JPH11184090A - Positive type photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure satisfactory dry etching resistance, suitability to a standard developer and excellent adhesion to a substrate and to prevent defective development and cracking by incorporating a resin which increases its alkali solubility when decomposed by the action of an acid and contains a polymer contg. specified repeating units. SOLUTION: The photoresist compsn. contains a resin which increases its alkali solubility when decomposed by the action of an acid and contains a polymer contg. repeating units represented by formula I or II. In the formulae I and II, R1 -R16 may be the same or different and are each H, alkyl which may have a substituent, halogen, cyano, -COOH, -COeO-R31 (R31 is alkyl or cycloalkyl), a group which is decomposed by the action of an acid, -C(=O)-O-A- R18 or -C(=O)-X2 -A-R18 , m/n is 1/9 to 9/1, min and p+q are each 10-100, (p) and (q) are each 0-100, X. is a divalent combining group such as S and R18 is H, alkyl or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition for use in an ultra-microlithography process such as the production of an VLSI or a high-capacity microchip and other photofabrication processes. More specifically, the present invention relates to a positive photoresist composition capable of forming a high-definition pattern using a far 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 VLSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to satisfy 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. For example,
When using 248 nm light of a KrF excimer laser, a hydroxystyrene-based polymer having a low light absorption is particularly used.
There has been proposed a resist composition using a polymer having an acetal group or a ketal group introduced as a protective group. JP-A-2-141636, JP-A-2-19847, JP-A-4
For example, Japanese Patent Application Laid-Open No. 5-281745 and Japanese Patent Application Laid-Open No. 5-281745 are examples. In addition, similar compositions using a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group as an acid-decomposable group are disclosed in JP-A-2-209977 and JP-A-3-209.
206458 and JP-A-2-19847. These are 24 KrF excimer lasers.
Although suitable when using 8 nm light, sensitivity is low when using an ArF excimer laser as the light source, because the absorbance is still essentially too high. In addition, there are other disadvantages associated therewith, such as deterioration of resolution, deterioration of focus tolerance, deterioration of pattern profile, and the like, and many points still need improvement.

[0005] Accordingly, a photoresist composition for an ArF light source is a photoresist composition in which a (meth) acrylic resin having a lower absorption than a partially hydroxylated styrene resin is combined with a compound capable of generating an acid by light. Resist compositions have been proposed. For example, JP-A-7-1
No. 99467 and No. 7-252324. 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 both an acrylic ester and a fumaric ester as a repeating unit. It is a fact that no good performance has been obtained.

Further, a resin into which an alicyclic hydrocarbon moiety has been introduced for the purpose of imparting dry etching resistance has been proposed. However, the introduction of an alicyclic hydrocarbon moiety has a disadvantage that the system becomes extremely hydrophobic. In addition, phenomena such as difficulty in developing with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution, and peeling of the resist from the substrate during the development are observed. 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. Although some results have been obtained, concerns about 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 a resist, many measures have been taken to supplement a hydrophobic alicyclic hydrocarbon site by introducing a hydrophilic group. In general, measures have been taken to copolymerize monomers having a carboxylic acid moiety such as acrylic acid or methacrylic acid with monomers having an alicyclic hydrocarbon group. Although there is a tendency to improve the properties, there are many problems such as the deterioration of dry etching resistance and the remarkable loss of resist film, and the above-mentioned problem has not been solved. Further, Japanese Patent Application Laid-Open No. 7-234511 discloses HEMA.
The aim was to solve the developability by copolymerizing a monomer having a hydroxyl group or a cyano group in the molecule instead of a carboxylic acid group such as or acrylonitrile with a monomer having an alicyclic hydrocarbon group, It was not enough.

Recently, the Journal of Photopolymer
Science and Technology, Vol. 9, 1996, p509-522 and Jo
urnal of Photopolymer Science and Technology, Vol.
As described in 10,1997, p545-550, improvement of substrate adhesion has been studied by focusing on a lactone structure such as mevalonic lactone. However, the developing property is insufficient, such as the necessity of an overcoat layer which complicates the process for securing the developing property, and the substrate adhesion is also insufficient.

In addition, Japanese Patent Application Laid-Open No. 8-259626 and Jour
nal of Photopolymer Science and Technology, Vol. 9,
1996, p377-385, Journal of Photopolymer Science a
In ndTechnology, Vol. 9, 1996, p447-456, a monomer having a carboxylic acid group and an alicyclic hydrocarbon moiety in one molecule at the same time has been studied, and dry etching resistance, developability, and substrate adhesion have been studied. However, problems such as lack of substrate adhesion and lack of suitability for a standard developer due to extremely high solubility in the developer are encountered. Journal of Photo
polymer Science and Technology, Vol.10, 1997, p561
Although improvements have been made by copolymerizing an alicyclic hydrocarbon monomer having an alcoholic hydroxyl group as described in US Pat. No. -570, it has not yet reached a satisfactory level.

On the other hand, in addition to the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain has also been studied. I have. However, this system also has the above problem, and improvement by a similar approach is being studied. For example, Journal of Photopoly
mer Science and Technology, Vol.10, 1997, p529-534
And Journal of Photopolymer Science and Technology,
In Vol. 10, 1997, p521-528, the introduction of hydroxyl groups into the norbornene polymer main chain is studied from the viewpoint of imparting substrate adhesion. However, satisfactory results have not been obtained in both the developability and the substrate adhesion. Also, SPIE, Vol. 3049, pp. 92-105 (1988) describes a polymer obtained by ring-opening polymerization of a norbornene ring or a polymer having a norbornene ring in its main chain and having a carboxyl group and a t-butyl ester group. Compositions containing coalescence are disclosed. However, this technique also has a disadvantage that neither the substrate adhesion nor the suitability for a standard developer is practically sufficient.

Further, EP-A-789278 A2 discloses a polymer obtained by ring-opening polymerization of a norbornene ring or a polymer having a norbornene ring in a main chain and containing a resin containing an acid-decomposable group and a carboxyl group. Compositions are disclosed. WO 97/33198 discloses a photoresist composition containing a resin obtained by polymerizing a monomer having a norbornene ring having an acid-decomposable group. However, these techniques have a new disadvantage that the number of development defects increases and cracking occurs.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide dry etching resistance by solving the problem of the above-mentioned technology for improving the performance of microphotofabrication using far ultraviolet light, particularly excimer laser light. To overcome the disadvantages caused by the introduction of alicyclic hydrocarbon sites for the purpose of
That is, the standard developer (2.
An object of the present invention is to provide a resist composition which is excellent in suitability and substrate adhesion, and satisfies necessary characteristics such as sensitivity and pattern profile. Among them, the object of the present invention is suitable for an ArF excimer laser light source, the dry etching resistance is at a sufficient level, it has the suitability for a standard developing solution, the substrate has excellent adhesiveness, and further, development defects and cracking It is an object of the present invention to provide a positive photoresist composition for deep ultraviolet exposure, which can prevent generation and has an excellent resist pattern profile.

[0014]

Means for Solving the Problems The present inventors diligently studied constituent materials of a resist composition in a positive-type chemical amplification system and found that a resin containing a polymer having a specific structure as a constituent unit and a photoacid The inventors have found that the object can be achieved by a combination of generators, and have reached the present invention. That is, the above object is achieved by a method having the following configuration.

(1) A positive-working photoresist composition for deep-ultraviolet light exposure comprising a resin which decomposes under the action of an acid to increase its solubility in alkali and a compound which generates an acid upon irradiation with actinic rays or radiation. Wherein the resin which decomposes to increase the solubility in alkali by the action of the above contains a polymer containing a repeating unit represented by the following general formula [I] or a repeating unit represented by the following general formula [II] Positive photoresist composition for deep ultraviolet exposure.

[0016]

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Where R₁~ R₁₆It may be the same or different
A hydrogen atom, an alkyl group which may have a substituent,
Halogen atom, cyano group, -COOH group, -CO-O-
R₃₁(R₃₁Represents an alkyl group or a cyclic alkyl group),
A group decomposed by the action of an acid, -C (= O) -O-A-R
₁₈Or -C (= O) -X_Two-AR₁₈Where R
₁~ R₈Or R₉~ R₁₆At least one of them is acid
Is a group that decomposes by use, and₁~ R₈Or R₉~
R₁₆At least one of which is -C (= O) -X _Two-A-
R₁₈M / n; 1/9 to 9/1 m + n, p + q; 10 to 100 p, q;_TwoA sulfur atom, -NH-, -NHSO_Two-, -NHS
O_TwoA divalent linking group selected from NH-, R₁₈A hydrogen atom, an alkyl group, a cyclic alkyl group, -CO
OH, -CN, a hydroxyl group, an optionally substituted
Coxy group, -CO-NH-R₃₀, -CO-NH-SO_Two
-R₃₀Or -COOR₃₅ R₃₀An alkyl group which may have a substituent,
A cyclic alkyl group which may have R₃₅An alkyl group which may have a substituent,
A cyclic alkyl group which may have, or -Y (Y is the following
Is a group shown in

[0018]

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R _{19 to} R ₂₆ : hydrogen atom, alkyl group which may have a substituent, A: single bond, alkylene group, substituted alkylene group, ether group, thioether group, carbonyl group, ester group, amide group , A sulfonamide group, a urethane group, or a urea group alone or in combination of two or more groups. a, b; 1 or 2

(2) A positive photoresist composition for deep ultraviolet exposure comprising a resin which decomposes under the action of an acid to increase its solubility in alkali and a compound which generates an acid upon irradiation with actinic rays or radiation. Wherein the resin which decomposes to increase the solubility in alkali by the action of the above contains a polymer containing a repeating unit represented by the following general formula [I] or a repeating unit represented by the following general formula [II] Positive photoresist composition for deep ultraviolet exposure.

[0021]

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Where R₁~ R₁₆It may be the same or different
A hydrogen atom, an alkyl group which may have a substituent,
Halogen atom, cyano group, -COOH group, -CO-O-
R₃₁(R₃₁Represents an alkyl group or a cyclic alkyl group),
-C (= O) -X₁-AR ₁₈Decomposes by the action of acid
Group or -C (= O) -OC (R₃₂) (R₃₃) -R ₃₄
Where R₁~ R₈Or R₉~ R₁₆Less of
One is a group that decomposes under the action of an acid, and₁
~ R₈Or R₉~ R₁₆At least one of them is -C (=
O) -OC (R₃₂) (R₃₃) -R₃₄M / n; 1/9 to 9/1 m + n, p + q; 10 to 100 p, q;₁An oxygen atom, a sulfur atom, -NH-, -NHSO
_Two-, -NHSO_TwoA divalent linking group selected from NH-, R₁₈A hydrogen atom, an alkyl group, a cyclic alkyl group, -CO
OH, -CN, a hydroxyl group, an optionally substituted alkoxy group, -CO-NH
-R₃₀, -CO-NH-SO_Two-R₃₀Or -COOR
₃₅ R₃₀An alkyl group which may have a substituent,
A cyclic alkyl group which may have R₃₂, R₃₃A hydrogen atom, which may be the same or different,
A halogen atom, an optionally substituted alkyl group R₃₄A hydrogen atom, -COOH, -COOR₃₅, -CN,
-CO-NH-R₃₅, -CO-NH-SO_Two-R₃₅,
A alkyl group, or a hydroxyl group, an alkoxy group, -COOH,
-COOR₃₅, -CN, -CO-NH-R₃₅, -CO-
NH-SO_Two-R_{Three Five}A containing at least one group of
Rualkyl group, R₃₅An alkyl group which may have a substituent,
A cyclic alkyl group which may have, or -Y Y is a group shown below.

[0023]

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R _{19 to} R ₂₆ : hydrogen atom, alkyl group which may have a substituent, a, b; 1 or 2

In the present invention, the resin used in the positive-type chemically amplified resist composition contains an acid-decomposable group and a group having a specific structure, and further specifies the skeleton structure, thereby achieving the above object. Was achieved.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. First, it is decomposed by the action of acid,
Contains a resin having increased solubility in an alkali developer, that is, a polymer containing a monomer repeating unit represented by the general formula [I] or a monomer repeating unit represented by the general formula [II] The resin will be described. In the general formula [I] or the general formula [II], the group decomposed by the action of an acid in R _{1 to} R ₁₆ (also referred to as an acid-decomposable group) includes —C (＝ O) —O—R ₀ . The groups represented are mentioned. Here, R ₀ is t
Tertiary alkyl groups such as -butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-alkoxyethyl group such as 1-isobutoxyethyl group and 1-cyclohexyloxyethyl group , An alkoxymethyl group such as 1-methoxymethyl group and 1-ethoxymethyl group, a trialkylsilyl group such as a tetrahydropyranyl group, a tetrahydrofuranyl group, a trimethylsilyl group, a t-butyldimethylsilyl group and a diisopropylmethylsilyl group; An oxocyclohexyl group can be exemplified. R _{1 to} R ₁₆ , R _{18 to} R ₂₆ , R ₃₀ , R ₃₁ , R ₃₂ ,
As the alkyl group for R ₃₃ , R ₃₄ and R ₃₅ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. 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.

As the cyclic alkyl group for R ₁₈ , R ₃₀ , R ₃₁ and R ₃₅ , a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-
Examples thereof include a 2-adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. .

Examples of the alkoxy group for R ₁₈ and R ₃₄ 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-mentioned alkyl group, cyclic alkyl 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 and the like. 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.

Examples of the alkylene group and substituted alkylene group in A include the following groups. -[C (R _a ) (R _b )] _r-wherein R _a and R _b each represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy 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 selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Represents a substituent. 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. r represents an integer of 1 to 10. In the above general formula [I] or general formula [II], examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

In the above formula (I) or (II)
In the general formula [I], R₁~ R₈At least one of
Or R in general formula [II]₉~ R₁₆Less of
One is -C (= O) -X_Two-AR₁₈Or -C
(= O) -OC (R₃₂) (R₃₃) -R₃₄And
R in the general formula [I]₁~ R₈At least one of
Or R in general formula [II]₉~ R₁₆At least one of
One represents an acid-decomposable group. The above general formula [I] or general formula
In [II], the acid-decomposable group and —C (＝ O) —X
_Two-AR₁₈Or -C (= O) -OC (R₃₂)
(R₃₃) -R₃₄May be included in the same repeating unit
Alternatively, they may be included in separate repeating units. −C (=
O) -X_Two-AR₁₈As a preferred group of the group represented by
Include the groups shown below. -C (= O) -X_Two-[C (R_a) (R_b)]_s-R₁₈ -C (= O) -X_Two-[C (R_a) (R_b)]_s−C (=
O) -X₁-[C (R _a) (R_b)]_s-R₁₈ -C (= O) -X_Two-[C (R_a) (R_b)]_s-O-
[C (R_a) (R_b)]_s-R₁₈ Further, preferred groups of these groups include the following groups.
I can do it. -C (= O) -X_Two-[C (R_a) (R_b)]
_s-R₁₈Is -C (= O) -NH-R (where R is
Represents an alkyl group or a cyclic alkyl group. ) -C (= O) -NH- [C (R_a) (R_b)]_s-COO
H—C (＝ O) —NH— [C (R_a) (R_b)]_s-COO
R₃₅ -C (= O) -NH- [C (R_a) (R_b)]_s-CN-C (= O) -NH- [C (R_a) (R_b)]_s-OH-C (= O) -NH- [C (R_a) (R_b)]_s-OR₃₀ -C (= O) -NH- [C (R_a) (R_b)]_s-CO-
NH-R₃₀ -C (= O) -NH- [C (R_a) (R_b)]_s-CO-
NH-SO_Two-R₃₀ —C (＝ O) —NH—SO_Two-R₃₀ —C (＝ O) —NH—SO_Two-NH-R₃₀ -C (= O) -SR₃₀ -C (= O) -S- [C (R_a) (R_b)]_s-COOH-C (= O) -S- [C (R_a) (R_b)]_s-COOR
₃₅ -C (= O) -S- [C (R_a) (R_b)]_s-CN-C (= O) -S- [C (R_a) (R_b)]_s-CO-N
HR₃₀ -C (= O) -S- [C (R_a) (R_b)]_s-CO-N
H-SO_Two-R₃₀ Is preferred.

-C (= O) -X_Two-[C (R_a)
(R_b)]_s-C (= O) -X₁-[C (R _a)
(R_b)]_s-R₁₈Represents -C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -OR₃₅ -C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -O- [C (R_a) (R_b)]_s-COOH-C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -O- [C (R_a) (R_b)]_s-COOR₃₅ -C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -O- [C (R_a) (R_b)]_s-CN-C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -NH-R₃₀ -C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -NH- [C (R _a) (R_b)]_s-COOH-C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -NH- [C (R _a) (R_b)]_s-COOR₃₀ -C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -NH- [C (R _a) (R_b)]_s-CN-C (= O) -NH- [C (R_a) (R_b)]_s−C (=
O) -NH-SO_Two-R₃₀ Is preferred.

-C (= O) -X _2- [C (R _a )
(R _b )] _s -O- [C (R _a ) (R _b )] _s -R ₁₈ includes -C (＝ O) -NH- [C (R _a ) (R _b )] _s -O -R
₃₀ -C (= O) -NH- [C (R _a ) (R _b )] _s -O-
[C (R _a ) (R _b )] _s -COOH-C (= O) -NH- [C (R _a ) (R _b )] _s -O-
[C (R _a ) (R _b )] _s -COOR ₃₅ -C (= O) -NH- [C (R _a ) (R _b )] _s -O-
[C (R _a ) (R _b )] _s -CN-C (= O) -NH- [C (R _a ) (R _b )] _s -O-
[C (R _a ) (R _b )] _s -CO-NH-R ₃₀ -C (= O) -NH- [C (R _a ) (R _b )] _s -O-
[C (R _a ) (R _b )] _s -CO-NH-SO ₂ -R ₃₀ is preferred.

-C (= O) -OC (R₃₂) (R₃₃)-
R₃₄Preferred examples of the group represented by are shown below.
Groups. -C (= O) -OC (R₃₂) (R₃₃) -COOH-C (= O) -OC (R₃₂) (R₃₃) -COOR₃₅ -C (= O) -OC (R₃₂) (R₃₃) -CN-C (= O) -OC (R₃₂) (R₃₃) -CO-NH-
R₃₀ -C (= O) -OC (R₃₂) (R₃₃) -CO-NH-
SO_Two-R₃₀ -C (= O) -OC (R₃₂) (R₃₃)-[C (R_a)
(R_b)]_s-COOH-C (= O) -OC (R₃₂) (R₃₃)-[C (R_a)
(R_b)]_s-COOR ₃₅ -C (= O) -OC (R₃₂) (R₃₃)-[C (R_a)
(R_b)]_s-CN-C (= O) -OC (R₃₂) (R₃₃)-[C (R_a)
(R_b)]_s-CO-NH-R₃₀ -C (= O) -OC (R₃₂) (R₃₃)-[C (R_a)
(R_b)]_s-CO-NH-SO_Two-R₃₀ In the above, s represents an integer of 0 to 10.

Hereinafter, in a polymer containing a repeating unit represented by the general formula [I] or the general formula [II], -C (=
O) Specific examples of the repeating unit containing a -X-A-R _18. However, the content of the present invention is not limited to these.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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Hereinafter, in a polymer containing a repeating unit represented by the general formula [I] or [II], -C (=
_{O) -O-C (R 32} ) ( Specific examples of the repeating units containing R ₃₃₎ -R _34. However, the content of the present invention is not limited to these.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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The resin according to the present invention has the general formula [I]
Alternatively, in addition to containing one or more kinds of the repeating unit represented by the general formula [II], dry etching resistance, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution, which is a general requirement of a resist, heat resistance It can be used as a copolymer with various monomer repeating units for the purpose of adjusting properties, sensitivity and the like. Preferable examples of the copolymer component include repeating units represented by the following general formula [III] or [IV] (ring-opening polymerization type), or the following general formulas [V] or [VI] (non-ring-opening polymerization type). Can be.

[0075]

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Here, Z is an oxygen atom, -NH-, -N
_{(-R 30) -, - N} (-OSO 2 R 30) - represents, R ₃₀
Has the same meaning as described above. In the above, -C (= O) -X
₂ -A-R ₁₈ or -C (= O) -O-C (R 32)
(R ₃₃₎ showed Specific examples of the repeating unit containing a -R _34, can be copolymerizable therewith, formulas other than those [I]
Alternatively, specific examples of the units constituting the repeating unit represented by the general formula [II], and specific examples of the repeating units represented by the above general formulas [III] to [VI] are shown below. Is not limited to these. Note that -C (=
O) Specific examples of the repeating unit represented by the general formula [I] or [II], which can be copolymerized with the repeating unit containing -X ₂ -A-R ₁₈ , are [Ia-1] to [Ia-1] Ia
-72], represented by [IIa-1] to [IIa-71],
Note -C (= O) -O-C (R 32) (R 33) copolymerizable with the repeating units containing -R _34, repeating of general formula other than those [I] or formula [II] Specific examples of the unit are [Ia'-1] to [Ia'-91], [II
a'-1] to [IIa'-91].

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[0090]

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[0100]

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[0101]

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[0102]

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[0103]

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[0107]

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[0115]

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In the above resin of the present invention, the molar ratio of each repeating unit is determined by the dry etching resistance of the resist, the suitability for a standard developing solution, the substrate adhesion, the resist profile, and the resolution, heat resistance, It is set as appropriate to adjust properties, sensitivity, and the like.

However, in the resin of the present invention, the content of the repeating unit represented by the general formula [I] or the general formula [II] is at least 10 mol% in all monomer repeating units.
Preferably 20 mol% or more, more preferably 30 mol%
That is all. In the resin of the present invention, the content of the repeating unit containing an acid-decomposable group is from 10 to 90 mol%, preferably from 12 to 85 mol%, of all monomer repeating units.
Mol%, more preferably 15 to 80 mol%. When the content of the repeating unit containing an acid-decomposable group is less than 10 mol%, a problem tends to occur in image formation. Further, in the resin in the present _{invention, -C (= O) -X 2} -A-R 18 or -C (= O) -O-C (R 32) of the repeating units containing (R ₃₃₎ -R ₃₄ The content is 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, based on all the monomer repeating units. If the content of the repeating unit containing the above group is less than 10 mol%, the effect of the present invention tends to decrease. In the resin of the present invention, the general formula [III] or [IV], or the general formula [V]
Alternatively, the content of the repeating unit represented by [VI] is 0 to 50 mol%, preferably 0 to 40 mol%, and more preferably 0 to 30 mol%, based on all monomer repeating units. When the content of the repeating unit containing the above group exceeds 50 mol%, the effect of the present invention tends to decrease.

The resin of the present invention preferably further contains a carboxyl group for imparting adhesion. The content of the carboxyl group in the resin is 0.05 to 2.0 meq / g, preferably 0.1 to 1.8 meq / g.
g, more preferably 0.3 to 1.5 meq / g.

Such a resin can be further copolymerized as a repeating unit with the following monomers as long as the effects of the present invention can be effectively obtained, but are not limited thereto. . Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film-forming property (glass transition point), (3) alkali developability, (4)
Fine adjustment of film loss (hydrophilic / hydrophobic, alkali-soluble group selection), (5) adhesiveness of the unexposed portion to the substrate, and (6) dry etching resistance can be performed.

Examples of such a comonomer include acrylic esters, methacrylic esters,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, 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, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.), N-
Hydroxyethyl-N-methylacrylamide, N-2
-Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as 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 (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples include maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile, and the like.

In addition, any addition-polymerizable unsaturated compound copolymerizable with the repeating unit represented by the general formula [I] or [II] may be used. The content of the repeating unit based on the further monomer as described above in the resin is represented by the general formula [I]
Alternatively, it is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%, based on the total number of moles of the repeating structural units represented by the general formula [II]. If it exceeds 99 mol%, the effect of the present invention is not sufficiently exhibited, so that it is not preferable.

The weight average molecular weight of the resin according to the present invention is preferably from 2,000 to 200,000. When the weight average molecular weight is less than 2,000, heat resistance and dry etching resistance are deteriorated.
If it exceeds 000, a very unfavorable result such as deterioration of the developability and an extremely high viscosity will result in deterioration of the film-forming property.

The resin used in the present invention, which is decomposed by the action of an acid and has increased solubility in alkali, can be obtained by polymerizing a monomer having a norbornene skeleton and, if necessary, conducting a polymer reaction. The polymerization reaction can be obtained by radical polymerization using a general radical initiator such as an azo initiator, but more preferably, non-ring-opening polymerization using a Pd catalyst or the like or coordination polymerization such as a transition metal complex. It is synthesized by ring-opening polymerization using a catalyst. The resin obtained by the ring-opening polymerization is preferably reduced and used from the viewpoint of stability and optical absorption. A resin having a repeating unit represented by the general formula [I] is obtained by ring-opening polymerization, and a resin having a repeating unit represented by the general formula [II] is obtained by non-ring-opening polymerization.

In the resin of the present invention, which is decomposed by an acid and has increased solubility in an alkaline developer, the resin represented by the general formula [I]
Or a repeating structural unit represented by the general formula [II], characterized in that each contains one or more kinds, whereby the substrate adhesion, standard developer suitability, sensitivity, etc. Which can prevent development defects and cracking from occurring, and provide a positive photoresist composition for deep ultraviolet exposure that has an excellent pattern profile and is suitable for production. That is, the resin according to the present invention has a specific main chain skeleton, and further contains a specific group, whereby the substrate adhesion is improved, there is no development residue, and the light absorption in the deep ultraviolet region is strong. Since there is substantially no group in the main chain or side chain, the irradiation light sufficiently spreads near the substrate surface of the coating film, which results in high sensitivity and an excellent pattern profile. In addition, development defects and cracking can be prevented, and the obtained pattern profile is more excellent. Low transmission density is a necessary condition, which does not immediately lead to excellent resist properties, and it is needless to say that other influencing factors are involved, but the resin according to the present invention satisfies such requirements. Meets

The positive photoresist composition of the present invention comprises
It mainly contains the resin as described above and a photoacid generator. The addition amount of the above resin in the entire composition is preferably 40 to 99% by weight, more preferably 50 to 99% by weight, based on the total resist solids.
~ 97% by weight.

Next, the photoacid generator in the positive photoresist composition of the present invention will be described. The photoacid generator needs to satisfy two properties. That is,
(1) transparency to exposure light (provided that there is no light bleaching property); and (2) sufficient photodegradability to ensure resist sensitivity. However, at present, there is no clear guideline for molecular design that satisfies such contradictory requirements. For example, the following examples can be given. That is, JP-A-7-25846 and JP-A-7-2823
7, JP-A-7-92675, JP-A-8-2
Aliphatic alkulfonium salts having a 2-oxocyclohexyl group described in JP-A-7102, and N-
Hydroxysuccinimide sulfonates and the like can be mentioned. Furthermore, J. Photopolym. Sci. Techn
ol., Vol 7, No. 3, p 423 (1994) and the like, and sulfonium salts represented by the following general formula (VI), disulfones represented by the following general formula (VII), and the following general formula The compound represented by (VIII) can be mentioned.

[0136]

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Here, R _{12 to} R ₁₅ each represent an alkyl group or a cyclic alkyl group. These may be the same or different from each other. Further, N-hydroxymaleimide sulphonates represented by the following general formula (IX) are also suitable.

[0138]

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Here, R ₁₆ and R ₁₇ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group. R ₁₆ and R ₁₇ may be bonded via an alkylene group to form a ring. R ₁₈ represents an alkyl group, a perfluoroalkyl group, a cycloalkyl group or a substituted camphor. Such N-hydroxymaleimide sulphonates are particularly preferred in terms of photosensitivity.

The alkyl group having 1 to 6 carbon atoms for R ₁₆ and R ₁₇ in the general formula (IX) includes a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group,
An n-hexyl group can be mentioned. Among them, preferred are a methyl group, an ethyl group and a propyl group, and a methyl group and an ethyl group are more preferred. Examples of the cycloalkyl group having 6 or less carbon atoms include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Preferably, they are a cyclopentyl group and a cyclohexyl group. R ₁₆ ,
Examples of the case where R ₁₇ forms a ring with each other by an alkylene chain include a case where a cyclohexyl group, a norbornyl group, and a tricyclodecanyl group are formed.

The alkyl group represented by R ₁₈ is a straight-chain alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group.
Alkyl groups, isopropyl groups, isobutyl groups, t
Examples thereof include a branched alkyl group having 1 to 20 carbon atoms such as an tert-butyl group and a neopentyl group. It is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferably 4 to 15 carbon atoms.
Linear or branched alkyl groups. Examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group and other straight-chain carbon atoms having 1 to 20 carbon atoms.
And a branched perfluoroalkyl group having 1 to 20 carbon atoms such as a perfluoroalkyl group, a heptafluoroisopropyl group, and a nonafluoro tert-butyl group. Preferably, it is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. As the cyclic alkyl group, a monocyclic cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group, a decalyl group,
Examples thereof include a plurality of cyclic alkyl groups such as a norbornyl group and a tricyclodecanyl group.

The amount of such a photoacid generator added to the composition is 0.1 to 0.1% of the total solid content of the positive photoresist composition.
To 20% by weight, more preferably 0.5 to 15% by weight.
%, More preferably 1 to 10% by weight.

In the positive photoresist composition of the present invention, the following photoacid generator may be used in addition to the above photoacid generator.

The amount of the photoacid generator which can be used in combination as described below in the composition is 2% by weight or less, more preferably 1% by weight, in the solid content of the whole positive photoresist composition.
The following is good. For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,14
Ammonium salts described in No. 0 etc., DCNecker etal, Macr
omolecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Co.
nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc., phosphonium salts, JVCrivello et al.
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201.
No., JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17,7
3 (1985), JVCrivello et al. J. Org.Chem., 43, 3055 (19
78), WRWatt et al, J. Polymer Sci., Polymer Chem. E
d., 22, 1789 (1984), JVCrivello etal, Polymer Bul
l., 14,279 (1985), JVCrivello etal, Macromorecules,
14 (5), 1141 (1981), JVCrivelloetal, J. PolymerSci.,
Polymer Chem.Ed., 17,2877 (1979), EP 370,693
No. 3,902,114, No. 233,567, No. 297,443, No.
297,442; U.S. Pat.Nos. 4,933,377; 161,811;
No. 410,201, No. 339,049, No. 4,760,013, No. 4,73
No. 4,444, No. 2,833,827, Dokoku Patent No. 2,904,626,
The sulfonium salts described in JP-A-3,604,580 and JP-A-3,604,581, etc., JVCrivello et al., Macromorecules, 10 (6), 1307
(1977), JVCrivello et al., J. PolymerSci., Polymer C
hem.Ed., 17,1047 (1979) and the like,
CSWen etal, Teh, Proc.Conf.Rad.Curing ASIA, p478 To
kyo, Oct (1988) etc., onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-160 -239736
No., JP-A-61-169835, JP-A-61-169837, JP-A-61-169837
No. 62-58241, JP-A-62-212401, JP-A-63-70243,
Organic halogen compounds described in JP-A-63-298339, etc.
Meier et al., J. Rad. Curing, 13 (4), 26 (1986), TPGillet
al, Inorg.Chem., 19, 3007 (1980), D. Astruc, Acc.
s., 19 (12), 377 (1896), and organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer
Sci., 25, 753 (1987), E. Reichmanis et al., J. Pholimer S
ci., PolymerChem. Ed., 23, 1 (1985), QQZhu et al., J. Pho
tochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedro
n Lett., (24) 2205 (1973), DHR Barton et al., J. Chem So
c., 3571 (1965), PMCollins et al., J. Chem.SoC., Perkin
I, 1695 (1975), M. Rudinsteinetal, Tetrahedron Lett.,
(17), 1445 (1975), JWWalker etal J. Am. Chem. Soc., 11
0,7170 (1988), SCBusman et al., J. Imaging Technol., 1
1 (4), 191 (1985), HMHoulihan et al, Macormolecules, 2
1,2001 (1988), PMCollins et al., J. Chem. Soc., Chem. Com
mun., 532 (1972), S. Hayase et al, Macromolecules, 18, 179.
9 (1985), E. Reichmanis et al., J. Electrochem. Soc., Soli
d State Sci.Technol., 130 (6), FMHoulihan et al, Mac
romolcules, 21, 2001 (1988), European Patent No. 0290,750, ibid.
46,083, 156,535, 271,851, 0,388,343
No. 3,901,710, U.S. Pat.No. 4,181,531, JP-A-60-198538, JP-A-53-133022, etc.
etal, Polymer Preprints Japan, 35 (8), G. Berner etal,
J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer
Preprints, Japan, 37 (3), European Patent Nos. 0199,672 and 8451
No. 5, 199,672, 044,115, 0101, 122, U.S. Patent Nos. 618,564, 4,371,605, 4,431,774
No., JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-14
Compounds that generate sulfonic acid upon photolysis, such as iminosulfonates described in JP-A-61-166.
And the disulfone compound described in JP-A-544.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Ra
pid Commun., 9,625 (1988), Y.Yamada et al., Makromol.C
hem., 152, 153, 163 (1972), JVCrivello etal, J. Polym
erSci., Polymer Chem. Ed., 17,3845 (1979), U.S. Patent No. 3,849,137, Dokoku Patent No. 3,914,407, JP-A-63-266.
No. 53, JP-A-55-164824, JP-A-62-69263, JP-A-Showa
63-146038, JP-A-63-163452, JP-A-62-153853
And the compounds described in JP-A-63-146029 and the like can be used.

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

Among the above-mentioned compounds which can be used together and which generate an acid by being decomposed by irradiation with actinic rays or radiation, those 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 (PA)
An S-triazine derivative represented by G2).

[0148]

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

[0150]

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[0151]

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[0152]

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

[0154]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Here, preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group,
And mercapto groups and halogen atoms.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group. .

[0157] Z ^- represents a counter anion, CF ₃ SO ₃ ^-
And the like, such as perfluoroalkanesulfonic acid anions and pentafluorobenzenesulfonic acid anions. Also R
Two of ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar
² may be bonded via each single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapcz
yk etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycoke
tal, J. Org.Chem., 35, 2532, (1970), E. Goethas et al, Bu
ll.Soc.Chem.Belg., 73,546, (1964), HM Leicester,
J. Ame. Chem. Soc., 51, 3587 (1929), JVCrivello etal,
J. Polym. Chem. Ed., 18,2677 (1980), U.S. Pat.
It can be synthesized by the methods described in JP-A Nos. 8 and 4,247,473 and JP-A-53-101,331. (3) Disulfone derivatives represented by the following general formula (PAG5) or iminosulfonate derivatives represented by the following general formula (PAG6).

[0167]

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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.

[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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The positive photoresist composition is suitable for improving the alkali solubility of the system and for adjusting the glass transition temperature of the system to prevent the film from becoming brittle and from deteriorating the heat resistance. An alkali-soluble low molecular weight compound may be added. Examples of the alkali-soluble low molecular weight compound include a dialkyl sulfonamide compound, a dialkyl sulfonyl imide (—SO ₂ —NH—CO—) compound, and a dialkyl disulfonyl imide (—SO ₂ —NH
Compounds containing an acidic group in the molecule, such as —SO ₂ —) compounds, may be mentioned. The content of the alkali-soluble low molecular compound is 4 to the binder resin.
The content is preferably 0% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less.

The composition according to the present invention may be used after being dissolved in a specific solvent. As such a solvent, any solvent may be used as long as the solid components are sufficiently dissolved and the solution is an organic solvent capable of forming a uniform coating film by a method such as a spin coating method. In addition, 2
More than one kind may be mixed and used. Specifically, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, methyl cellosolve acetate, ethyl cellosolve acetate,
Propylene glycol monoethyl ether acetate,
Methyl lactate, ethyl lactate, 2-methoxybutyl acetate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidinone, cyclohexanone, Cyclopentanone, cyclohexanol, methyl ethyl ketone, 1,4-dioxane,
Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, 2-
Examples include heptanone, but are not limited thereto.

The positive photoresist composition of the present invention may further contain other components such as a surfactant, a dye, a stabilizer, a coating improver, and a dye, if necessary. 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 0.4 to 1.5 μm. As the exposure means, A
Preferably, the exposure wavelength is in the range of 170 to 220 nm, such as rF excimer laser stepper exposure,
Particularly preferred is an ArF excimer laser stepper.

[0177]

EXAMPLES Next, 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: (Ring-Opening Polymerization) (1) Synthesis of Resin A (Repeating Unit [I-1], [I-
13] [I-22], [I-31]; Ring-opening polymerization) 5-norbornene-2,3-dicarboxylic anhydride and a reaction product thereof with cyclopentadiene (5 by mole ratio)
0/50) in dry chlorobenzene.
The solution was added to a dry chlorobenzene solution of 0.1 mol% of tungsten hexachloride and 0.3 mol% of triethylamine, and stirred.
The mixture was stirred at 30 ° C. for 18 hours and reprecipitated in methanol to take out a white acid anhydride resin. Next, this was reacted with glycine to open the acid anhydride site, and then reacted with t-butyl alcohol in the presence of dicyclohexylcarbodiimide to obtain the desired resin A. The repeating units [I-1], [I-13], [I-22], and [I-
31] was determined by NMR measurement to be 20/30/20/3.
It was 0. After GPC measurement of the obtained resin A,
The weight average molecular weight in terms of standard polyhydroxystyrene was 16,400. (2) Synthesis of Resins B-J and Resins A'-I '
Resins B to J and Resins A ′ to having the described repeating units
I 'was synthesized.

[0178]

[Table 1]

[0179]

[Table 2]

(3) Synthesis of Comparative Resin R-1 Resin R-1 having the following structure was synthesized according to the method described in SPIE, 1997, Vol. 3049, 92-103. The weight average molecular weight of the resin R-1 in terms of standard polyhydroxystyrene is 18,20.
It was 0.

[0181]

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Synthesis Example: (Non-Ring-Opening Polymerization) (4) Synthesis of Resin K (Repeating Units [II-1], [II-
13], [II-69]) Di of 80 g of 5-norbornene-2,3-dicarboxylic anhydride, 2-cyanoethoxycarbonylmethylacrylamide and dicyclopentadiene
Els-Alder reaction 20 g and literature Journal of O
5 g of the catalyst [Pd (CH ₃ CN) ₄ ] (BF ₄ ) ₂ synthesized by the method described in rganometallic Chemistry, 1988, vol. 358, 567-588 was dissolved in nitromethane and stirred at room temperature for 6 hours. After concentrating the obtained reaction solution, the obtained solid was washed with acetonitrile / water solvent to obtain a white resin. Further, this resin was reacted with glycine to open the acid anhydride site, and then reacted with t-butanol in the presence of dicyclohexylcarbodiimide to obtain the desired resin K. The composition ratio of the repeating units [II-1], [II-13], and [II-69] in the resin K was 20/60/20 / from NMR measurement. GPC measurement of the obtained resin K showed that the weight average molecular weight in terms of standard polyhydroxystyrene was 8,400. (5) Synthesis of Resins L to R and Resins J 'to P' Resins L to R and Resins J 'to P' shown in Tables 3 and 4 below were synthesized by the same polymerization method as in (4) above.

[0183]

[Table 3]

[0184]

[Table 4]

(6) Synthesis of Comparative Resin R-2 According to the method described in SPIE, 1997, Vol. 3049, 92-103,
Polymerization was performed using [Pd (CH ₃ CN) ₄ ] (BF ₄ ) ₂ as a catalyst.
The same treatment as in Synthesis Example (4) was performed to obtain a resin R-2 as a white powder. The weight average molecular weight of the resin R-2 in terms of standard polyhydroxystyrene was 9,900.

[0186]

Embedded image

(7) Synthesis of Comparative Resin R-3 Resin R-3 having the following structure was synthesized according to the method described in Synthesis Example 9 of EP-A-789278A2.
The weight average molecular weight of the resin R-3 in terms of standard polyhydroxystyrene was 32,000.

[0188]

Embedded image

(8) Synthesis of Comparative Resin R-4 Bicyclo [2.2.1] hept- was prepared in the same manner as described in Example 21 of WO 97/33198.
T- of 5-ene-2-methyl acetate and norbornene
Butyl ester copolymer (Mw; 52000, Wn;
21000).

Examples and Comparative Examples 1.2 g of each resin synthesized in the above synthesis example and 0.25 g of triphenylsulfonium triflate were added to propylene glycol monoethyl ether acetate at a solid content of 14% by weight. After dissolving, filtration with a 0.1 μm micro filter,
A positive photoresist composition solution was prepared.

(Evaluation Test) The obtained positive photoresist composition solution was applied on a silicon wafer by using a spin coater, dried at 120 ° C. for 90 seconds, and about 0.5 μm
Was prepared and exposed to an ArF excimer laser (193 nm). A heat treatment after the exposure was performed at 130 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile.

[Pattern profile]: The resist pattern profile obtained above was observed with a scanning electron microscope and evaluated with a 0.25 micron profile. A rectangular one was marked with a circle, a taper, a T-top, and a round top. What showed the shape was evaluated as x.

[Substrate adhesion] (minimum line width of remaining fine line):
The resist pattern profile obtained above was observed with a scanning electron microscope, and evaluated based on the line width of the remaining thinnest line. A pattern having higher adhesion has a pattern with a finer line width remaining, while a pattern having lower adhesion cannot be adhered to a substrate interface with a smaller line width, and the pattern is peeled off.

[Suitability of standard developer]: Evaluated by the amount of film loss in the unexposed portion of the resist pattern profile obtained as described above. Was evaluated.

[Number of development defects]: Bare S of 6 inches
Each resist film was applied to a thickness of 0.5 μm on the i-substrate and dried at 130 ° C. for 60 seconds on a vacuum suction hot plate. Next, a 0.35 μm contact hole pattern (Hole)
Nik through a test mask with a duty ratio = 1: 3)
After exposure with the on-stepper NSR-1505EX, post-exposure heating was performed at 130 ° C. for 90 seconds. Subsequently, after paddle development with 2.38% TMAH (aqueous solution of tetramethylammonium hydroxide) for 60 seconds, 30% with pure water.
Washed with water for 2 seconds and spin dried. The sample thus obtained was used for KLA-2112 manufactured by KLA-Tencor Corporation.
The number of development defects was measured by a machine, and the obtained primary data value was defined as the number of development defects.

[Number of cracking]: 4 inch Bare
Each resist film is applied to a thickness of 0.5 μm on a Si substrate,
Dried at 30 ° C. for 90 seconds. Then stepper NSR-
Using a 1505EX, a large 1 mm × 3 mm rectangular pattern is exposed at a dose of ² mJ / cm ² to 100 mJ / cm 2.
Exposure was performed for 50 shots in steps of mJ / cm ² , and post-exposure heating was performed at 130 ° C. for 90 seconds. Then 2.38% TMA
After developing with H, the pattern for 5 shots counted from the pattern irradiated with light of the exposure amount at which the coating film was first melted in the exposed portion was observed with an optical microscope, and the number of cracks was counted. Tables 5 and 6 show the evaluation results.

[0197]

[Table 5]

[0198]

[Table 6]

As is clear from the results in Tables 5 and 6, all of the comparative examples have problems in terms of substrate adhesion, standard developer suitability, pattern profile, number of development defects, and number of cracks. On the other hand, all of the positive photoresist compositions of the present invention are at a satisfactory level. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure.

[0200]

The present invention is particularly suitable for light in the wavelength region of 170 nm to 220 nm, has excellent standard developer characteristics, excellent substrate adhesion, high sensitivity, and further reduces the number of development defects and the number of cracking. Is realized, and a positive photoresist composition which can obtain a good resist pattern profile can be provided.

Claims (2)

[Claims] Claims 1. An acid which decomposes under the action of an acid to alkali
Resin that increases solubility and irradiation with actinic rays or radiation
For deep ultraviolet exposure containing a compound that generates an acid
In a di-type photoresist composition, the acid
Resin that decomposes and increases solubility in alkali
The repeating unit represented by the general formula [I] or the following general formula
Contains a polymer containing a repeating unit represented by (II)
Positive photoresist for deep ultraviolet exposure
Composition. Embedded imageWhere R₁~ R₁₆A hydrogen source, which may be the same or different
, An alkyl group which may have a substituent, a halogen atom
, Cyano group, -COOH group, -CO-OR₃₁(R₃₁
Represents an alkyl group or a cyclic alkyl group).
A more decomposable group, -C (= O) -O-A-R₁₈Or -C
(= O) -X_Two-AR₁₈Where R₁~ R₈or
Is R₉~ R₁₆At least one of them is separated by the action of an acid.
Group to be understood and R₁~ R₈Or R₉~ R₁₆Out of
At least one is -C (= O) -X _Two-AR₁₈M / n; 1/9 to 9/1 m + n, p + q; 10 to 100 p, q;_TwoA sulfur atom, -NH-, -NHSO_Two-, -NHS
O_TwoA divalent linking group selected from NH-, R₁₈A hydrogen atom, an alkyl group, a cyclic alkyl group, -CO
OH, -CN, a hydroxyl group, an optionally substituted
Coxy group, -CO-NH-R₃₀, -CO-NH-SO_Two
-R₃₀Or -COOR₃₅ R₃₀An alkyl group which may have a substituent,
A cyclic alkyl group which may have R₃₅An alkyl group which may have a substituent,
A cyclic alkyl group which may have, or -Y (Y is the following
Is a group shown in the formula)R₁₉~ R₂₆A hydrogen atom or an optionally substituted alkyl group;
A, single bond, alkylene group, substituted alkylene group, ether
Group, thioether group, carbonyl group, ester group,
Mido group, sulfonamide group, urethane group, or urea
Singly or two or more groups selected from the group consisting of groups
Represents a combination. a, b; 1 or 2 2. Decomposition by the action of an acid to alkali
Resin that increases solubility and irradiation with actinic rays or radiation
For deep ultraviolet exposure containing a compound that generates an acid
In a di-type photoresist composition, the acid
Resin that decomposes and increases solubility in alkali
The repeating unit represented by the general formula [I] or the following general formula
Contains a polymer containing a repeating unit represented by (II)
Positive photoresist for deep ultraviolet exposure
Composition. Embedded imageWhere R₁~ R₁₆A hydrogen source, which may be the same or different
, An alkyl group which may have a substituent, a halogen atom
, Cyano group, -COOH group, -CO-OR₃₁(R₃₁
Represents an alkyl group or a cyclic alkyl group), -C (=
O) -X₁-AR ₁₈, A group decomposed by the action of an acid or
-C (= O) -OC (R₃₂) (R₃₃) -R ₃₄Represents
Where R₁~ R₈Or R₉~ R₁₆At least one of
Is a group that decomposes under the action of an acid;₁~ R₈or
Is R₉~ R₁₆At least one of which is -C (= O) -O
-C (R₃₂) (R₃₃) -R₃₄M / n; 1/9 to 9/1 m + n, p + q; 10 to 100 p, q;₁An oxygen atom, a sulfur atom, -NH-, -NHSO
_Two-, -NHSO_TwoA divalent linking group selected from NH-, R₁₈A hydrogen atom, an alkyl group, a cyclic alkyl group, -CO
OH, -CN, a hydroxyl group, an optionally substituted
Coxy group, -CO-NH-R₃₀, -CO-NH-SO_Two
-R₃₀Or -COOR₃₅ R₃₀An alkyl group which may have a substituent,
A cyclic alkyl group which may have R₃₂, R₃₃A hydrogen atom, which may be the same or different,
A halogen atom, an optionally substituted alkyl group R₃₄A hydrogen atom, -COOH, -COOR₃₅, -CN,
-CO-NH-R₃₅, -CO-NH-SO_Two-R₃₅,
A alkyl group, or a hydroxyl group, an alkoxy group, -COOH,
-COOR₃₅, -CN, -CO-NH-R₃₅, -CO-
NH-SO_Two-R_{Three Five}A containing at least one group of
Rualkyl group, R₃₅An alkyl group which may have a substituent,
The cyclic alkyl group which may be contained, or -Y Y is a group represented by the following.R₁₉~ R₂₆A hydrogen atom or an optionally substituted alkyl group;
A or b; 1 or 2