No. 5
No. 436098, No. 5576143, No. 5294451
The surfactants described in Nos. 1 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 EF301, EF303, (Shin-Akita Kasei Co., Ltd.)
Made), Florard FC430, 431 (Sumitomo 3M
Co., Ltd.), Megafac F171, F173, F17
6, F189, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 10
4, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S
Fluorine-based and / or silicon-based surfactants such as -366 (manufactured by Troy Chemical Co., Ltd.). Polysiloxane polymer KP-341 (produced by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The content of the (E) surfactant is usually 0.001 to 2 parts by weight, preferably 0.003 to 0.1 parts by weight, per 100 parts by weight of the solid content in the composition of the present invention.
0 parts by weight. These surfactants can be used alone or in combination of two or more.

The positive resist composition of the present invention, if necessary, has a molecular weight of 2000 or less, has a group decomposable 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, US Pat. No. 5310619, US Pat. No. 5,372,912, J. Photopolym. Sci., Tech., Vol.
10, No. 3,511 (1997), which contains an acid-decomposable group, a cholic acid derivative, a dehydrocholic acid derivative, a deoxycholic acid derivative, a lithocholic acid derivative,
An alicyclic compound such as a ursocholic acid derivative or an abietic acid derivative, or an aromatic compound such as a naphthalene derivative having an acid-decomposable group can be used as the low-molecular acid-decomposable compound. Further, the low molecular weight acid-decomposable dissolution-inhibiting compound described in JP-A-6-51519 can be used in an addition range of 220 nm at a level that does not deteriorate the transmittance, and a 1,2-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 development defects but also improves dry etching resistance.

In the positive resist composition of the present invention, if necessary, an antihalation agent for a developing solution,
It may contain a plasticizer, a surfactant, a photosensitizer, an adhesion aid, a crosslinking agent, a photobase generator and the like.

As the 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 and anthracene-9-carboxy. 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.

A photosensitizer may 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 is usually dissolved, for example, in a solvent capable of dissolving the above components, and then, for example, usually has a pore size of 0.05 μm.
It is prepared as a solution by filtering with a filter of about m to 0.2 μm. Examples of the solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone,
Methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
Methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate Examples include organic solvents such as propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran.

In the present invention, it is preferable to use a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed as the organic solvent. This can reduce the generation of particles during storage of the resist solution. As the solvent containing a hydroxyl group, for example,
Examples thereof include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate. Of these, propylene glycol monomethyl ether and ethyl lactate are particularly preferable. preferable. Examples of the solvent containing no hydroxyl group include propylene glycol monomethyl ether acetate, ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide and dimethyl sulfoxide. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone,
γ-Butyrolactone, cyclohexanone and butyl acetate are particularly preferable, and propylene glycol monomethyl ether acetate, ethylethoxypropionate and 2-heptanone are most preferable. The mixing ratio (weight) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to
99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. A mixed solvent containing 50% by weight or more of a solvent containing no hydroxyl group is particularly preferable from the viewpoint of coating uniformity.

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. Incidentally, the resist composition of the present invention may be a composition for any exposure source, but particularly 220 nm.
It is preferably a composition for exposure with far ultraviolet light having the following wavelengths.

The resist composition of the present invention is applied onto a substrate by a suitable coating method such as a spinner or coater, prebaked (pre-exposure heating), and exposed through a predetermined mask with exposure light preferably having a wavelength of 220 nm or less. And PEB
A good resist pattern can be obtained by performing (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 applied 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 prebaking, 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 surfactants, anionic surfactants, cationic surfactants, antifoaming agents, etc. 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.

[0278]

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. )

[0281]

[Table 1]

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

[0283]

[Chemical 112]

[0284]

[Chemical 113]

[0285]

[Chemical 114]

[0286]

[Chemical 115]

[0287]

[Chemical formula 116]

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.)

[0290]

[Table 2]

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

[0292]

[Chemical 117]

[0293]

[Chemical 118]

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.

[0296]

[Table 3]

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

[0298]

[Chemical formula 119]

[0299]

[Chemical 120]

[0300]

[Chemical 121]

[0301]

[Chemical formula 122]

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.

[0304]

[Table 4]

Further, the following resins (45) to (69)
Shows the structure of.

[0306]

[Chemical 123]

[0307]

[Chemical formula 124]

[0308]

[Chemical 125]

[0309]

[Chemical formula 126]

[0310]

[Chemical 127]

Examples 1 to 69 and Comparative Examples 1 to 4 (Preparation and Evaluation of Positive Resist Composition) Each of the resins shown in Tables 5 to 7 synthesized in the above Synthesis Example was 1.25 g (however, Comparative Example In the above, a photoacid generator, a dissolution accelerator of the present invention 0.06 g, an organic basic compound (amine) 3 mg if necessary, and a surfactant (10 mg) as required are compounded as shown in Tables 5 to 7. Then, the positive resist compositions of Examples 1 to 69 and Comparative Examples 1 to 4 were dissolved in the solvents described in Tables 5 to 7 at a solid content of 14% by weight and filtered with a 0.1 μm microfilter. The thing was prepared.

[0312]

[Table 5]

[0313]

[Table 6]

[0314]

[Table 7]

Abbreviations in Tables 5 to 7 are as follows.

Photoacid generator: Specific example z1 of component (A) above
~ Z40

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.)
Made)

Amine: represents 1,1,5-diazabicyclo [4.3.0] -5-nonene (DBN), 2: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 3: tri-n-butylamine 4: triphenylimidazole 5: antipyrine 6: 2,6-diisopropylaniline

Abbreviations for solvents are as follows. In addition, the ratio in the case of multiple use in Tables 5 to 7 is a weight ratio. A1: Propylene glycol methyl ether acetate A2: 2-heptanone A3: Ethyl ethoxy propionate A4: γ-butyrolactone A5: Cyclohexanone B1: Propylene glycol methyl ether B2: Ethyl lactate

(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 and sensitivity were evaluated as follows. The evaluation results are shown in Tables 8 to 10.

[Edge Roughness]: The edge roughness is measured with the edge roughness of an isolated pattern (line width 130 nm) using a length-measuring scanning electron microscope (SEM), and a plurality of line pattern edges are measured in a measurement monitor. At the position, and the variance (3σ) of variations in the detected position was used as an index of edge roughness. The smaller this value is, the more preferable.

[Sensitivity]: The sensitivity was measured by the minimum exposure dose (mj / cm ² ) that reproduces a 0.15 μm line pattern on the mask.

[0323]

[Table 8]

[0324]

[Table 9]

[0325]

[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 edge roughness and sensitivity.

[0327]

INDUSTRIAL APPLICABILITY The positive resist composition of the present invention is used for far-ultraviolet light having a wavelength of 220 nm or less, particularly Ar having a wavelength of 193 nm.
It is suitable for F excimer laser light and has excellent edge roughness and sensitivity. Therefore, it is preferably used for lithography using deep ultraviolet rays such as ArF excimer laser exposure.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA01 AA03 AB16 AC04 AC08                       AD03 BE00 BE10 BG00 CB08                       CB10 CB14 CB41 CC03 CC20                       FA17                 4J100 AL08P AR09Q AR11Q BA02P                       BA03Q BA04Q BA11Q BA12P                       BA14P BA15P BA16Q BA20P                       BA20Q BC02P BC04P BC08P                       BC09P BC09Q BC12P BC53Q                       JA38

Claims (6)

[Claims] 1. A resin (A) having an aliphatic cyclic hydrocarbon group, the dissolution rate of which in an alkali developing solution is increased by the action of an acid, which is represented by the following general formula (pI) to general formula (pVI). A resin containing at least one selected from the group of repeating units having a partial structure containing an alicyclic hydrocarbon and a repeating unit represented by the following general formula (II): (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 2] 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. (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C)
A positive resist composition comprising a compound that accelerates the dissolution rate of a film in an alkaline developer. 2. Z'in the general formula (II) includes 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 1, wherein the positive resist composition represents 3. The general formula (II) is represented by the following general formula (II-
The positive resist composition according to claim 1, which is represented by the formula (A) or the general formula (II-B). [Chemical 3] 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. ) 4. The compound according to claim 1, wherein the compound (C) is a compound selected from the group consisting of carboxylic acid, alcohol, sulfonamide, nitrile, malonic acid derivative, and malonic acid ester. The positive resist composition according to any one of items. 5. The positive resist composition according to claim 1, further comprising a mixed solvent obtained by mixing a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group. . 6. The positive resist composition according to claim 1, wherein the positive resist composition is a composition for exposure by far ultraviolet light having a wavelength of 220 nm or less.