JP2002296782A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition excellent in the resolution for contact holes and adoptability for halftone exposure. SOLUTION: The positive photoresist composition contains the following resin and compounds which generate acids by irradiation of active rays or radiation. The resin contains repeating units having aliphatic cyclic hydrocarbon groups and repeating units containing no aromatic part but containing crosslinked parts of specified structures and the resin increases the dissolving rate with respect to an alkali developer by the effect of acids.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity micro chip, or other photofabrication processes.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to meet the need, the wavelength used in an exposure apparatus used for photolithography is becoming shorter and shorter, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. Up to now.
A chemically amplified resist is used for forming a pattern in lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes under the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low molecular compound.

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced therein for the purpose of imparting dry etching resistance has been proposed. However, such a phenomenon that the development with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution in the past, becomes difficult, and the resist is peeled off from the substrate during the development. Can be seen. In response to such a resist hydrophobization, measures such as mixing an organic solvent such as isopropyl alcohol with a developing solution have been studied, and although tentative results have been obtained, the swelling of the resist film and the process become complicated. This does not necessarily mean that the problem has been solved. In the approach of improving the resist, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon sites by introducing a hydrophilic group.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in its main chain, maleic anhydride, and a monomer having a carboxyl group. Materials are disclosed. JP-A-10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator. JP-A-11-109632 describes that a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group is used for a radiation-sensitive material.

As described above, a resin containing an acid-decomposable group used for a photoresist for exposure to far ultraviolet rays generally contains an aliphatic cyclic hydrocarbon group in the molecule at the same time. For this reason, the resin becomes hydrophobic, and there is a problem caused by the hydrophobicity. Various means for improving the above have been studied, but the above techniques still have many insufficient points, and improvements are desired.

In order to cope with further miniaturization of patterns, it is general to use a modified illumination method or a phase shift mask. Ring and zone illumination is used for line and space patterns, and halftone phase is used for contact holes. Shift masks are often used. It has been desired to have a high resolution when using annular illumination and a wide defocus latitude. The fact that the defocus latitude is wide means that the fluctuation of the line width due to defocus is small. When a halftone phase shift mask is used, there is a problem of a side lobe in which a pattern portion is dissolved by a small amount of transmitted light, and this solution has been desired.

JP-A-11-143079 and JP-A-11-265067 disclose radiation-sensitive resin compositions containing a resin obtained by copolymerizing a repeating unit having a specific cross-linking structure. However, there are problems with the resolution of the contact hole, suitability for halftone exposure, and the like.

[0009]

As described above, the known techniques of the conventional photoresist composition have problems in the resolution of the contact hole and the suitability for halftone exposure, and further improvement has been desired. Accordingly, an object of the present invention is to provide a positive resist composition having excellent contact hole resolution and halftone exposure suitability.

[0010]

Means for Solving the Problems As a result of intensive studies on the constituent materials of the positive type chemically amplified resist composition, the present inventors have achieved the object of the present invention by using a specific acid-decomposable resin. This led to the present invention. That is,
The above object is achieved by the following constitutions.

(1) (A) It contains a repeating unit having an aliphatic cyclic hydrocarbon group and a repeating unit containing no aromatic moiety and having a cross-linking moiety having a structure represented by the following general formula (a): A positive resist composition comprising: a resin whose dissolution rate in an alkaline developer is increased by the action of an acid; and (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation.

[0012]

Embedded image

In the formula (a), R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an optionally substituted substituent having 1 carbon atom.
Represents up to 4 alkyl groups.

(2) The positive resist composition as described in (1) above, wherein the resin (A) contains a repeating unit having a structure represented by the following general formula (b).

[0015]

Embedded image

In the formula (b), R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an optionally substituted substituent having 1 carbon atom.
Represents up to 4 alkyl groups. R _{103 to} R ₁₀₈ each independently represent a hydrogen atom, an alkyl group, a cyano group, or a halogen atom which may have a substituent. A represents at least one divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, and a sulfonamide group.

(3) The positive resist composition as described in (1) above, wherein the resin (A) contains a repeating unit having a structure represented by the following general formula (c).

[0018]

Embedded image

In the formula (c), R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an optionally substituted substituent having 1 carbon atom.
Represents up to 4 alkyl groups. R _{103 to} R ₁₀₈ each independently represent a hydrogen atom, an alkyl group, a cyano group, or a halogen atom which may have a substituent. A represents at least one divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, and a sulfonamide group.

(4) The resin of (A) is represented by the following general formula (p)
I) to at least one selected from the group consisting of a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pVI) and a repeating unit represented by the following general formula (II)
The positive resist composition according to any one of the above (1) to (3), comprising a seed.

[0021]

Embedded image

(Wherein R ₁₁ is a methyl group, an ethyl group, n
-Represents a propyl group, isopropyl group, n-butyl group, isobutyl group or 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 represent a group having 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 any of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group. R
_{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms. R _{22 to} R ₂₅ are each independently
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, 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. )

[0023]

Embedded image

In the 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 may have a substituent and has two bonded carbon atoms (C—C).

(5) Z ′ in the general formula (II)
Represents an atomic group for forming a bridged alicyclic structure which contains two bonded carbon atoms (C-C) and may have a substituent (4). 4. The positive resist composition according to item 1.

(6) The positive resist composition according to the above (4), wherein the general formula (II) is the following general formula (II-A) or (II-B).

[0027]

Embedded image

In the formulas (II-A) and (II-B): R ₁₃ ′ to R _13
16 ′ is each independently a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposed by the action of an acid, —C (＝ O) —XA′-R ₁₇ ′, or substituted Represents an alkyl group or a cyclic hydrocarbon group which may have a group. Here, R ₅ represents an alkyl group, a cyclic hydrocarbon group or the following —Y group which may have a substituent. 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. Further, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n represents 0 or 1.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group,
An alkoxy group which may have a substituent, -CO-NH
—R ₆ , —CO—NH—SO ₂ —R ₆ or the following —Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A —Y group;

[0029]

Embedded image

(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.)

[0031]

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

The (A) acid-decomposable resin of the present invention includes a repeating unit having an aliphatic cyclic hydrocarbon group and a cross-linking site having a structure represented by the following general formula (a), which does not include an aromatic site. And a dissolving rate in an alkali developing solution which is increased by the action of an acid.

In the formula (a), R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an optionally substituted substituent having 1 carbon atom.
Represents up to 4 alkyl groups. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.

Further substituents in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group and the like. As a halogen atom,
Examples thereof include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
The acyl group includes a formyl group and an acetyl group, and the acyloxy group includes an acetoxy group.

The resin (A) of the present invention preferably contains a repeating unit having a structure represented by the following general formula (b).

[0036]

Embedded image

In the formula (b), R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an optionally substituted substituent having 1 carbon atom.
Represents up to 4 alkyl groups. R _{103 to} R ₁₀₈ each independently represent a hydrogen atom, an alkyl group, a cyano group, or a halogen atom which may have a substituent. A represents at least one divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, and a sulfonamide group.

The alkyl group of R _{103 to} R ₁₀₈ 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 more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group,
An isobutyl group, a sec-butyl group and a t-butyl group.

Examples of the alkylene group in the above A include a group represented by the following formula. -[C (R _a ) (R _b )] _r-wherein R _a and R _{b each} represent a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, a hydroxyl group, or an alkoxy group; May be the same or different. 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, and more preferably selected from a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples of the substituent 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 a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r
Represents an integer of 1 to 10.

The cycloalkylene group in the above A may be a divalent group having an alicyclic hydrocarbon structure. Further, the alicyclic hydrocarbon structure may have a substituent. Below, of the alicyclic hydrocarbon structure,
The structural example of an alicyclic part is shown.

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, 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 structures include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. As the alkyl group, a methyl group,
Preferred are lower alkyl groups such as ethyl group, propyl group, isopropyl group and butyl group, more preferably methyl group,
Represents a substituent selected from the group consisting of an ethyl group, a propyl group, and an 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 a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Individuals can be mentioned.

The resin (A) of the present invention preferably contains a repeating unit having a structure represented by the following general formula (c).

[0047]

Embedded image

The formula _{(c), R 101 ~R 108} , A have the same meanings as R ₁₀₁ to R _108, A in the general formula (b).

The following are specific examples of monomers which do not contain an aromatic moiety and correspond to a repeating unit having a crosslinked moiety having the structure represented by the above general formula (a). It is not limited to.

[0050]

Embedded image

[0051]

Embedded image

Examples of the repeating unit having an aliphatic cyclic hydrocarbon group in the resin (A) of the present invention include those having an alicyclic hydrocarbon group in a main chain or a side chain. It is preferable to contain at least one selected from the group consisting of a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pVI) and a repeating unit represented by the following general formula (II) .

In the general formulas (pI) to (pVI), R
The alkyl group for _{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 include a sec-butyl group and a t-butyl group. Further, as a further substituent of the above alkyl group, one having 1 carbon atom
And 4 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.

[0054] The alicyclic hydrocarbon group in which the alicyclic hydrocarbon group, or Z and the carbon atoms in R ₁₁ to R ₂₅ form, also monocyclic, or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably from 6 to 30, particularly preferably from 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part among alicyclic hydrocarbon groups is shown.

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, 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, and more preferably a methyl group, an ethyl group, a propyl group, and a substituent selected from the group consisting of 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 a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

The resins represented by the general formulas (pI) to (pV)
The structure represented by I) can be used for protecting an alkali-soluble group. Examples of the alkali-soluble group include various groups known in this technical field. Specific examples 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) to above resin
The alkali-soluble group protected by the structure represented by (pVI) is preferably the following general formulas (pVII) to (pVII).
XI).

[0061]

Embedded image

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

[0063]

Embedded image

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 Rs may be the same or different. A is singly or two or more selected from the group consisting of 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, and a urea group. Represents a combination of groups. Ra represents any one of the above formulas (pI) to (pVI).

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) will be shown.

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

In the general formula (II), R ₁₁ ′ and R ₁₂ ′
Is independently 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 has two bonded carbon atoms (CC) and may have a substituent.

Examples of the halogen atom for R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. R ₁₁ ′, R ₁₂ ′, R ₂₁ ′ to R
_As the alkyl group at ₃₀ ′, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and still more preferable. Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group,
They are a sec-butyl group and a t-butyl group.

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

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 on the resin. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon of the formula is preferred. Examples of the skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

[0076]

Embedded image

[0077]

Embedded image

Preferable bridged alicyclic hydrocarbon skeletons include (5), (6), (7),
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47).

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

The above formula (II-A) or (II-B)
In the formula, R ₁₃ ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group decomposed by the action of an acid, —C (（O) —XA ′. -R
₁₇ ′ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. R ₅ represents an alkyl group, a cyclic hydrocarbon group or the above-mentioned —Y group which may have a substituent. X is an oxygen atom, a sulfur atom, -NH-, -NH
Represents SO ₂ — or —NHSO ₂ NH—. A ′ represents a single bond or a divalent linking group. Further, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n is 0
Or represents 1. R ₁₇ ′ represents —COOH, —COOR ₅ ,
—CN, a hydroxyl group, an optionally substituted alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆
Or represents the following -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. The-
In the Y group, R ₂₁ ′ to R ₃₀ ′ each independently represent a hydrogen atom or an alkyl group which may have a substituent;
b represents 1 or 2.

In the resin according to the present invention, the acid-decomposable group may be contained in the above-mentioned —C (＝ O) —XA′-R ₁₇ ′, or may be substituted for Z ′ in the general formula (II). It may be included as a group. The structure of the acid-decomposable group is -C (= O) -X _1-
It is represented by R ₀ . In the formula, R ₀ is a t-butyl group,
tertiary alkyl groups such as t-amyl group, isobornyl group, 1
-An ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-alkoxyethyl group such as a 1-cyclohexyloxyethyl group, a 1-methoxymethyl group,
An alkoxymethyl group such as an ethoxymethyl group, a 3-oxoalkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilyl ester group, a 3-oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, mevalonic Lactone residues and the like can be mentioned. X ₁ has the same meaning as X described above.

Examples of the halogen atom in R ₁₃ ′ to R ₁₆ ′ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

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.
It is six linear or branched alkyl groups, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

Examples of the cyclic hydrocarbon group for R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group,
Cyclohexyl group, adamantyl group, 2-methyl-2-
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, a tetracyclododecanyl group, and the like can be given. As the ring formed by bonding at least two of R ₁₃ ′ to R ₁₆ ′, cyclopentene,
Rings having 5 to 12 carbon atoms such as cyclohexene, cycloheptane, cyclooctane and the like can be mentioned.

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

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

The divalent linking group represented by A ′ is selected from the group consisting of 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 and a urea group. The selected one or a combination of two or more groups can be mentioned. Examples of the alkylene group and substituted alkylene group in A ′ include groups represented by the following formula. -[C (R _a ) (R _b )] _r-wherein R _a and R _b represent 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 a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group and an isopropyl group. As the substituent of the substituted alkyl group,
Examples 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 a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

In the resin according to the present invention, the groups decomposed by the action of an acid are represented by the 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 repeating units of a copolymer component described later.
It can be contained in various kinds of repeating units.

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

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

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

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).

[0111]

Embedded image

[0112] 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, or a combination of two or more groups selected from the group consisting of an ester group. _{Ra 1, Rb 1, Rc 1} , Rd 1, Re 1 each independently represents 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;
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 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Can be mentioned.

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

Further substituents in the above alkyl group include carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, alkoxy group, substituted alkoxy group, acetylamide group, alkoxycarbonyl group, An acyl group is exemplified. Here, 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. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (IV) will be shown, but it should not be construed that the invention is limited thereto.

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

In the specific example of the above general formula (IV), (IV-17) to (IV-17)
(IV-36) is preferred. Further, as the structure of the general formula (IV), those having an acrylate structure are preferable from the viewpoint that edge roughness is improved.

Further, the following general formulas (V-1) to (V-4)
And a repeating unit having a group represented by any of the above.

[0122]

Embedded image

In the general formulas (V-1) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Two of R _{1b to} R _5b may combine 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 a linear or branched alkyl group, and may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
Twelve linear or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and still more preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group. The cycloalkyl group in 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, a cyclooctyl group and the like. The alkenyl group in R _{1b to} R _5b is preferably an alkenyl group having 2 to 6 carbon atoms 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 (V-4) may be connected to any of the carbon atoms constituting the cyclic skeleton.

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

The repeating units having groups represented by formulas (V-1) to (V-4) include those represented by formula (II-
A) or (II-B) wherein 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 group represented by the general formula (V-
1) to (V-4)), or a repeating unit represented by the following general formula (AI).

[0127]

Embedded image

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. Preferred substituents which the alkyl group of _Rb0 may have are those represented by the general formulas (V-1) to (V-1).
Preferred examples of the substituent which may be possessed by the alkyl group as R _1b in (V-4) include those exemplified above. Examples of the halogen atom for 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 obtained by 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.

[0129]

[Of 60]

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 a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group and an 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 a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. 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.

Hereinafter, specific examples of the repeating unit represented by the general formula (AI) will be shown, but the content of the present invention is not limited thereto.

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

[0138]

Embedded image

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

[0140]

Embedded image

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. Represents R _6a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom.

In formula (VI), examples of the alkylene group represented by A ₆ include groups represented by the following formula. -[C (Rnf) (Rng)] r- In the above formula, Rnf and Rng are a hydrogen atom, an alkyl group,
Represents a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, which may be the same or different. 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, and more preferably selected from a methyl group, an ethyl group, a propyl group and an 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 a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r is an integer of 1 to 10. General formula (VI)
In the above, examples of the cycloalkylene group for A ₆ include those having 3 to 10 carbon atoms, and a cyclopentylene group,
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, a formyl group and a benzoyl group), and an acyloxy group ( For example, a propylcarbonyloxy group, a benzoyloxy group), an alkyl group (preferably having 1 to 4 carbon atoms), a carboxyl group, a hydroxyl group, an alkylsulfonylsulfamoyl group (such as —CONHSO ₂ CH ₃ ) are exemplified. still,
The alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), 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 atom constituting the bridged alicyclic ring structure including Z _6. Good.

Hereinafter, specific examples of the repeating unit represented by the general formula (VI) will be shown, but it should not be construed that the invention is limited thereto.

[0146]

Embedded image

[0147]

Embedded image

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

[0149]

Embedded image

[0150] In the general formula _{(VII), R 2 c~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 group represented by the formula (VII) is preferably a dihydroxy compound or a monohydroxy compound, more preferably a dihydroxy compound.

As the repeating unit having a group represented by the general formula (VII), the above-mentioned general formula (II-A) or (II-
B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by the general formula (VII) (for example, —COO
R ₅ of R ₅ represents a group represented by formulas (V-1) to (V-4)), or a repeating unit represented by the following formula (AII).

[0153]

Embedded image

[0154] In formula (AII), R ₁ c represents a hydrogen atom or a methyl group. R ₂ c~R ₄ c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group.

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

[0156]

Embedded image

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

[0158]

Embedded image

In the general formula (VIII), Z ₂ represents —O— or —
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.

In the general formula (VIII), Z ₂ represents-
Represents O- or -N ( _R41 )-. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OS
Represents O ₂ -R 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, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably methyl, ethyl, propyl, isopropyl, 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 or camphor residue as R ₄₂ 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, an iodine atom), and an alkoxy group (preferably having 1 to 1 carbon atoms).
4, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., an acyl group (preferably having 2 to 5 carbon atoms, for example, a formyl group, an acetyl group, etc.), an acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group).

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

[0164]

[Of 75]

[0165]

Embedded image

The acid-decomposable resin which is the component (A) has, in addition to the above-mentioned repeating structural units, dry etching resistance, suitability for a standard developing solution, substrate adhesion, resist profile, and general necessary properties of a 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 repeating structural units corresponding to the following monomers, but are not limited thereto. 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 adjustment of (3) alkali developability, (4) film loss (hydrophobicity, selection of alkali-soluble group), (5) adhesion of unexposed portion to substrate, (6) dry etching resistance, etc. becomes possible. . As such monomers, for example, acrylates, methacrylates, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate,
Amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-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 and the like.

Methacrylates (preferably alkyl methacrylates 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 and the like.

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

Methacrylamides: methacrylamide,
N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group,
Butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkylmethacrylamide (alkyl group includes ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-
Methyl methacrylamide and the like.

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

Vinyl ethers: alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
-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 and the like.

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, 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;

Others crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like.

In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with a monomer corresponding to the above-mentioned various repeating structural units, it 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, the suitability for a standard developer, the substrate adhesion, the resist profile, and the resolving power, heat resistance, which is a general required performance of the resist. It is set as appropriate to adjust properties, sensitivity, and the like.

Preferred embodiments of the acid-decomposable resin of the present invention include the following. (1) A structure represented by the above general formula (a) which does not include a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI) and an aromatic moiety, and (2) Structure containing the repeating unit represented by the general formula (II) and the aromatic unit but not represented by the general formula (a) (Main chain type) containing a repeating unit containing a cross-linking site of (2). However, in (2), for example, the following may be further mentioned. (3) a repeating unit having the repeating unit represented by the general formula (II), a repeating unit having a maleic anhydride derivative and a (meth) acrylate structure, and containing no aromatic moiety, Containing a repeating unit containing a crosslinking site (hybrid type)

The content of the repeating unit having an aliphatic cyclic hydrocarbon group in the acid-decomposable resin is preferably from 30 to 80 mol%, more preferably from 35 to 7 mol%, based on all repeating structural units.
It is 5 mol%, more preferably 40 to 70 mol%. In the acid-decomposable resin, the content of the repeating unit containing no aromatic moiety and containing the crosslinked moiety having the structure represented by the general formula (a) is 0.1 to 15 mol% in all repeating structural units. It is preferably 0.3 to 12 mol%, more preferably 0.5 to 8 mol%.

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

The content of the repeating structural unit based on the monomer of the further copolymer component in the resin can be appropriately set according to the desired resist properties. 99 moles with respect to the total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by the formula (pI) to (pVI) and the repeating unit represented by the general formula (II) % Or less, more preferably 90 mol% or less, and still more preferably 80 mol% or less.

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

The weight average molecular weight of the resin according to the present invention is G
It is preferably from 1,000 to 200,000 in terms of polystyrene according to the PC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable. When the weight average molecular weight exceeds 200,000, the developability is deteriorated and the viscosity becomes extremely high, so that the film forming property is deteriorated. And so on, which produces very unfavorable results.

In the positive photoresist composition for exposure to far ultraviolet rays of the present invention, the amount of all the resins according to the present invention in the total composition is from 40 to 99.
It is preferably 99% by weight, more preferably 50 to 99.9.
7% by weight.

[2] (B) Compound that Generates Acid by Irradiation with Actinic Ray or Radiation (Photoacid Generator) The photoacid generator used in the present invention is a compound that generates an acid by irradiation with actinic ray or radiation. It is. As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Publicly known light (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray,
A compound that generates an acid by a molecular beam or an ion beam and a mixture thereof can be appropriately selected and used.

Examples of other photoacid generators used in the present invention include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts.
Organic halogen compound, organic metal / organic halide, o
A photoacid generator having a nitrobenzyl-type protecting group; a compound represented by photolysis such as iminosulfonate that generates sulfonic acid; a disulfone compound; a diazoketosulfone; and a diazodisulfone compound.
Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

Furthermore, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

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

[0190]

Embedded image

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0192]

Embedded image

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

[0194]

Embedded image

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

Z ^- represents a counter anion, for example, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Condensed polynuclear aromatic sulfonic acid anions such as perfluoroalkanesulfonic acid anions such as O ₄ ⁻ and CF ₃ SO ₃ ⁻ , pentafluorobenzenesulfonic acid anion and naphthalene-1-sulfonic acid anion, anthraquinonesulfonic acid anion and sulfonic acid group Dyes and the like may be included, but are not limited thereto.

Further, 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 following compounds, but are not limited thereto.

[0199]

Embedded image

[0200]

Embedded image

[0201]

Embedded image

[0202]

Embedded image

[0203]

Embedded image

[0204]

Embedded image

[0205]

Embedded image

[0206]

Embedded image

[0207]

Embedded image

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

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0210]

Embedded image

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

Specific examples include the following compounds, but are not limited thereto.

[0213]

Embedded image

[0214]

Embedded image

[0215]

Embedded image

[0216]

Embedded image

[0219]

Embedded image

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

[0219]

Embedded image

Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0221]

Embedded image

[0222]

Embedded image

The amount of the photoacid generator to be added is generally in the range of 0.001 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably the solid content in the composition. Is used in the range of 0.5 to 10% by weight. If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity tends to decrease. The margin (especially baking) tends to be narrow.

[3] Other Additives The positive resist composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant,
A photosensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like can be contained.

The positive resist composition of the present invention preferably contains a fluorine-based and / or silicon-based surfactant. The positive resist composition of the present invention preferably contains one or more of a fluorine-based surfactant, a silicon-based surfactant and a surfactant containing both a fluorine atom and a silicon atom. . When the positive resist composition of the present invention contains the above-mentioned acid-decomposable resin and the above-mentioned surfactant, it is particularly effective when the line width of the pattern is narrower, and the development defects are further improved. As these surfactants, for example, JP-A-62-36663, JP-A-61-2
No. 26746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834
, JP-A-9-54432 and JP-A-9-5988, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (Shin-Akita Kasei
Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Limited)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102,
103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-
366 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant. In addition, polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.)
Can also be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combination.

Examples of the other surfactants that can be used include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like. Polyoxyethylene alkyl allyl ethers such as ethylene alkyl ethers, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostea Sorbitan esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene Nonions such as polyoxyethylene sorbitan fatty acid esters such as rubitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants and the like. The amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention.

Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable.

[0229]

Embedded image

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl having 1 to 6 carbon atoms. Group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0231]

Embedded image

(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ independently represent an alkyl group having 1 to 6 carbon atoms.) Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine,
Substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted amino And alkyl morpholine. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group,
A hydroxyl group and a cyano group.

Preferred specific examples of the nitrogen-containing basic compound include guanidine, 1,1-dimethylguanidine,
1,3,3, -tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
-Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-amino Ethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-
3-methyl-1-p-tolylpyrazole, pyrazine, 2
-(Aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-
Aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona-
5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2]
Octane, 2,4,5-triphenylimidazole, N
-Methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMET
U) and other tertiary morpholine derivatives, JP-A-11-5257
No. 5 hindered amines (for example, those described in the gazette [0005]) and the like, but are not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] Tertiary morpholines such as octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, CHMETU, etc., and bis Hindered amines such as (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate and the like can be mentioned. Among them, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-
Diazabicyclo [5.4.0] undec-7-ene,
1,4-diazabicyclo [2.2.2] octane, 4-
Dimethylaminopyridine, hexamethylenetetramine,
CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate is preferred.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire photosensitive resin composition. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

The positive resist composition of the present invention is applied to a support by dissolving the above components in a solvent that dissolves the above components. As the solvent used here, 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, lactic acid Ethyl, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

Of the above, preferred solvents are 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone and tetrahydrofuran.

Such a positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. The inorganic substrate that can be used in the present invention is a normal BareSi substrate, SO
Examples of the substrate include a G substrate and a substrate having an inorganic antireflection film described below. In the present invention, a commercially available inorganic or organic antireflection film can be used, if necessary.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type comprising a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
No. 611, consisting of a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light absorbing agent; a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680; No. 6,118,631 containing a resin binder and a methylolmelamine-based thermal crosslinking agent; Japanese Patent Application Laid-Open No. 6-118656, an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule; JP-A-8-87115, comprising a methylolmelamine and a benzophenone-based light-absorbing agent;
No. 79509 in which a low molecular weight light absorbing agent is added to a polyvinyl alcohol resin. As an organic anti-reflection film, DUV3 manufactured by Brewer Science Co., Ltd.
0 series, DUV-40 series, ARC25, Shipley's AC-2, AC-3, AR19, AR20
Etc. can also be used.

The resist solution is coated on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the above antireflection film if necessary), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia;
Primary amines such as ethylamine and n-propylamine;
Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0242]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Synthesis Example (1) Synthesis of Monomer Corresponding to Crosslinking Repeating Unit of Resin (1) 26 g of 2-hydroxyethyl methacrylate, 50 mL of methyl ethyl ketone, and 0.4 g of PPTS (pyridinium p-toluenesulfonate) were in the form of an eggplant. The flask was charged and stirred. When the reaction liquid becomes homogeneous, t
-Butyl vinyl ether (10 g) was added, and the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the reaction solution was heated at 30 ° C.
It concentrated under reduced pressure (15 mmHg). After 100 mL of ethyl acetate and 0.3 g of triethylamine were added to the concentrated reaction solution, it was washed with water. After repeating the washing twice,
After drying with gSO ₄ , concentration and purification by silica gel column chromatography, the desired monomer (21 g) was obtained. A monomer corresponding to another crosslinking repeating unit can be synthesized in the same manner.

Synthesis Example (2) Synthesis of resin (1) (side chain type) 2-Ethyl-2-adamantyl methacrylate, butyrolactone methacrylate, 2-hydroxyethyl methacrylate cross-linking monomer was charged at a ratio of 58/38/4, and methyl ethyl ketone was prepared. / Tetrahydrofuran = 6/4
To prepare 100 mL of a solution having a solid concentration of 24%. To this solution, V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added at 1 mol% / methicatoethanol 4 mol%, and added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 6 hours under a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 4 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and 1 L of a mixed solvent of distilled water / ISO propyl alcohol = 2/1.
The resin (1) as a white powder crystallized and precipitated was recovered. The polymer composition ratio determined from C ¹³ NMR was 49/46.
/ 5. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 16,900.
The 2-hydroxyethyl methacrylate crosslinking monomer was synthesized in the above synthesis example (1).

Resins (2) to (10) were synthesized in the same manner as in Synthesis Example (2). The following resin (2) to
The composition ratio and molecular weight of (10) are shown. (Repeat unit 1,
2, 3, and 4 are the order from the left of the structural formula. )

[0246]

[Table 1]

The structures of the resins (1) to (10) are shown below.

[0248]

Embedded image

[0249]

Embedded image

[0250]

Embedded image

[0251]

Embedded image

Synthesis Example (3) Synthesis of Resin (11) (Main Chain Type, Hybrid Type) Norbornene carboxylic acid t-amyl ester, norbornene and maleic anhydride, and a cross-linked monomer of 2-hydroxyethyl acrylate (molar ratio: 37) / 10/50 /
3) and THF (reaction concentration: 60% by weight) were charged into a separable flask and heated at 60 ° C under a nitrogen stream. When the reaction temperature becomes stable, radical initiator V manufactured by Wako Pure Chemical Industries, Ltd.
-601 was added at 4 mol% to start the reaction. Heat for 12 hours. After diluting the obtained reaction mixture twice with tetrahydrofuran, hexane / methyl tBu ether =
The mixture was put into a 1/1 mixed solution to precipitate a white powder. The precipitated powder was taken out by filtration, dissolved again in THF, reprecipitated in a mixed solution of hexane / methyl tBu ether = 1/1, and dried to obtain the target resin (11). When the molecular weight analysis of the obtained resin (11) by GPC was attempted, it was 14300 (weight average) in terms of polystyrene. From the NMR spectrum, the molar ratio of norbornene carboxylic acid t-butyl ester / norbornene / maleic anhydride / crosslinking monomer repeating unit of resin (11) was 3
It was confirmed that the ratio was 6/11/50/3.

The resin (1) was prepared in the same manner as in Synthesis Example (3).
2) to (22) were synthesized. The following resin (12) to
The composition ratio and molecular weight of (22) are shown. (Alicyclic olefin units 1 and 2 are in the order from the left of the structural formula. Acrylic units 1 and 2 are in the order from the left in the structural formula.)

[0254]

[Table 2]

The following resins (11) to (22)
The structure of is shown.

[0256]

Embedded image

[0257]

Embedded image

[0258]

Embedded image

[0259]

Embedded image

Examples 1 to 22 and Comparative Example 1 (Preparation and Evaluation of Positive Resist Composition) Each of the resins shown in Table 3 synthesized in the above Synthesis Examples was 1.4.
g Photoacid generator, 3 mg of organic basic compound (amine), (Comparative Example 1
g) If necessary, a surfactant (10 mg) was blended as shown in Table 3, and the solid content was 14% by weight, respectively.
And dissolved in propylene glycol monomethyl ether acetate at a ratio of 0.1%, and then filtered through a 0.1 μm microfilter to prepare positive resist compositions of Examples 1 to 22 and Comparative Example 1.

[0261]

[Table 3]

As the resin R used in the comparative example, a copolymer (A-1) described in JP-A-11-265067 was used. The structure of the resin R is shown below.

[0263]

Embedded image

The structure of PAG (a) is shown below.

[0265]

Embedded image

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

As the amine, 1 represents 1,5-diazabicyclo [4.3.0] -5-nonene (DBN);
2 is bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) sebagate 3, tri-n-butylamine 4, triphenylimidazole 5, antipyrine 6, 2,6-diisopropylaniline 7, tri-n-octylamine.

(Evaluation Test) First, Brewer Sci
ARC-25 manufactured by ence Co., Ltd. was applied to a silicon wafer with a thickness of 78 nm using a spin coater and dried, and then the obtained positive photoresist composition solution was applied thereon using a spin coater. 10 and Comparative Example 1
Was dried at 130 ° C. and at 140 ° C. for 90 seconds to form a positive photoresist film of about 0.4 μm, which was exposed to an ArF excimer laser (193 nm). The heat treatment after the exposure was performed in Examples 1 to 10 and Comparative Example 1 at 130.
℃, otherwise at 90 ℃ 90 seconds, 2.38% tetramethylammonium hydroxide aqueous solution development,
After rinsing with distilled water, a resist pattern profile was obtained. The resist pattern of the silicon wafer thus obtained was observed with a scanning microscope (SEM), and the resist was evaluated as follows. Table 4 shows the results of these evaluations.

[Resolution]: The resolution of a contact hole is represented by the limit contact hole size (μm) that can be resolved with an exposure amount that reproduces a contact hole size of 0.16 μm (pitch is １ ／).

[Side lobe resistance]: The evaluation of the side lobe resistance is as follows. Eopt is the exposure amount that reproduces a 0.18 μm (1/2) mask size to 0.15 μm, and the exposure amount is further increased to start the side lobes. The exposure amount was defined as Elimit, and Elimit / Eopt was evaluated. The larger the value, the better.

[0271]

[Table 4]

As is evident from the results in Table 4, the positive resist composition of the present invention has a contact hole resolution,
It can be seen that the halftone exposure suitability is excellent.

[0273]

The positive resist composition of the present invention is suitable for far ultraviolet light, particularly ArF excimer laser light having a wavelength of 193 nm, and has excellent contact hole resolution and halftone exposure suitability. Therefore, it is suitably used for lithography using far ultraviolet rays such as ArF excimer laser exposure.

Continued on front page F-term (reference) 2H025 AA02 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB08 CB10 CB14 CB41 CB45 FA17 4J002 AA031 BG041 BG051 BG071 BK001 EB016 EB106 EN136 EQ016 EV236 EV296 EW176 EY006 EZ006 FD006 206

Claims (6)

[Claims] 1. A resin comprising a repeating unit (A) having an aliphatic cyclic hydrocarbon group and a repeating unit not containing an aromatic moiety but having a crosslinking moiety having a structure represented by the following general formula (a). A positive resist composition comprising: a resin whose dissolution rate in an alkali developer is increased by the action of an acid; and (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation. Embedded image In the formula (a), R ₁₀₁ and R ₁₀₂ independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. 2. The positive resist composition according to claim 1, wherein the resin (A) contains a repeating unit having a structure represented by the following general formula (b). Embedded image In the formula (b), R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. R _{103 to} R ₁₀₈ each independently represent a hydrogen atom, an alkyl group, a cyano group, or a halogen atom which may have a substituent. A represents at least one divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, and a sulfonamide group. 3. The positive resist composition according to claim 1, wherein the resin (A) contains a repeating unit having a structure represented by the following general formula (c). Embedded image In the formula (c), R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 4 carbon atoms. R _{103 to} R ₁₀₈ each independently represent a hydrogen atom, an alkyl group, a cyano group, or a halogen atom which may have a substituent. A represents at least one divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, and a sulfonamide group. 4. The resin of (A) has the following general formula (pI):
It is characterized by containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formula (pVI) and at least one selected from the group of a repeating unit represented by the following general formula (II). The positive resist composition according to claim 1. Embedded image (Wherein, 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 for forming R ₁₂
To R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ or R ₁₅ ,
Any of R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁
Each independently represents a hydrogen atom, a C1 to C4 linear or branched alkyl group or an alicyclic hydrocarbon group,
However, at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, any of R ₁₉ and 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 be bonded to each other to form a ring. ) In the formula (II): R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom,
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 may have a substituent and has two bonded carbon atoms (C—C). 5. Z ′ in the general formula (II) contains two bonded carbon atoms (CC) and forms a bridged alicyclic structure which may have a substituent. 5. The positive resist composition according to claim 4, wherein 6. The compound represented by the following general formula (II)
The positive resist composition according to claim 4, which is represented by A) or the general formula (II-B). Embedded image In the formulas (II-A) and (II-B), R ₁₃ ′ to R ₁₆ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, —COO
H, —COOR ₅ , a group decomposed 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,
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. Further, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. 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 represent a hydrogen atom or an alkyl group which may have a substituent. A, b
Represents 1 or 2. )