JP2002049154A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photoresist composition having good resolution even in the case of a contact hole pattern and a trench pattern in the production of a semiconductor device. SOLUTION: The positive type photoresist composition contains a resin containing specified repeating structural units and having a dissolution rate in an alkali developing solution increased by the action of an acid, a compound which generates the acid when irradiated with active light or radiation and a specified dissolution inhibiting compound.

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. More specifically, the present invention relates to a positive photoresist composition for deep ultraviolet exposure which can form a high-definition pattern by using light having a wavelength of not more than 250 nm, particularly a deep ultraviolet region including excimer laser light.

[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 ultra LSIs, it has become necessary to process ultrafine patterns having a line width of less than half a micron. Have been. In order to meet this need, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays is used.
The use of is being considered. 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 photoresist composition obtained by combining a (meth) acrylic resin having a lower absorption than a partially hydroxylated styrene resin with a compound capable of generating an acid by light is used. Proposed. For example, JP-A-7-199467 and JP-A-7-2523
No. 24 etc. Among them, JP-A-6-289615 discloses a resin in which a tertiary carbon organic group is ester-bonded to oxygen of a carboxyl group of acrylic acid.

Further, Japanese Patent Application Laid-Open No. Hei 7-234511 discloses an acid-decomposable resin having an acrylic ester or a fumaric ester as a repeating structural unit. The fact is that performance has not been obtained.

Further, there has been proposed a resin into which an alicyclic hydrocarbon site is introduced for the purpose of imparting dry etching resistance. JP-A-9-73173, JP-A-9-90637
JP-A-10-161313 discloses an acid-sensitive group containing a structural unit containing an alkali-soluble group protected by a structure containing an alicyclic group, and the alkali-soluble group being eliminated by an acid to make the group alkali-soluble. A resist material using a hydrophilic compound is described.

[0007] Japanese Patent Application Laid-Open Nos. 9-90637 and 10-
JP-A-2070769 and JP-A-10-274852 describe resist compositions containing an acid-decomposable resin having a specific lactone structure.

Since lithography processes for manufacturing devices using design rules of 0.18 μm and 0.13 μm or less often use light having a wavelength of 193 nm as exposure radiation, resist polymers which do not contain much ethylenic unsaturation are used. Is desired. JP-A-10-1073
No. 9 and JP-A-10-307401, the wavelength 193
Although the transparency to nm has been improved, the sensitivity is not always high, and when lithography of 0.13 μm or less is considered, resist performance such as insufficient resolution is insufficient. JP-A-10-130340 discloses that
A chemically amplified resist containing a terpolymer having a specific repeating structural unit having a norbornene structure in the main chain is disclosed.

However, such a chemically amplified resist has not been satisfactory with respect to the resolution of minute contact hole patterns and trench patterns. A contact hole is a hole through which metal for an electrode of a semiconductor device passes to the surface of the semiconductor.In recent years, in the manufacture of semiconductor devices, in addition to forming fine line widths, the size of the contact hole has been miniaturized. There is a need for a positive photoresist composition that can resolve minute contact hole patterns. However, it has not been known at all what resist material should be designed to resolve a minute contact hole. Also, it has been found that a resist suitable for obtaining a fine line width is not necessarily suitable for resolving a fine contact hole pattern. A trench refers to a groove-shaped pattern formed by a series of contact holes. The size of the trench has been reduced as in the case of the contact hole, and a positive photoresist composition capable of resolving a minute trench pattern has been desired.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photoresist composition having good resolution for a contact hole pattern and a trench pattern in the manufacture of a semiconductor device. .

[0011]

Means for Solving the Problems The present inventors diligently studied constituent materials of a positive-type chemically amplified resist composition, and found that an acid-decomposable resin having a repeating structural unit having a specific structure and a specific compound were used. It has been found that the object of the present invention is achieved by using in combination. That is,
The above object is achieved by the following constitutions.

(1) (A) It contains a repeating structural unit represented by the following general formula (I) and a repeating structural unit represented by the following general formula (II), and the action of an acid increases the dissolution rate in an alkali developing solution. Resin, (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and
(C) A positive photoresist composition comprising a compound represented by the following general formula (CI) or (CII).

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

In the general formula (I), R _{11 to} R ₁₄ each independently represent a hydrogen atom or an alkyl group which may have a substituent. a is 0 or 1; In the general formula (II), R ₁ is
Represents a hydrogen atom or a methyl group. A represents a single bond, an alkylene group, a cycloalkylene 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. W
Represents a group represented by -C (Ra) (Rb) (Rc) or a group represented by -CH (Rd) -O-Re. Here, Ra, Rb, and Rc each independently represent a halogen atom, an alkoxy group, an alkoxycarbonyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, which may have an acyl group or an acyloxy group. However, Ra and Rb may combine with each other to form an alicyclic monocyclic ring. Rd represents a hydrogen atom or an alkyl group. As Re, a linear or branched alkyl group having 1 to 20 carbon atoms, which may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group as a substituent, or 3 carbon atoms Represents up to 20 cycloalkyl groups.

In the general formula (CI), X represents an oxygen atom, a sulfur atom, -N ( _R53 )-, or a single bond. R ₅₁ , R ₅₂
And R ₅₃ each independently represent a hydrogen atom or an alkyl group, and R ′ represents a group constituting an acid-decomposable group by —C (＝ O) —O—R ′. R represents a bridged hydrocarbon, a saturated cyclic hydrocarbon or an n1 valent residue containing a naphthalene ring. n1
Represents an integer of 1 to 4, and q1 represents an integer of 0 to 10.
In Formula (CII), R ₆₀ represents an alkyl group or a halogen atom, and R ₆₁ represents a group constituting an acid-decomposable group by —O—R ₆₁ . m1 represents an integer of 0 to 4. p1 is 1 to 4
Indicates an integer.

(2) (A) It contains a repeating structural unit represented by the above general formula (I) and a repeating structural unit represented by the above general formula (II), and the action of an acid increases the dissolution rate in an alkali developing solution. Resin, (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and
(C) A compound having at least two structures having at least one substituent having a carboxylic acid group protected by an acid labile group on a polycyclic structure represented by the following general formula (CIII) A positive photoresist composition comprising:

[0019]

Embedded image

(3) The positive photoresist composition as described in (1) or (2) above, wherein the resin (A) further contains a repeating structural unit represented by the following general formula (III): .

[0021]

Embedded image

In the formula (III): Z ₂ represents —O— or —N (R
₃ ) represents-. Here, R ₃ is a hydrogen atom, a hydroxyl group or —O
It represents an SO ₂ -R _4. R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. (4) The positive photoresist as described in any of (1) to (3) above, further comprising (D) an organic basic compound and a fluorine-based and / or silicon-based surfactant. Composition.

[0023]

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 (hereinafter also referred to as “acid-decomposable resin”). In the general formula (I) showing the repeating structural unit of the acid-decomposable resin, R _{11 to} R ₁₄ represent a hydrogen atom or an alkyl group which may have a substituent. The alkyl group of R _{11 to} R ₁₄ is preferably a group having 1 to 12 carbon atoms, more preferably a group having 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, Preferred examples include -butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group. Examples of the substituent of the alkyl group include a hydroxy group, an alkoxy group and an alkoxyalkoxy group, and preferably have 4 or less carbon atoms. In the general formula (I), a is 0 or 1.

In the general formula (II) representing a repeating structural unit of the acid-decomposable resin, R ₁ represents a hydrogen atom or a methyl group.
In the general formula (II), examples of the alkylene group represented by A include groups represented by the following formula. -[C (Rf) (Rg)] r- 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. . As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. 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. In the general formula (II), examples of the cycloalkylene group represented by A include those having 3 to 10 carbon atoms, such as a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.

W in the general formula (II) is a group constituting a group which is decomposed by the action of an acid together with the ester structure (-COO-), and is represented by -C (Ra) (Rb) (Rc)
Or a group represented by -CH (Rd) -O-Re. Here, Ra, Rb, and Rc each may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group, or an acyloxy group as a substituent, and may have a straight-chain or 1 to 20 carbon atoms. Represents a branched alkyl group or a cycloalkyl group having 3 to 20 carbon atoms. However, Ra and Rb may combine with each other to form an alicyclic monocyclic ring. Rd represents a hydrogen atom or an alkyl group. As Re, a linear or branched alkyl group having 1 to 20 carbon atoms, which may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group as a substituent, or 3 carbon atoms Represents up to 20 cycloalkyl groups.

Ra, Rb, Rc, Re have 1 to 2 carbon atoms
The zero linear or branched alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 carbon atom.
And specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl And a nonyl group and a decyl group. Ra, Rb, Rc,
As a cycloalkyl group having 3 to 20 carbon atoms of Re,
Examples thereof include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the alkyl group for Rd, an alkyl group having 1 to 4 carbon atoms is preferred, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group,
-Butyl group, isobutyl group, sec-butyl group, t-butyl group and the like. Examples of the alicyclic monocycle formed by combining Ra and Rb with each other include cyclopentane, cyclohexane, cyclooctane, and the like.

Ra, Rb, Rc, Re have 1 to 2 carbon atoms
In a further substituent of 0 linear or branched alkyl groups or cycloalkyl groups having 3 to 20 carbon atoms: an alkoxy group, an alkoxy group in an alkoxycarbonyl group includes a methoxy group, an ethoxy group, a propoxy group, Examples thereof include those having 1 to 4 carbon atoms such as a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the acyl group include a formyl group and a benzoyl group. Examples of the acyloxy group include a propylcarbonyloxy group and a benzoyloxy group. The general formula (I
As W in I), a tertiary alkyl group such as a t-butyl group, a t-amyl group, a 2-cyclohexyl-2-propyl group and a 1-methylcyclohexyl group, an alkoxy group such as an ethoxymethyl group and an ethoxyethoxymethyl group are preferable. Examples thereof include 1-alkoxyethyl groups such as a methyl group, a 1-ethoxyethyl group, and a 1-isopropoxyethyl group.

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

[0029]

Embedded image

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

[0031]

Embedded image

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

In the general formula (III), Z ₂ represents —O— or —N (R ₃ ) —. Here, R ₃ represents a hydrogen atom, a hydroxyl group or —O—SO ₂ —R ₄ . R ₄ is an alkyl group,
Represents a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group for R ₄ 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. , More preferably a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the haloalkyl group for R ₄ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ₄ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

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

[0037]

Embedded image

[0038]

Embedded image

The acid-decomposable resin as the component (A) is, in addition to the above-mentioned repeating structural units, dry etching resistance, suitability for a standard developer, 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, 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 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 a monomer, for example, an addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like can be used. And the like.

Specific examples include the following monomers. Acrylic esters (preferably alkyl acrylate having an alkyl group having 1 to 10 carbon atoms): methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic Acid-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate,
Trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate,
Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

Methacrylic 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 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 (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol etc.

Vinyl ethers: alkyl vinyl ethers (for example, 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 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, acrylonitrile, methacrylonitrile, maleilenitrile and the like.

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

In the acid-decomposable resin, the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, the suitability for a standard developing solution, 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.

The content of the repeating structural unit represented by the general formula (I) in the acid-decomposable resin is determined as follows:
It is preferably from 25 to 70 mol%, more preferably from 28 to 6 mol%.
It is 5 mol%, more preferably 30 to 60 mol%. In the acid-decomposable resin, the content of the repeating structural unit represented by the general formula (II) is 2 to 50 in all the repeating structural units.
Mol% is preferred, more preferably 4 to 45 mol%, and still more preferably 6 to 40 mol%. In acid-decomposable resin,
The content of the repeating structural unit represented by the general formula (III) is preferably from 20 to 80 mol%, more preferably from 25 to 70 mol%, even more preferably from 30 to 60 mol%, in all the repeating structural units.

The content of a repeating structural unit based on a copolymer component other than the repeating structural unit represented by the general formula (I), (II) or (III) in the resin may also affect the desired resist performance. In general, it is preferably 99 mol% or less, more preferably 90 mol%, based on the total number of moles of the repeating structural units represented by formulas (I) and (II). %, More preferably 80% by mole or less.

The molecular weight of the acid-decomposable resin as described above is weight average (Mw: value in terms of polystyrene by GPC method).
In the range of preferably from 1,000 to 1,000,000, more preferably from 1,500 to 500,000, further preferably from 2,000 to 200,000, and still more preferably from 2,500 to 100,000. Yes, the bigger,
While the heat resistance and the like are improved, the developability and the like are lowered, and the balance is adjusted to a preferable range by these balances. The acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization).

In the positive photoresist composition of the present invention, the amount of the acid-decomposable resin in the entire resist composition is preferably 40 to 99.99% by weight, more preferably 50 to 99.99% by weight, based on the total solid content. 97% by weight.

Preferred specific examples of combinations of repeating structural units of the acid-decomposable resin (A) are shown below.

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[2] (B) Compound that Generates Acid upon Irradiation with Actinic Ray or Radiation (Photoacid Generator) The photoacid generator used in the present invention is a compound that generates an acid upon 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.

Further, 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 which decompose upon irradiation with an electron beam to generate an acid, those which are particularly effectively used will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0065]

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.

[0067]

Embedded image

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

[0069]

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, 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.

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image

[0081]

Embedded image

[0082]

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).

[0085]

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.

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

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

[0093]

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.

[0095]

Embedded image

[0096]

Embedded image

The amount of these photoacid generators to be added is generally in the range of 0.01 to 30% by weight, preferably 0.3 to 20% by weight, more preferably 0.3 to 20% by weight, based on the solids 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 0.01% by weight, the sensitivity tends to decrease. (Especially baking) The margin becomes narrow, which is not preferable.

[3] (C) Dissolution Inhibiting Compound In addition to the above resin and photoacid generator, the positive photosensitive composition of the present invention comprises, as a dissolution inhibitor, the compound represented by the above general formula (CI) or
A compound represented by (CII) or a structure having at least one substituent containing a carboxylic acid group protected by an acid labile group on a polycyclic structure represented by the general formula (CIII), Contains two compounds. In the general formula (CI), X represents an oxygen atom, a sulfur atom, -N
(R ₅₃ ) — or a single bond. In R ₅₁ , R ₅₂ and R ₅₃ of the general formula (CI), the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group or t-butyl group, hexyl group, 2-ethylhexyl group,
Those having 1 to 8 carbon atoms such as an octyl group are exemplified. In the general formula (CI), -C (= O) -OR '
Is a group that is decomposed by the action of an acid (also referred to as an acid-decomposable group). Here, R ′ may be a tertiary alkyl group (preferably having 4 to 20 carbon atoms ) such as a t-butyl group, a methoxy t-butyl group, a t-amyl group, an isobornyl group, or a substituent. A 1-alkoxyethyl group such as a 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, 1- [2- (n-butoxy) ethoxy] ethyl group ( (Preferably 2 to 10 carbon atoms), which may have a substituent, an alkoxymethyl group (preferably 2 to 10 carbon atoms) such as a 1-methoxymethyl group and a 1-ethoxymethyl group; Trialkyl groups such as an optionally substituted tetrahydropyranyl group, an optionally substituted tetrahydrofuranyl group, a trimethylsilyl group, a t-butyldimethylsilyl group, and a diisopropylmethylsilyl group. Silyl groups can be exemplified (preferably having a carbon number of 3 to 20), 3-oxo-cyclohexyl group. The tertiary alkyl group for R ′ may form an alicyclic ring. Preferred substituents that the alkoxymethyl group and alkoxyethyl group of R ′ may have include a halogen atom, — (OCH ₂ CH ₂ ) ₂ OCH ₃ , —S (CH ₂ ) ₂ CH ₃ , and —SC (CH ₃ ) ₃ ,-
O-adamantane, -O-CO-adamantane and the like can be mentioned.
Preferred substituents that the tetrahydropyranyl group and the tetrahydrofuranyl group may have include a carbonyl group and an alkyl group having 1 to 5 carbon atoms.

R represents a bridged hydrocarbon, a saturated cyclic hydrocarbon or an n 1 -valent residue containing a naphthalene ring. Examples of the n1 valent residue containing a bridged hydrocarbon include adamantane, norbornane, tricyclodecane, tetracycloundecane, and pinene having n1 bonds.
Examples of the n1 valent residue containing a saturated cyclic hydrocarbon include terpene and steroid. N containing a naphthalene ring
Examples of the monovalent residue include a naphthalene ring having n1 bonds. The above-mentioned bridged hydrocarbon, saturated cyclic hydrocarbon or naphthalene ring may have a substituent at a position other than a bond. Preferred substituents include
Hydroxyl group, halogen atom, cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, 2 to 2 carbon atoms
5 acyl groups, C 2 to C 5 acyloxy groups, C 2 to C 5 alkoxycarbonyl groups, and C 2 to C 10 alkoxyalkyleneoxy which may be substituted by alkoxy or alkoxyalkyleneoxy. Can be q1 is an integer of 0 to 10, preferably 0 to 10
7, more preferably 0-5.

In R ₆₀ of the formula (CII), the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-
Examples thereof include those having 1 to 8 carbon atoms such as a butyl group or a t-butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group. In the general formula (CII), -OR ₆₁ is a group that is decomposed by the action of an acid (also referred to as an acid-decomposable group). Here, R ₆₁ is a t-butyl group, methoxy t
A tertiary alkyl group (preferably having 4 to 20 carbon atoms) such as a -butyl group, a t-amyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-cyclohexyloxyethyl group, 1- [2- (n-butoxy)
[Ethoxy] ethyl may have a substituent such as a 1-alkoxyethyl group (preferably having 2 to 10 carbon atoms), a 1-methoxymethyl group, a 1-ethoxymethyl group or the like which may have a substituent. An alkoxymethyl group (preferably having 2 to 2 carbon atoms)
10) a tertiary alkoxycarbonyl group (preferably having 4 to 20 carbon atoms) such as a t-butoxycarbonyl group and a t-amyloxycarbonyl group; a tetrahydropyranyl group which may have a substituent; And a trialkylsilyl group such as a tetrahydrofuranyl group, a trimethylsilyl group, a t-butyldimethylsilyl group, and a diisopropylmethylsilyl group, and a 3-oxocyclohexyl group. For each of q1, n1, m1, and p1,
When two or more, the plurality of residues present may be the same or different.

The synthesis of the compounds represented by the above general formulas (CI) and (CII) of the present invention is carried out by synthesizing a corresponding carboxylic acid or a carboxylic acid derivative such as acid chloride or a corresponding naphthol derivative with R'-OH. , R'-X (halogen) or a corresponding olefin, or a reaction of a naphthol derivative with a dialkoxycarbonyl ether.

In the positive photosensitive composition of the present invention, the dissolution inhibitors represented by the general formulas (CI) and (CII) can be used alone or in combination of two or more. good. In the positive photosensitive composition of the present invention, the total amount of the compound represented by the general formula (CI) or (CII) is usually 1 to 4 with respect to the total solid content.
0% by weight, preferably 3 to 30% by weight.

Specific examples of the compounds represented by the general formula (CI) include the following [CI-1] to [CI-10]
8], and specific examples of the compound represented by the general formula (CII) include the compounds represented by the following [CII-1] to [CII-52]. It is not limited to these.

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

Next, as a dissolution inhibitor in a further embodiment of the present invention, a substituent containing a carboxylic acid group protected by an acid labile group on the polycyclic structure represented by the above general formula (CIII) ( A compound (oligomer-type dissolution inhibitor) having at least two structures having at least one substituent having an acid labile group will be described.

The oligomer type dissolution inhibitor is preferably a polycyclic structure represented by the above general formula (CIII), a substituent having at least one acid labile group on the polycyclic structure and at least one substituent. A saturated polycyclic hydrocarbon compound A having a hydroxy (OH) group and a linear, branched or cyclic bifunctional saturated hydrocarbon compound B (where the functional group is a carboxylic acid group or a carboxylic acid halide (for example, (A chloride) group) to obtain a condensation reaction product.

The condensation reaction product has 2 to 50 polycyclic moieties derived from the saturated polycyclic hydrocarbon compound A. As the condensation reaction proceeds, the number of polycyclic moieties per molecule varies. In the present invention, the condensation reaction product desirably has an average of about 5 to about 20 polycyclic moieties.

The bifunctional saturated hydrocarbon compound B preferably has 1 to 15 carbon atoms, such as alkanes, alkoxyalkanes, cycloalkanes and polycycloalkanes, such as dicarboxylic acids or dicarboxylic acid halides. Is preferred. Substituent group having a saturated polycyclic labile groups acid in hydrocarbon compound A (functional group are excluded) is 2
It is desirable to have at least 12 and no more than 12 carbon atoms.
However, when the compound has 9 or more carbon atoms, the saturated polycyclic hydrocarbon compound A preferably has two or more hydroxy groups.

The saturated polycyclic hydrocarbon compound A has a carboxylic acid group protected by an acid labile group. Carboxylic acid group protection by acid labile groups reduces the solubility of the compound in aqueous alkaline solutions. Therefore,
The dissolution inhibitor having such an acid labile group imparts a desired alkali aqueous solution insolubility to the resist composition before exposure to radiation.

Upon irradiation, and generally post-baking, the acid labile groups are eliminated, resulting in a sufficient amount of carboxylic acid groups to render the resist material soluble in aqueous alkaline solutions. Suitable acid labile groups are, for example, t-butyl, t-amyl, 1-methylcyclohexyl, 3-oxocyclohexyl and bis (2-trimethylsilyl) ethyl and other substituents which are easily eliminated in the presence of photoacids. And so on.
These wide range of acid labile groups are well known to those skilled in the art. Further, the group defined as W in the above formula (II) can also be mentioned as an example of the acid labile group. In the presence of acids, these groups form free carboxylic acids and acidolisis or acid-catalyzed hydrolysis products.

The saturated polycyclic hydrocarbon compound A preferably has 1 to 3 hydroxy groups, and the hydroxy groups are preferably present on a 6-membered ring. Cholic acid esters are an example of a polycyclic compound having three hydroxy groups in the polycyclic moiety (one hydroxy group on each 6-membered ring). Deoxycholate has two hydroxy groups on the polycyclic moiety (one on each of the two six-membered rings).
(Wherein there are two hydroxy groups).

In the positive resist composition of the present invention, a cholate compound having a structure represented by the following general formula (IV) may be used as a dissolution inhibitor together with the oligomer-type dissolution inhibitor.

[0135]

Embedded image

(In the above general formula (IV), X is an acid labile group, and R _{10 is} present or absent.
R ₁₀ is a lower alkylene group having 6 or less carbon atoms, for example, butylene or isobutylene. Polycyclic moieties have one or more hydroxy substituents. )

The polycyclic moiety of the compound represented by formula (IV) has one or more hydroxy groups, and the hydroxy groups are generally present on a 6-membered ring. Cholic acid esters are an example of a polycyclic compound having three hydroxy groups in the polycyclic moiety (one hydroxy group on each 6-membered ring). Deoxycholate has two hydroxy groups on the polycyclic moiety (one on each of the two six-membered rings).
(Wherein there are two hydroxy groups).

When the oligomer-type dissolution inhibitor is used in combination with the above-mentioned cholic acid ester-based compound (hereinafter referred to as “monomer compound”), the oligomer dissolution inhibitor may be used in combination with 90 to 90
Desirably, it is composed of 10% by weight and 10 to 90% by weight of the monomer compound.

When the oligomer type dissolution inhibitor and the above-mentioned monomer compound are used in combination, the total amount thereof is
It is preferably blended in an amount of 1 to 40% by weight, more preferably 3 to 30% by weight, based on the total solid content in the composition.

[4] (D) Organic Basic Compound The preferred (D) organic basic compound that can be used in the present invention is a compound having a higher basicity than phenol. Among them, a nitrogen-containing basic compound is preferable. (D) By adding an organic basic compound, the sensitivity fluctuation over time is improved. For example, (D) a compound having the following structure can be exemplified as the organic basic compound.

[0141]

Embedded image

Here, R²⁵⁰, R²⁵¹And R²⁵²Are each
Independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
1-6 aminoalkyl groups, hydroxy having 1-6 carbon atoms
Alkyl group or substituted or unsubstituted 6 to 20 carbon atoms
An aryl group, where R ²⁵¹And R²⁵²Are connected to each other
To form a ring.

[0143]

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 organic basic compounds are used alone or in combination of two or more. The amount of the organic basic compound to be used is generally 0.001 to 10% by weight, preferably 0.1 to 10% by weight, based on the solid content of the entire photosensitive resin composition.
01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the organic basic compound cannot be obtained. Meanwhile, 1
If it exceeds 0% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

[5] (F) Fluorine and / or Silicon Surfactant The positive photoresist composition of the present invention preferably contains a fluorine and / or silicon surfactant.
The positive photoresist composition of the present invention may contain a fluorine-based surfactant, a silicon-based surfactant, or a surfactant containing both a fluorine atom and a silicon atom, or may contain two or more kinds. preferable. When the positive photoresist composition of the present invention contains the above-mentioned acid-decomposable resin and the above-mentioned surfactant, the density dependency is improved.

As these surfactants, for example, those described in
No. 62-36663, JP-A-61-226746, JP-A-61-226745,
JP-A-62-170950, JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, JP-A-9-54432, JP-A-9-598
No. 8, U.S. Pat.No. 5,405,720, No. 5360692, No. 5529881,
No. 5296330, No. 5436098, No. 5576143, No. 5294511
And No. 5824451. The following commercially available surfactants can also be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC
430, 431 (Sumitomo 3M Limited), Mega Fuck F171,
F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troysol S-366 (Troy Chemical Co., Ltd.) )) Or a silicon-based surfactant. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The blending amount of the fluorine-based and / or silicon-based surfactant is based on the solid content in the composition of the present invention.
Usually 0.001% by weight to 2% by weight, preferably 0.01% by weight
% By weight to 1% by weight. These surfactants may be added alone or in some combination. Examples of the surfactant that can be used in addition to the above include, specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. , Polyoxyethylene octyl phenol ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenol ether,
Sorbitan fatty acid esters such as polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, and polyoxyethylene sorbitan Nonionic interfaces such as polyoxyethylene sorbitan fatty acid esters such as monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate Activators and the like can be mentioned. 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.

The positive photoresist composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound other than those described above, a dye, a plasticizer, a sensitizer, and a compound which promotes solubility in a developing solution. Can be contained.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components, and coated on a support. 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, ethylene carbonate, propylene carbonate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, methyl 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, ethylene carbonate, propylene carbonate, butyl acetate, methyl lactate, ethyl lactate, Examples thereof include methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, and tetrahydrofuran.

Such a positive photoresist 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. In the present invention, if necessary, a commercially available inorganic or organic antireflection film can be used.

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, AC-2 and AC-3 manufactured by Shipley Co. can also be used.

The resist solution is coated on a substrate (eg, a silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the antireflection film as required), 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.

[0158]

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 of Resin (1) Norphorpenene, tert-butyl acrylate, and maleic anhydride were charged into a reaction vessel at a molar ratio of 40/20/40, and dissolved in methyl ethyl ketone to prepare a solution having a solid content of 60% by weight. This was heated at 60 ° C. under a nitrogen stream. When the reaction temperature becomes stable, radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd.
1 was added at 1 mol% to start the reaction. After heating for 10 hours, the reaction mixture was diluted twice with methyl ethyl ketone, and then poured into a large amount of tert-butyl methyl ether to precipitate a white powder. The precipitated powder was taken out by filtration, dried, and the resin (1) exemplified above, which was the target product, was obtained. When the molecular weight analysis of the obtained resin (1) by GPC was attempted, it was 15300 (weight average) in terms of polystyrene. From the NMR spectrum, the composition of the resin (1) was found to be norbornene / t-butyl acrylate /
The molar ratio of maleic anhydride was 38/17/45.
The resins (2) to (15) exemplified above were synthesized in the same manner as in the synthesis of the resin (1). Table 1 shows the composition ratio and the weight average molecular weight (Mw) of the resin.

[0160]

[Table 1]

Synthesis of Oligomeric Dissolution Inhibitor (A) T-butyl deoxycholate (2 g, 4 g, previously dried under vacuum at 60 ° C. overnight) was placed in a Schlenk tube dried in an oven and purged with argon. .457 mmol),
(Distilled from CaH ₂₎ N-methylmorpholine (1.
(1 mL, 10 mmol) and methylene chloride (8 mL) were charged to synthesize t-butyl deoxycholate.

Cooled to 0 ° C. and distilled glutaryl dichloride (0.552 g, 4.324 mmol,
97 mol%) was added slowly using a hermetic syringe. As the addition was over, salt precipitation began. The resulting slurry was stirred and allowed to warm to room temperature over 30 minutes, then warmed at 40 ° C. for 30 minutes.

Thereafter, the mixture was treated with methylene chloride (40
mL) and water (40 mL). The organic layer was washed four times with dilute aqueous ammonium acetate and concentrated to give a solid. This solid was freeze-dried from dioxane to obtain a powder.

This powder was dispersed in water (100 mL) and stirred for 1 hour. The powder was recovered by filtration and dried in vacuo. The yield was 1.5 g (64% yield). When this method was repeated using tetrahydrofuran (THF), the yield was 1.7 g (74% yield). The structure of the resulting oligomer is shown below. This oligomer is referred to as a dissolution inhibitor A.

[0165]

Embedded image

Oligo (t-butyldeoxycholate-co-glutarate) end-capped with t-butyldeoxycholate (where tBu represents a t-butyl substituent,
Y represents either hydrogen or another unit in the structure defined by parentheses having the subscript M or l. )

The number of units M per molecule is from about 5 to about 20. As mentioned above, the condensation reaction can take place at any OH group on the polycyclic compound. Therefore, the above structure is shown as an aid in explaining the reaction product, and not the actual structure of the obtained product.

Synthesis of Oligomeric Dissolution Inhibitor (B) In a Schlenk tube dried in an oven and purged with argon, t-butyl deoxycholate (2 g, 4 g, previously dried under vacuum at 60 ° C. overnight) was added. .457 mmol),
(Distilled from CaH ₂₎ N-methylmorpholine (3.
26 g (32.2 mmol) and THF (35 mL) were charged to synthesize t-butyl deoxycholate.

Cooled to 0 ° C. and distilled glutaryl dichloride (1.232 mL, 9.654 mmol,
1.632 g) was added slowly using an airtight syringe. The Schlenk tube was sealed and heated to 60 ° C. overnight. The reaction solution was then diluted with methanol (20%) and precipitated in water (500 mL) containing acetic acid to neutralize N-methylmorpholine.

The dilution / precipitation was repeated twice. The polymer was recovered by filtration, washed with distilled water and dried in a vacuum at 60 ° C. The yield was 4 g (74% yield). The structure of the resulting oligomer is shown below. This oligomer is referred to as a dissolution inhibitor B.

[0171]

Embedded image

Oligo (t-butylcholate-co-glutarate) end-capped with t-butylcholate (wherein
tBu represents a t-butyl substituent, and Y represents either hydrogen or another unit in the structure defined by parentheses having the subscript M or l. )

The number of units M per molecule is from about 5 to about 20. As mentioned above, the condensation reaction can take place at any OH group on the polycyclic compound. Therefore, the condensation reaction product of a cholate having three hydroxy substituents (that is, a cholate) tends to have a branched structure. The above structure is shown as an aid in explaining the reaction product and not the actual structure of the product obtained.

Examples 1 to 20 and Comparative Example 1 (Preparation and Evaluation of Positive Photoresist Composition) 2 g of the resin shown in Table 2, 200 mg of dissolution inhibitor (the ratio of a plurality of compounds used in Table 2 is weight ratio), light 50 mg of an acid generator, 5 mg of an organic basic compound, and 5 mg of a surfactant were blended, and each was dissolved in propylene glycol monomethyl ether acetate at a solid content of 10% by weight, and then filtered through a 0.1 μm microfilter. 1 to 20 positive resist compositions were prepared. As Comparative Example 1, a positive resist composition was prepared in the same manner as described above, using the resins and photoacid generators shown in Table 2.

As the surfactant, 1: Megafac F176 (manufactured by Dainippon Ink Co., Ltd.)
(Fluorine type) 2: Megafac R08 (Dai Nippon Ink Co., Ltd.) (Fluorine and silicone type) 3: Polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.) 4: Polyoxyethylene nonyl phenyl ether 5 : Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)

Examples of the organic basic compound include: 1: DBU (1,8-diazabicyclo [5.4.0]-
7-undecene) 2: 4-DMAP (4-dimethylaminopyridine) 3: TPI (2,4,5-triphenylimidazole) Resin (R): Example 3 of JP-A-10-130340
(R2 = t-butyl) was used.

[0177]

[Table 2]

(Evaluation Test) An antireflection film made of Shipley was coated on a silicon wafer by AR19, baked at 215 ° C. for 90 seconds, and coated to a thickness of 850 A. The above-prepared resist solution is applied onto the substrate thus obtained, and 135
It was baked at 90 ° C. for 90 seconds to apply a film having a thickness of 0.30 μm.
The wafer thus obtained was exposed to an ArF excimer laser stepper (ArF exposing machine 9300, manufactured by ISI) with a resolving power mask being changed while changing the exposure amount. After heating in a clean room at 150 ° C for 90 seconds,
Tetramethylammonium hydroxide developer (developed at 2.38% by weight for 60 seconds, rinsed with distilled water,
Dry to obtain a pattern.

[Contact Hole Pattern Resolution] For each resist, the diameter (μm) of the contact hole that can be resolved with the minimum exposure amount to reproduce a contact hole having a diameter of 0.20 μm was taken as the resolution. [Trench pattern resolution] For each resist, a trench pattern slit width (μm) that can be resolved with a minimum exposure amount to reproduce a trench pattern having a diameter of 0.20 μm with a binary mask was taken as the resolution. The results are shown in Table 3.

[0180]

[Table 3]

As shown in Table 3 above, it can be seen that the positive photoresist composition of the present invention has excellent resolving power for contact holes and trench patterns.

[0182]

According to the present invention, it is possible to provide a positive photoresist composition capable of favorably resolving a contact hole and a trench pattern in the production of a semiconductor device.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/372 C08K 5/372 5/541 C08L 45/00 C08L 45/00 G03F 7/004 501 G03F 7 / 004 501 504 504 C08K 5/54 H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA02 AB16 AC04 AD03 BE00 BE07 BE10 BF11 BG00 CB43 CC04 CC20 FA17 4J002 BK001 EB106 EH117 EH157 EU028 EU128 EU028 EU008 EU028 EU028 EU028 EU008 EU028 EU008 EU028 EU028 EU008 EU028 EU008 EU028 EU008 EU028 EU028 EU008 EU028 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU028 EU128 EU128 EU128 EU128 EU028 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU028 EU128 EU128 EU128 EU128 EU128 EU028 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU128 EU0 EU EU EU EU226 EU238 EV216 EV266 EV296 EX037 GP03 4J100 AL03Q AL08Q AM43R AM45R AM47R AR11P BA03P BA03R BA04Q BA05Q BA06Q BA11R BA14P BA20P BA20Q BA58R BB18R BC04Q BC08R CA04 CA05 JA38

Claims (4)

[Claims] (A) It contains a repeating structural unit represented by the following general formula (I) and a repeating structural unit represented by the following general formula (II), and the action of an acid increases the dissolution rate in an alkali developing solution. A positive photoresist comprising a resin, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (C) a compound represented by the following general formula (CI) or (CII). Composition. Embedded image Embedded image Embedded image In the general formula (I), R _{11 to} R ₁₄ each independently represent a hydrogen atom or an alkyl group which may have a substituent. a is 0 or 1; In the general formula (II), R ₁ represents a hydrogen atom or a methyl group. A represents a single bond, an alkylene group, a cycloalkylene 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. W is -C (Ra)
(Rb) a group represented by (Rc) or —CH (Rd)
Represents a group represented by —O—Re. Where Ra, Rb,
Rc is each independently a linear or branched alkyl group having 1 to 20 carbon atoms which may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group as a substituent; 3-20 carbon atoms
Cycloalkyl groups. Where Ra and Rb are
It may combine with each other to form an alicyclic monocyclic ring. Rd represents a hydrogen atom or an alkyl group. As Re,
A linear or branched alkyl group having 1 to 20 carbon atoms or 3 to 20 carbon atoms which may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group as a substituent. Represents a cycloalkyl group. In the general formula (CI), X represents an oxygen atom, a sulfur atom, -N ( _R53 )-, or a single bond. R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom or an alkyl group;
R ′ represents a group constituting an acid-decomposable group at —COOR ′. R represents a bridged hydrocarbon, a saturated cyclic hydrocarbon or an n1 valent residue containing a naphthalene ring. n1 represents an integer of 1 to 4, and q1 represents an integer of 0 to 10. General formula (CI
In I), R ₆₀ represents an alkyl group or a halogen atom,
R ₆₁ represents a group constituting an acid-decomposable group by -OR ₆₁ ;
m1 represents an integer of 0 to 4. p1 represents an integer of 1 to 4. (A) It contains a repeating structural unit represented by the following general formula (I) and a repeating structural unit represented by the following general formula (II), and the action of an acid increases the dissolution rate in an alkali developing solution. Resin, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (C) a carboxylic acid group protected on the polycyclic structure represented by the following general formula (CIII) by an acid labile group A positive photoresist composition comprising a compound having at least two structures having at least one substituent containing: Embedded image Embedded image Embedded image In the general formula (I), R _{11 to} R ₁₄ each independently represent a hydrogen atom or an alkyl group which may have a substituent. a is 0 or 1; In the general formula (II), R ₁ represents a hydrogen atom or a methyl group. A represents a single bond, an alkylene group, a cycloalkylene 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. W is -C (Ra)
(Rb) a group represented by (Rc) or —CH (Rd)
Represents a group represented by —O—Re. Where Ra, Rb,
Rc is each independently a linear or branched alkyl group having 1 to 20 carbon atoms which may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group as a substituent; 3-20 carbon atoms
Cycloalkyl groups. Where Ra and Rb are
It may combine with each other to form an alicyclic monocyclic ring. Rd represents a hydrogen atom or an alkyl group. As Re,
A linear or branched alkyl group having 1 to 20 carbon atoms or 3 to 20 carbon atoms which may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group or an acyloxy group as a substituent. Represents a cycloalkyl group. 3. The resin (A) further comprises the following general formula (III):
The positive photoresist composition according to claim 1, further comprising a repeating structural unit represented by the formula: Embedded image In the formula (III), Z ₂ represents —O— or —N (R ₃ ) —. Here, R ₃ is a hydrogen atom, a hydroxyl group or —OSO ₂ —R
Represents ₄ . R ₄ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. 4. The positive-type photo according to claim 1, further comprising (D) an organic basic compound, and (E) a fluorine-based and / or silicon-based surfactant. Resist composition.