JP2002174903A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photoresist composition having excellent resolution and edge roughness of line pattern and hardly causing developing defect in the manufacture of a semiconductor device. SOLUTION: The photoresist composition contains a resin (A) which contains a repeating unit having a specific partial structural and a repeating unit expressed by a specific structure and the solubility of which in an alkali developer increases by the action of an acid and a compound (B) generating the acid by active ray or radioactive ray irradiation.

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 used for manufacturing semiconductor integrated circuit elements, masks for manufacturing integrated circuits, printed wiring boards, liquid crystal panels, and the like.

[0002]

2. Description of the Related Art As a pattern forming method for manufacturing electronic components such as a semiconductor device, a magnetic bubble memory, and an integrated circuit, a method utilizing a photoresist which is sensitive to ultraviolet light or visible light has been widely used. Have been. There are two types of photoresist: a negative type, in which the irradiated part is insoluble in the developer by light irradiation, and a positive type, in which the exposed part is solubilized.The negative type has higher sensitivity than the positive type and is necessary for wet etching. Until recently, photoresists occupied the mainstream because of their excellent adhesion to substrates and chemical resistance.

However, with the increase in density and integration of semiconductor devices and the like, the line width and spacing of patterns have become extremely small.
In addition, since dry etching has been adopted for etching the substrate, photoresists have been desired to have high resolution and high dry etching resistance,
At present, positive photoresists occupy the majority. In particular, among positive photoresists, sensitivity,
Because of its excellent resolution and dry etching resistance, for example, JC Strieta, Kodak Microelectronics Seminar Proceedings, p. 116 (1976) (JC Strieter, Kodak Micro)
Electronics Seminar Proceedings, 116 (1976)), etc. The alkali development type positive photoresist based on alkali-soluble novolak resin is the mainstream of the current process.

However, in recent years, multifunctional electronic devices have been
As the sophistication increases, there is a strong demand for finer patterns to achieve higher densities and higher integration. That is, since the vertical dimension of the integrated circuit is not much reduced as compared with the horizontal dimension of the integrated circuit, the ratio of the height to the width of the resist pattern has to be increased. For this reason, it has become more difficult to suppress the dimensional change of the resist pattern on a wafer having a complicated step structure as the pattern becomes finer. further,
Problems have also arisen with various types of exposure methods as the minimum dimensions are reduced. For example, in light exposure, the interference effect of reflected light due to the step of the substrate has a great effect on dimensional accuracy, whereas in electron beam exposure, the fine resist is exposed due to the proximity effect caused by backscattering of electrons. It is no longer possible to increase the height to width ratio of the pattern.

It has been found that many of these problems are eliminated by using a multilayer resist system. For a description of multilayer resist systems, see Solid State Technology, 74 (1981) [Solid State Technolog
y, 74 (1981)], but many other studies on this system have been published. Generally, a multilayer resist method includes a three-layer resist method and a two-layer resist method. In the three-layer resist method, an organic flattening film is applied on a stepped substrate, an inorganic intermediate layer and a resist are stacked thereon, and the resist is patterned. Then, the inorganic intermediate layer is dry-etched using the resist as a mask. This is a method of patterning an organic flattening film by O2 RIE (reactive ion etching) using the inorganic intermediate layer as a mask. Basically, this method has been studied from an early stage because conventional techniques can be used, but the process is very complicated, or the organic film, the inorganic film, and the organic film have different three-layer physical properties. The problem is that cracks and pinholes are likely to occur in the intermediate layer due to the overlapping of the objects.

In contrast to the three-layer resist method, the two-layer resist method uses a resist having both properties of the resist and the inorganic intermediate layer in the three-layer resist method, that is, a resist having oxygen plasma resistance. In addition, the generation of cracks and pinholes is suppressed, and the process is simplified because the number of layers is reduced from three to two. However, in the three-layer resist method, a conventional resist can be used as the upper resist, whereas in the two-layer resist method, there is a problem that a new resist having oxygen plasma resistance has to be developed.

[0007] From the above background, it has excellent oxygen plasma resistance which can be used as an upper layer resist such as a two-layer resist method.
There has been a demand for the development of a high-sensitivity, high-resolution positive photoresist, in particular, an alkali developing type resist that can be used without changing the current process.

Further, in the manufacture of VLSI, which requires processing of an ultrafine pattern having a line width of half a micron or less, the wavelength used by an exposure apparatus used for lithography has been shortened, and now a KrF excimer laser beam is used. The use of ArF excimer laser light has been studied. In such short wavelength optical lithography, a resist generally called a chemically amplified type is used. In particular, when an ArF excimer laser beam is used, it is not appropriate to introduce a phenol structure into a binder resin, which is a main component of the resist, from the viewpoint of optical transparency of the film. In general, a resin polymer containing, as an image-forming portion, a structure capable of decomposing with an acid to generate a carboxylic acid, such as an ester, a 1-alkyladamantyl ester, or a THP-protected carboxylic acid, is used as a binder.

The Si-containing polymer containing an image-forming portion transparent to ArF excimer laser light is disclosed in, for example, JP-A-8-160623, JP-A-10-324748,
It is disclosed in JP-A-11-60733 and JP-A-11-60734. Also, SPIE, Vol. 3678, 2
Item 41 is a chemically amplified resist using a vinyl polymer containing a tris (trimethylsilyl) silylethyl group at the terminal of an acid-decomposable ester, SPIE, 3678
Nos. 214, 562 discloses chemically amplified resists using vinyl polymers containing trimethyl-bis (trimethylsilyl) disilaheptylmethylpropyl ester at the end of acid-decomposable esters. However, there is a problem that the resolution and the edge roughness of the line pattern are poor for an ultrafine pattern. Here, the edge roughness refers to when the pattern is viewed from directly above because the top and bottom edges of the resist line pattern fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Means that the edge looks uneven. In addition, since the hydrophobicity of the coating film is high, the permeability of the exposed portion of the alkali developing solution is poor, so that a large number of development defects occur.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photoresist composition which is excellent in resolution and edge roughness of a line pattern and has few development defects in the production of semiconductor devices.

[0011]

Means for Solving the Problems As a result of intensive studies on the resist composition in a positive-type chemical amplification system, the present inventors have found that the use of an acid-decomposable resin copolymerized with a specific repeating unit enables the present invention to be used. I found that my goal was achieved. That is, the above object of the present invention is achieved by using a positive photoresist composition having the following constitution.

(1) (A) a repeating unit having a partial structure represented by the following general formula (I):
(B) a compound which generates an acid upon irradiation with actinic rays or radiation; Photoresist composition.

[0013]

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In the formula (I), m1 represents an integer of 1 to 6. R ¹ and R ² each represent an alkyl group or a cyclic alkyl group, or R ¹ and R ² may combine with each other to form a cyclic alkyl group. R ³ and R ⁴ each represent a hydrogen atom, an alkyl group or a cyclic alkyl group;
³ and R ⁴ may combine with each other to form a cyclic alkyl group. R ^{5 to} R ⁷ each represent an alkyl group, a cyclic alkyl group,
Represents an aryl group, an allyl group, a trialkylsilyl group or a trialkylsilyloxy group.

[0015]

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In the formula (II), Y represents a group selected from a hydrogen atom, a methyl group, a cyano group and a chlorine atom. L ¹ represents a single bond or a divalent linking group. X ¹ is —CO ₂ —, —O—,
Represents a group selected from —CONH— and —CON (R) —.
Here, R represents an optionally substituted alkyl or aryl group having 1 to 10 carbon atoms. A represents a group having a lactone structure, a group having a lactam structure, and -OH and -O as substituents.
CH _3, -OCORa, -OCOORa, -OCONH
Ra, -OCON (Ra) (Rb), -NHCORa, -N
_{HCOORa, -NHSO 2 Ra, -N (} R) CORa,
-N (R) COORa, -N ( R) SO 2 Ra, -COO
_{R, -CONHRa, -CONHSO 2 Ra,} -CON
_{(R) SO 2 Ra, -CON} (Ra) (Rb), - represents a saturated aliphatic group containing at least one functional group selected from the group consisting of CN. Here, R, Ra, and Rb each independently represent an alkyl or aryl group having 1 to 10 carbon atoms which may be substituted.

(2) The repeating unit having a partial structure represented by the general formula (I) is a repeating unit represented by the following general formula (III) or (IV): The positive photoresist composition according to 1).

[0018]

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In the formula (III), Y, R ^{1 to} R ⁷ and m 1 are as defined above. L ² represents a single bond or a divalent linking group.

[0020]

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In the formula (IV), R ^{1 to} R ⁷ and m 1 are as defined above. M ¹ represents an atomic group for forming an alicyclic structure which may have a substituent together with the two bonded carbon atoms. L ³ represents a single bond or a divalent linking group, one of which is linked to a carbon atom forming a ring. m2 represents 1 or 2.

(3) A in the general formula (II) is
The positive photoresist composition according to the above (1) or (2), which is a group represented by the following general formula (V).

[0023]

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In the formula (V), X ² represents —CO—O—, —CO
Represents a group selected from NH— and —CON (R) —. R ⁸ is each independently a hydrogen atom, an alkyl group which may have a substituent, —OH, —OCH ₃ , —OCora, —OC
OORa, -OCONHRa, -OCON (Ra) (R
b), - NHCORa, -NHCOORa, -NHSO 2
Ra, -N (R) CORa, -N (R) COORa, -N
_{(R) SO 2 Ra, -COOR} , -CONHRa, -CO
_{NHSO 2 Ra, -CON (R)} SO 2 Ra, -CON (R
a) represents a group selected from the group consisting of (Rb) and -CN. Here, R, Ra, and Rb are as defined above. m3 represents an integer of 0 to 2; n represents an integer of 0 to 5;

(4) The positive electrode according to (3), wherein the group represented by the general formula (V) is a group represented by the following general formula (VI) or (VII). -Type photoresist composition.

[0026]

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[0027]

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(5) The resin (A), the compound (B) which generates an acid upon irradiation with actinic rays or radiation, and (C) an organic solvent dissolving the above (A) and (B),
And (D) the positive photoresist composition according to any one of the above (1) to (4), comprising an organic basic compound.

(6) The positive type as described in any of (1) to (5) above, wherein the component (B) is a compound which generates an organic sulfonic acid upon irradiation with actinic rays or radiation. Photoresist composition.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. (A) Resin whose solubility in an alkali developer is increased by the action of an acid (also referred to as an acid-decomposable polymer or an acid-decomposable resin) The resin (A) of the present invention has a partial structure represented by the above general formula (I) And a repeating unit represented by the above general formula (II).

In the general formula (I), the alkyl group represented by R ^{1 to} R ⁴ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
6 linear or branched alkyl groups, more preferably methyl group, ethyl group, n-butyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-
A butyl group, and these alkyl groups may have a substituent. As the cyclic alkyl group represented by R ^{1 to} R ⁴ ,
Cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group which may have a substituent , Nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like.

As the alkyl group and cyclic alkyl group for R ^{5 to} R ⁷ , the same as those described above for R ^{1 to} R ⁴ can be mentioned. The aryl group may have a substituent, and specific examples include a phenyl group, a tolyl group, and a naphthyl group. As the alkyl group of the tolylalkylsilyl group, a straight-chain or branched alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, and n are more preferable.
-Propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group, and most preferred is a methyl group. As the alkyl group of the trialkylsilyloxy group, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
A butyl group, an i-butyl group, an s-butyl group, and a t-butyl group, among which the most preferred is a methyl group.

Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an aryl group. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a phenyl group and a tolyl group. And a naphthyl group.

Examples of the cyclic alkyl group formed by combining R ¹ and R ² and R ³ and R ⁴ with each other include cyclopentyl, cyclohexyl, cycloheptyl and adamantyl which may have a substituent. .

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

[0036]

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[0037]

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The acid-decomposable resin (A) having a partial structure represented by the general formula (I) of the present invention is represented by a repeating unit represented by the following general formula (III) or a repeating unit represented by the following general formula (IV) Those containing a repeating unit are preferred.

[0039]

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In the formula (III), R ^{1 to} R ⁷ and m 1 represent the formula (I)
As defined in. Y represents a hydrogen atom, a methyl group, a cyano group, or a chlorine atom. L ² represents a single bond or a divalent linking group.

[0041]

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In the formula (IV), R ^{1 to} R ⁷ and m 1 are represented by the formula (I)
As defined in. M ¹ represents an atomic group for forming an alicyclic structure which may have a substituent together with the two bonded carbon atoms. m2 represents 1 or 2. L ³ represents a single bond or a divalent linking group, one of which is linked to a carbon atom forming a ring.

In formula (III), the divalent linking group for L ² includes a single bond, an alkylene group, a substituted alkylene group, a cycloalkylene group optionally having a bridged structure, an ether group, and a thioether group. Carbonyl group, ester group, amide group, sulfonamide group, urethane group, urea group alone or in combination of two or more groups.

Examples of the alkylene group and substituted alkylene group for L ² include groups represented by the following formula. − [C (Rα) (Rβ)] _r −

In the formula, Rα and Rβ 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, and a propyl group are more preferable.
Selected from isopropyl groups.

Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. As the alkoxy group, a methoxy group, an ethoxy group,
Examples thereof include those having 1 to 4 carbon atoms such as a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

Examples of the cycloalkylene group which may have a bridged structure include those having 5 to 8 carbon atoms.
Specific examples include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a norbornylene group.

Specific examples of the repeating unit represented by the general formula (III) include the following, but the present invention is not limited thereto.

[0049]

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[0050]

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In the general formula (IV), the above-mentioned atomic group for forming an alicyclic structure by M ¹ forms a repeating unit of an alicyclic hydrocarbon which may have a substituent on the resin. Among these, an atomic group for forming a bridged alicyclic structure which forms a repeating unit of a 5- to 8-membered monocyclic or bridged alicyclic hydrocarbon is preferable. Examples of the skeleton of the bridged alicyclic hydrocarbon include those represented by the following structures.

[0052]

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[0053]

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The skeleton of the alicyclic hydrocarbon has a substituent.
May be. Such substituents include halogen atoms
, Cyano group, -COOH, -COOR ^Ten(This R^TenIs
It is separated by the action of an alkyl group, cyclic hydrocarbon group, or acid.
Shows a group to be understood), -CO-X-TR, or a substituent
Alkyl group or cyclic hydrocarbon group optionally having
Is mentioned. Where X is an oxygen atom, a sulfur atom, -NH
-Or-NHSO_TwoAnd T represents a divalent linking group.
R represents a hydrogen atom, a cyano group, a hydroxyl group, -COOH,-
COOR ¹¹, -CO-NH-R¹², May be replaced
Alkyl group, an optionally substituted alkoxy group or
Is an optionally substituted cyclic hydrocarbon group (forming a ring
Even if it has an ester group or a carbonyl group in the bond
Good). R¹¹Is an alkyl which may have a substituent
Or a cyclic hydrocarbon group which may have a substituent
(Ester group or carbonyl group in the bond forming the ring
May be included), and R¹²Has a substituent
Represents an optionally substituted alkyl group.

Examples of the divalent linking group represented by T include a single bond, an alkylene group, a substituted alkylene group, a cycloalkylene group optionally having a bridged structure, an ether group, a thioether group, a carbonyl group, an ester group, An amide group,
A single or a combination of two or more groups selected from the group consisting of a sulfonamide group, a urethane group, and a urea group may be mentioned.

As the divalent linking group for L ³ ,
Examples thereof include an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a combination of two or more groups selected from the group consisting of urea groups. . Alkylene group in the L ^3, as the substituted alkylene group include the same ones divalent linking group L ² in formula (III).

Specific examples of the repeating unit represented by the general formula (IV) include the following, but the present invention is not limited thereto.

[0058]

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[0059]

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[0060]

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In the formula (II), Y has the same meaning as described above. L ¹ represents a single bond or a divalent linking group. X ¹ is -C
Represents a group selected from O ₂ —, —O—, —CONH—, and —CON (R) —. Here, R represents an optionally substituted alkyl or aryl group having 1 to 10 carbon atoms. A is a group containing a lactone structure, a group containing a lactam structure, -OH as a substituent, -OCH _3, -OCORa, -OCOOR
a, -OCONHRa, -OCON (Ra) (Rb), -N
_{HCORa, -NHCOORa, -NHSO 2 Ra,} -
N (R) CORa, -N ( R) COORa, -N (R) SO 2
Ra, -COOR, -CONHRa, -CONHSO _{2
Ra, -CON (R) SO 2} Ra, -CON (Ra) (R
b) represents a saturated aliphatic group containing at least one functional group selected from the group of -CN. Where R, Ra, Rb
Each independently has 1 to 10 carbon atoms which may be substituted
Represents an alkyl or aryl group.

X ¹ is preferably —CO ₂ — or —CON (R) —, more preferably —CO ₂ —.

Examples of the divalent linking group for L ¹ include a single bond, an alkylene group, a substituted alkylene group, a cycloalkylene group optionally having a bridged structure, an ether group, a thioether group, a carbonyl group, an ester group, A single group selected from the group consisting of an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups may be used.

In A, —OH, —OC and
H _3, -OCORa, -OCOORa, -OCONHR
a, -OCON (Ra) (Rb), -NHCORa, -NH
_{COORa, -NHSO 2 Ra, -N (} R) CORa, -
N (R) COORa, -N ( R) SO 2 Ra, -COOR,
_{-CONHRa, -CONHSO 2 Ra, -CON (} R)
The saturated aliphatic group containing at least one functional group selected from the group consisting of SO ₂ Ra, —CON (Ra) (Rb) and —CN includes a linear or branched alkyl group having 1 to 10 carbon atoms, And 3-20 bridged or unbridged alicyclic hydrocarbon groups.

The straight-chain or branched alkyl group having 1 to 10 carbon atoms includes methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, n-pentyl, n-hexyl and the like. And preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-
Butyl residue, more preferably methyl, ethyl,
n-propyl, i-propyl and n-butyl residues. Also,
A lower alkyl group having 1 to 3 carbon atoms such as methyl and ethyl may be further substituted at any position of these alkyl groups.

The bridged or unbridged alicyclic hydrocarbon group having 3 to 20 carbon atoms includes cyclopentane, cyclohexane, [2.2.1] bicycloheptane, and [2.2.2].
Residues such as bicyclooctane, isoboron, adamantane, tricyclodecane, and tetracyclododecane are exemplified, and preferably [2.2.1] bicycloheptane,
[2.2.2] Bicyclooctane, isoboron and adamantane residues, more preferably [2.2.1] bicycloheptane, [2.2.2] bicyclooctane and adamantane residues.

The substituents in the saturated aliphatic group in A include —OH, —OCH ₃ , —OCORa, and —OCON (R
a) (Rb), -COOR, -CON (Ra) (Rb), -C
N is preferred, more preferably —OCH ₃ , —OCOO
Ra, -COOR, and -CN. Where R, Ra, R
b has the same meaning as described above.

In A, as the group containing a lactone structure, there may be mentioned, for example, a group containing a β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone skeleton which may have a substituent. . Here, examples of the substituent include a lower alkyl group such as methyl, ethyl and propyl, and methoxy. In A, the group containing a lactam structure may have a substituent,
Examples include groups having a β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam skeleton, and the like. Here, examples of the substituent include a lower alkyl group such as methyl, ethyl and propyl, and methoxy.

Examples of the optionally substituted alkyl or aryl group having 1 to 10 carbon atoms for R, Ra and Rb include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and s- Butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, cyclohexyl, phenyl, naphthyl. Examples of the further substituent in the alkyl group and the aryl group include a lower alkyl group such as methyl and ethylpropyl or a methoxy group.

R is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group, more preferably a methyl group,
Ethyl, n-propyl, i-propyl and cyclohexyl, more preferably methyl, ethyl, n-propyl and i-propyl. As Ra and Rb, specifically, a methyl group, an ethyl group, an n-propyl group,
i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclohexyl group and phenyl group are preferred, and more preferably methyl group, ethyl group and n-butyl group.
A propyl group, an n-butyl group, a cyclohexyl group, and a phenyl group. More preferably, methyl group, ethyl group, n-
A propyl group and a cyclohexyl group.

Specific examples of the repeating unit represented by the general formula (II) include the following, but the present invention is not limited to these specific examples.

[0072]

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[0073]

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It is preferred that A in the general formula (II) is a group represented by the general formula (V), and among these, the group represented by the general formula (V) is a group represented by the general formula (VI) or (VII) More preferably, it is a group represented by

In the formula (V), X ² represents —CO—O—, —CO
Represents a group selected from NH— and —CON (R) —. R ⁸ independently represent a hydrogen atom, an optionally substituted alkyl _{group, -OH, -OCH 3, -OCORa,} -OC
OORa, -OCONHRa, -OCON (Ra) (R
b), - NHCORa, -NHCOORa, -NHSO 2
Ra, -N (R) CORa, -N (R) COORa, -N
_{(R) SO 2 Ra, -COOR} , -CONHRa, -CO
_{NHSO 2 Ra, -CON (R)} SO 2 Ra, -CON (R
a) represents a group selected from the group consisting of (Rb) and -CN. Here, R, Ra, and Rb are as defined above. m3 represents an integer of 0 to 2; n represents an integer of 0 to 5;

In the formula (V), X ² represents —CO—
O- is preferred. R ⁸ is preferably a hydrogen atom, a methyl group, an ethyl group, —OH, —OCH ₃ , —COOCH ₃ , or —CN, more preferably a hydrogen atom, a methyl group, —O
H, —COOH, and —CN. m3 is preferably 0 or 1. n is preferably from 0 to 2.

The above substituents include —OH, —OCH
₃ , -OCORa, -OCORa, -OCONHR
a, -OCON (Ra) (Rb), -NHCORa, -NH
_{COORa, -NHSO 2 Ra, -N (} R) CORa, -
N (R) COORa, -N ( R) SO 2 Ra, -COOR,
_{-CONHRa, -CONHSO 2 Ra, -CON (} R)
_{SO 2 Ra, -CON (Ra)} (Rb), - CN and the like.

Specific examples of the repeating unit containing the group represented by formula (V) include the following, but the present invention is not limited to these specific examples.

[0079]

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The resin of the present invention further has the following general formula (VIII)
It is preferable to further contain a repeating unit represented by Thereby, the coarse / dense dependency is further improved.

[0081]

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In the formula (VIII), Z represents an oxygen atom or ＮNR¹³
Represents R¹³Has a hydrogen atom, hydroxyl group, straight chain or branched
Alkyl group or —O—SO _Two-R¹⁴Represents R¹⁴Is
Represents an alkyl group or a trihalomethyl group.

In the general formula (VIII), the alkyl group of R ¹³ and R ¹⁴ is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms. And more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
An n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group.

The following are specific examples of the repeating unit represented by the above general formula (VIII), but the present invention is not limited to these specific examples.

[0085]

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[0086]

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The resin of the present invention has the following general formula (IX)
And a repeating unit represented by the formula:

[0088]

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In the formula (IX), Y ² represents a hydrogen atom, a methyl group,
Represents a cyano group or a chlorine atom. L ⁴ is a single bond or 2
Represents a valent linking group. Q represents a hydrogen atom or a group capable of decomposing with an acid to generate a carboxylic acid.

The divalent linking group for L ⁴ includes a single bond, an alkylene group, a substituted alkylene group, a cycloalkylene group optionally having a bridged structure, an ether group, a thioether group, a carbonyl group, an ester group, A single group selected from the group consisting of an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups may be used.

In the repeating unit (IX), the group capable of decomposing with an acid to generate a carboxylic acid is formed by decomposing / eliminating from the resin by the acid generated from the component (A) upon exposure to form a —COOH group. It is a group that occurs. Specific examples of such a group include 3 groups such as a t-butyl group and a t-amyl group.
Primary alkyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-alkoxyethyl group such as 1-cyclohexyloxyethyl group, 1-methoxymethyl group, 1-ethoxymethyl Alkoxymethyl group, tetrahydropyranyl group, tetrahydrofurfuryl group, trialkylsilyl group, 3-oxocyclohexyl group, 2-methyl-adamantyl group, mevalonic lactone residue, 2- (γ-butyrolact Nyloxycarbonyl) -2-propyl group.

Specific examples of the repeating unit represented by the general formula (IX) include the following, but the present invention is not limited to these specific examples.

[0093]

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[0094]

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The acid-decomposable resin of the present invention may have, in addition to the above-mentioned repeating structural units, resistance to dry etching, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution, heat resistance, which are general necessary properties of resist. Various repeating structural units can be contained for the purpose of adjusting properties, 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 monomers, for example, acrylates, methacrylates, acrylamides,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl 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, full Furyl 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 (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
-Methyl-2,2-dimethylpropyl vinyl ether,
2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether,
Dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and the like.

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloride acetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl Acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

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

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

In addition, 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 developer, the substrate adhesion, the resist profile, and the resolving power, heat resistance, which is a general required performance of the resist. It is set as appropriate to adjust properties, sensitivity, and the like.

In the resin according to the present invention, the repeating unit having a partial structure represented by the general formula (I) of the present invention (preferably the repeating unit represented by the general formula (III) or (IV)) is used. The content is appropriately determined in consideration of the desired O ₂ plasma etching resistance of the resist, sensitivity, prevention of pattern cracking, substrate adhesion, resist profile, and the resolution, heat resistance, and other necessary requirements of general resists. Can be set. In general, a repeating unit having a partial structure represented by the general formula (I) of the present invention;
And the content of the repeating unit represented by the general formula (II) is
5 mol% or more is appropriate in all the monomer repeating units of the resin, preferably 10 mol% or more, and more preferably 15 mol%.

The content of the repeating units represented by the general formulas (V) to (IX) in the resin can be appropriately set according to the desired resist properties.
The amount is suitably from 0 to 96 mol%, preferably from 35 to 94 mol%, and more preferably from 40 to 92 mol%. When other repeating units are contained, 50 mol% or less, preferably 40 mol%, of all repeating units.
Mol% or less, more preferably 30 mol% or less.

The resin according to the present invention comprises a repeating unit having a partial structure represented by the general formula (I) and a monomer corresponding to the repeating unit represented by the general formula (II) and a further copolymerization component When is used, it can be synthesized by copolymerizing the monomer of the copolymer component in the presence of a polymerization catalyst.

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

In the positive photoresist composition of the present invention, the compounding amount of the resin (polymer) according to the present invention in the whole composition is preferably 40 to 99.99% by weight, and more preferably the total solid content of the resist. 50 to 99.97% by weight
It is.

(B) Compounds which generate an acid upon irradiation with actinic rays or radiation The compounds used in the present invention which decompose upon irradiation with actinic rays or radiation to generate an acid include photoinitiators for cationic photopolymerization, Known light (400 to 200 nm ultraviolet light, far ultraviolet light, particularly preferably g-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.

Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 38
7 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,0
No. 56, Re 27,992, ammonium salts described in JP-A-3-140140, etc., DCNecker et al., Macromolecules, 17, 24.
68 (1984), CSwen et al., Teh, Proc. Conf. Rad. Curing AS
IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
4,069,056, etc., phosphonium salts, JVCrivell
o etal, Macromorecules, 10 (6), 1307 (1977), Chem. & E
ng. News, Nov. 28, p31 (1988), EP 104,143.
No., U.S. Pat.No. 339,049, No. 410,201, JP-A 2-15
No. 0,848, JP-A-2-296,514 and the like, iodonium salts, JVCrivello et al., Polymer J. 17, 73 (1985), J.
V. Crivello et al. J. Org. Chem., 43, 3055 (1978), WRWa
tt etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Che
m.Ed., 17,2877 (1979), European Patent Nos. 370,693, 161,
811, 410,201, 339,049, 233,567, 29
No. 7,443, No. 297,442, U.S. Pat.No. 3,902,114 No. 4,93
3,377, 4,760,013, 4,734,444, 2,833,827
No. 2,904,626, 3,604,580, 3,604,
No. 581, JP-A-7-28237, JP-A-8-27102, etc., sulfonium salts, JVCrivello et al., Macro
morecules, 10 (6), 1307 (1977), JVCrivello etal, JP
olymerSci., Polymer Chem.Ed., 17, 1047 (1979), etc., selenonium salts, CSWen et al., Teh, Proc. Conf. Rad.C
Onium salts such as arsonium salts described in uring ASIA, p478 Tokyo, Oct (1988), U.S. Patent No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070,
JP-A-60-239736, JP-A-61-169835, JP-A-61-169
No. 837, JP-A-62-58241, JP-A-62-212401, JP-A-62-212401
63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al, J. Rad. Curing, 13 (4), 26
(1986), TPGill et al, Inorg. Chem., 19, 3007 (198
0), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896),
Organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer Sci., 25, 753 (1987), E.
Reichmanis etal, J. Pholymer Sci., Polymer Chem. E
d., 23, 1 (1985), QQ Zhu et al., J. Photochem., 36, 85, 3
9, 317 (1987), B. Amit etal, Tetrahedron Lett., (24)
2205 (1973), DHR Barton et al., J. Chem Soc., 3571 (1
965), PM Collins et al., J. Chem. SoC., PerkinI, 1695 (19
75), M. Rudinstein et al., Tetrahedron Lett., (17), 14
45 (1975), JWWalker etal J. Am. Chem. Soc., 110, 7170
(1988), SCBusman et al., J. Imaging Technol., 11
(4), 191 (1985), HM Houlihan et al, Macormolecules,
21, 2001 (1988), PM Collins etal, J. Chem. Soc.,
Chem. Commun., 532 (1972), S. Hayase etal, Macromolec
ules, 18, 1799 (1985), E. Reichmanetal, J. Electrochem. So
c., SolidStateSci.Technol., 130 (6), FMHoulihan eta
l, Macromolcules, 21, 2001 (1988), EP 0290,750
Nos. 046,083, 156,535, 271,851, 0,38
No. 3,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, and a photoacid generator having a 0-nitrobenzyl-type protecting group described in 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, 845
No. 15, 044,115, No. 618,564, No. 0101,122, U.S. Pat.Nos. 4,371,605, 4,431,774, JP-A-64-18143
Compounds that generate sulfonic acid upon photolysis, such as iminosulfonates described in JP-A-2-245756, JP-A-3-140109, and the like; JP-A-61-166544;
Disulfone compounds described in JP-A-71270 and the like;
No. 103854, No. 3-103856, No. 4-210
No. 960 and the like, and diazoketosulfone and diazodisulfone compounds.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, ME Woodhouse etal, J. Am. Che.
m. Soc., 104, 5586 (1982), SPPappas etal, J. Imagi
ng Sci., 30 (5), 218 (1986), S. Kondo et al., Makromol. C
hem., Rapid Commun., 9, 625 (1988), Y. Yamadaetal, Mak
romol. Chem., 152, 153, 163 (1972), JVCrivello eta
l, J. PolymerSci., Polymer Chem. Ed., 17, 3845 (197
9), U.S. Patent No. 3,849,137, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263
No., JP-A-63-146038, JP-A-63-163452, JP-A-62-163452
Compounds described in JP-A-153853 and JP-A-63-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (19
80), A. Abad et al, Tetrahedron Lett., (47) 4555 (197
1), DHR Barton et al, J. Chem. Soc., (C), 329 (197
0), compounds which generate an acid by light described in US Pat. No. 3,779,778 and European Patent No. 126,712 can also be used.

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

(1) A sulfonium salt represented by the following general formula (PAG4).

[0119]

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Here, in the general formula (PAG4), Rs1 to Rs
and s3 each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferably it is an aryl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracene group, and a phenanthrene group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a pentyl group. Group, hexyl group, heptyl group and octyl group. Preferred examples of these 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, an acyl group, an acyloxy group, a hydroxy group, a mercapto group and a halogen atom. Can be

[0121] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^- perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, sulfonic acid anion having aliphatic hydrocarbon group or an aromatic hydrocarbon group such as a naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid Examples include anions, sulfonic acid group-containing dyes, and alkylsulfonic acids such as methanesulfonic acid, but are not limited thereto.

Two of Rs1 to Rs3 may be bonded via a single bond or a substituent.

Specific examples of the photoacid generator include, but are not limited to, the following compounds.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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The sulfonium salt represented by the general formula (PAG4) is described, for example, in JW Knapczyket al, J. Am. Che
m. Soc., 91, 145 (1969), AL Maycok et al, J. Or
g. Chem., 35, 2532, (1970), E. Goethas et al, Bul
l. Soc. Chem. Belg., 73, 546, (1964), HM Leices
ter, J. Ame.Chem. Soc., 51, 3587 (1929), JV Cri
vello et al, J. Polym. Chem. Ed., 18, 2677 (1980),
U.S. Pat.Nos. 2,807,648 and 4,247,473, JP 53
-101331 can be synthesized.

In the present invention, as the photoacid generator, a photoacid generator represented by the following general formula [sI] is particularly preferable. This can reduce the number of particles after preparing the resist composition solution and the increase in the number of particles after storage with time from the preparation.

[0133]

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In the general formula [sI], R _{s4 to} R _s6 each represent a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, Optionally substituted alkoxy group, optionally substituted alkoxycarbonyl group, optionally substituted acyl group, optionally substituted acyloxy group, nitro group, halogen atom, Represents a hydroxyl group and a carboxyl group. 1: 1-5 m: 0-5 n: 0-5. When l + m + 1 = 1, R _s4 represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an optionally substituted alkoxycarbonyl group, an optionally substituted acyl group, and an optionally substituted acyloxy group. X: R _x —SO ₃ , R _x : an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.

In the general formula [sI], R _{s4 to} R _s4
Examples of the alkyl group for _s6 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, and a heptyl group which may have a substituent. And those having 1 to 25 carbon atoms such as a group, an octyl group, a t-amyl group, a decanyl group, a dodecanyl group and a hexadecanyl group. The cycloalkyl group may have a substituent and has 3 to 25 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecanyl group, and a cyclohexadecanyl group. Things.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group and a sec-
Examples thereof include those having 1 to 25 carbon atoms such as -butoxy group or t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group, and n-dodecaneoxy group.

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group and a sec-butoxycarbonyl which may have a substituent. A group having 2 to 25 carbon atoms such as a t-butoxycarbonyl group, a pentyloxycarbonyl group, a t-amyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-octyloxycarbonyl group, an n-dodecaneoxycarbonyl group, etc. One.

Examples of the acyl group include a formyl group, an acetyl group, a butyryl group, a valeryl group, a hexanoyl group, an octanoyl group, a t-butylcarbonyl group and a t-amylcarbonyl group which may have a substituent. Carbon number 1
To 25. As the acyloxy group,
An acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, an n-
Examples thereof include those having 2 to 25 carbon atoms such as an octanecarbonyloxy group, an n-dodecanecarbonyloxy group, an n-hexadecanecarbonyloxy group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As a substituent for these groups, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Carboxy group,
Examples thereof include an alkoxycarbonyl group and a nitro group. When l + m + n = 1, R _s4 represents an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a substituent Represents an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, and an acyloxy group which may have a substituent. R _s4 preferably has 2 or more carbon atoms, more preferably 4 or more carbon atoms.

Among the above, as the alkyl group which may have a substituent of R _{s4 to} R _s6 , methyl, ethyl, propyl, isopropyl, butyl, t-
A butyl group, an n-pentyl group, a t-amyl group, an n-hexyl group, an n-octyl group, and a decanyl group are preferable.As the cycloalkyl group, a cyclohexyl group, a cyclooctyl group, which may have a substituent, A cyclododecanyl group is preferable, and as the alkoxy group, a methoxy group, an ethoxy group, an isopropoxy group, an n-
Butoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecaneoxy group is preferable, and the alkoxycarbonyl group is preferably a substituent. Methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n -Hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecaneoxycarbonyl group is preferable, and the acyl group may have a substituent, formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group. , Octanoyl group, t
-Butylcarbonyl group, t-amylcarbonyl group is preferable, and the acyloxy group may have a substituent,
Acetoxy group, ethylyloxy group, butyryloxy group,
A t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group are preferred.

The alkyl group having 5 or more carbon atoms and which may have a substituent is an n-pentyl group or a t-
Amyl, n-hexyl, n-octyl and decanyl are preferred. A cycloalkyl group having 5 or more carbon atoms, which may have a substituent, is a cyclohexyl group,
A cyclooctyl group and a cyclododecanyl group are preferred. Examples of the alkoxy group having 5 or more carbon atoms, which may have a substituent, include a pentyloxy group, a t-amyloxy group,
Hexyloxy, n-octyloxy and dodecaneoxy are preferred. An alkoxycarbonyl group having 5 or more carbon atoms, which may have a substituent, includes a pentyloxycarbonyl group, a t-amyloxycarbonyl group,
Hexyloxycarbonyl, n-octyloxycarbonyl and dodecaneoxycarbonyl are preferred. As the acyl group having 5 or more carbon atoms and which may have a substituent, a paleryl group, a hexanoyl group, an octanoyl group, and a t-amylcarbonyl group are preferable. As the acyloxy group having 5 or more carbon atoms and which may have a substituent, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group are preferable.

Examples of the substituent for these groups include a methoxy group, an ethoxy group, a t-butoxy group, a chlorine atom, a bromine atom, a cyano group, a hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group and a t-butoxycarbonyl group. An amyloxycarbonyl group is preferred.

The sulfonium compound represented by the general formula [sI] used in the present invention uses a sulfonic acid having a specific structure as described above as its counter anion, X ⁻ . Examples of the aliphatic hydrocarbon group which may have a substituent of R _X in the counter anion include a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group. R may be an aromatic group which may have a substituent.

Examples of the alkyl group for R _X include a methyl group, an ethyl group, a propyl group, an n
Examples thereof include those having 1 to 20 carbon atoms such as -butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group and dodecyl group. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, an adamantyl group, a norbornyl group, a camphor group, a tricyclodecanyl group, and a mentyl group which may have a substituent. Can be. Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent.

Among the above, the alkyl group which may have a substituent for R _X includes a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group,
2,2-trifluoroethyl group, n-propyl group, n-
Butyl group, nonafluorobutyl group, n-pentyl group, n
Examples of -hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group, dodecyl group and cyclic alkyl group include cyclopentyl group, cyclohexyl group and camphor group. As the aromatic group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a p-toluyl group, a p-toluyl group,
-Fluorophenyl group, p-chlorophenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, 6-hydroxy-2-naphthyl Groups.

Of the above substituents, more preferred R
Specific examples of s4 to Rs6 include a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, cyclohexyl, methoxy,
Ethoxy, isopropoxy, n-butoxy, t-
Butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n-octyloxy group, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyl Oxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group, butyryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group, t-amylcarbonyl group, acetoxy group, ethylyloxy group, butyryloxy group, t-butyryloxy Group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, hydroxyl group, chlorine atom, bromine atom and nitro group.

More preferred examples of the group having 5 or more carbon atoms include n-pentyl, t-amyl, n-hexyl, n-octyl, decanyl, cyclohexyl, pentyloxy, and t-yl. Amyloxy group, hexyloxy group, n-octyloxy group, dodecaneoxy group, pentyloxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, dodecaneoxycarbonyl group, pareryl group, hexanoyl A octanoyl group, a t-amylcarbonyl group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.

More preferred examples of the sulfonic acid substituent R _X include a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-butyl group, a nona Fluorobutyl group,
n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group , P-methoxyphenyl, dodecylphenyl, mesityl, triisopropylphenyl, 4-hydroxy-1-naphthyl, and 6-hydroxy-2-naphthyl.

The total number of carbon atoms of the generated acid is preferably from 1 to 30. The number is more preferably 1 to 28, and still more preferably 1 to 25. If the total number of carbon atoms is less than 1, the pattern formation may be hindered such as a t-top shape, and if it exceeds 30, the development residue may be undesirably generated.

Hereinafter, specific examples of the compound represented by the general formula [sI] include the following [sI-1] to [sI-20].
However, the present invention is not limited to this. These compounds are used alone or in combination of two or more.

[0151]

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[0152]

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[0153]

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(2) An oxazole derivative represented by the following formula (PAG1) or an S-triazine derivative represented by the following formula (PAG2) substituted by a trihalomethyl group.

[0155]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl, alkenyl, alkyl or —C
(Y) ₃ is shown. Y represents a chlorine atom or a bromine atom.

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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(3) An iodonium salt represented by the following general formula (PAG3).

[0162]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. 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, a mercapto group, and a halogen atom.

[0164] Za ^- include represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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

[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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The onium salts represented by the general formula (PAG3) are known, and are described, for example, in JW Knapczyk et al, J. A.
m. Chem. Soc., 91, 145 (1969), AL Maycok et al,
J. Org. Chem., 35, 2532, (1970), E. Goethas et al,
Bull. Soc. Chem. Belg., 73, 546, (1964), HM Le
icester, J. Ame.Chem. Soc., 51, 3587 (1929), JV
Crivello et al, J. Polym. Chem. Ed., 18, 2677 (198
0), U.S. Pat. Nos. 2,807,648 and 4,247,473, JP-A-53-101331, and the like.

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

[0174]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ^{20 6} are a substituted or unsubstituted alkyl group, an 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.

[0177]

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[0178]

[Of 60]

[0179]

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[0180]

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[0181]

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[0182]

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(5) Diazodisulfone Derivative Compound The diazodisulfone derivative compound includes compounds represented by the following general formula (PAG7).

[0184]

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Here, R ²¹¹ and R ²¹² each independently represent an alkyl group which may have a substituent, a cycloalkyl group or an aryl group which may have a substituent. As the alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 12 carbon atoms is more preferable. As the cycloalkyl group, a cyclopentyl group or a cyclohexyl group is preferable. As the aryl group, an aryl group which may have a substituent having 6 to 10 carbon atoms is preferable.

Here, the substituents include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
alkyl groups such as i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, and methoxy group , Ethoxy group, propoxy group, alkoxy group such as butoxy group, halogen atom, nitro group,
An acetyl group and the like can be mentioned.

Specific examples of the diazodisulfone derivative compound include the following compounds. Bis (methylsulfonyl) diazomethane, bis (ethylsulfonyl) diazomethane, bis (propylsulfonyl) diazomethane,
Bis (1-methylpropylsulfonyl) diazomethane,
Bis (butylsulfonyl) diazomethane, bis (1-methylbutylsulfonyl) diazomethane, bis (heptylsulfonyl) diazomethane, bis (octylsulfonyl) diazomethane, bis (nonylsulfonyl) diazomethane, bis (decylsulfonyl) diazomethane, bis (dodecylsulfonyl) Diazomethane, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (benzylsulfonyl) diazomethane, bis (2-chlorobenzylsulfonyl) diazomethane, bis (4-chlorobenzylsulfonyl) diazomethane, bis (phenylsulfonyl) Diazomethane, bis (4-methoxyphenylsulfonyl)
Diazomethane, bis (2-methylphenylsulfonyl)
Diazomethane, bis (3-methylphenylsulfonyl)
Diazomethane, bis (4-methylphenylsulfonyl)
Diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2,5-dimethylphenylsulfonyl) diazomethane, bis (3,4-dimethylphenylsulfonyl) diazomethane, bis (2,4,6-
Trimethylphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (2,4-difluorophenylsulfonyl) diazomethane, bis (2,4,6-trifluorophenylsulfonyl) diazomethane, bis (4-nitrophenylsulfonyl) ) Diazomethane.

(6) Diazoketosulfone derivative compound As the diazoketosulfone derivative compound, those represented by the following general formula (PAG8) can be mentioned.

[0189]

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Here, R ²¹¹ and R ²¹² are the same as those in (PAG7)
Has the same ^meanings as R ²¹¹ and R ²¹² . Specific examples of the diazoketosulfone derivative compound include the following compounds.

Methylsulfonyl-benzoyl-diazomethane, ethylsulfonyl-benzoyl-diazomethane,
Methylsulfonyl-4-bromobenzoyl-diazomethane, ethylsulfonyl-4-bromobenzoyl-diazomethane, phenylsulfonyl-benzoyl-diazomethane, phenylsulfonyl-2-methylphenyl-diazomethane, phenylsulfonyl-3-methylphenyl-diazomethane, phenylsulfonyl- 4-methylphenyl-diazomethane, phenylsulfonyl-3-methoxyphenyl-diazomethane, phenylsulfonyl-4-methoxyphenyl-diazomethane, phenylsulfonyl-3
-Chlorobenzoyl-diazomethane, phenylsulfonyl-4-chlorophenyl-diazomethane, tolylsulfonyl-3-chlorobenzoyl-diazomethane, tolylsulfonyl-4-chlorophenyl-diazomethane, phenylsulfonyl-4-fluorophenyl-diazomethane,
Tolylsulfonyl-4-fluorophenyl-diazomethane.

In the compounds of the above (1) to (6),
The compound of (1) is preferred, and the compound represented by the above general formula (sI) shows high resolution and is more preferred. still,
Two or more of the compounds (1) to (6) may be used in combination. In this case, it is preferable to use a combination of the compound (1) and at least one compound selected from the group consisting of the compounds (2) to (6), thereby exhibiting high resolution.

The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.1% based on the total weight of the resist composition (excluding the coating solvent).
It is used in the range of 01 to 20% by weight, preferably 0.1 to 20% by weight.
To 15% by weight, more preferably 0.5 to 10% by weight. The amount of the compound that decomposes by irradiation with actinic rays or radiation to generate an acid is 0.01% by weight.
If the amount is smaller, the sensitivity is lowered, and the amount of addition is 20% by weight.
If it is larger, the light absorption of the resist becomes too high, and the profile is deteriorated and the process (especially, baking) margin is undesirably reduced.

The positive photoresist composition of the present invention comprises
(D) It is preferable to contain an organic basic compound. This reduces the sensitivity fluctuation. Examples of the organic basic compound include those having the following structures.

[0195]

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

[0197]

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Represents the same or different and represents 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, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound 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 aminoalkylmorpholine and the like can be mentioned. 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 compounds are guanidine, 1,1-dimethylguanidine, 1,1,3,3,-
Tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine,
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 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,
-Pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
3,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU)
Grade morpholine derivatives, hindered amines described in JP-A-11-52575 (for example, [0005]
), But is not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2 .2.2] octane, 4-dimethylaminopyridine,
Hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines such as CHMETU, bis (1,2,2,6,6-pentamethyl-
Hindered amines such as (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, hexamethylene Preferred are tetramine, CHMETU, and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

These organic basic compounds are used alone or in combination of two or more. The amount of the organic basic compound used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total solid content of the resist composition.
% 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. On the other hand, 10% by weight
If it exceeds 300, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

The positive photoresist composition of the present invention comprises
Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, and a nonionic surfactant. Among them, a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom are particularly preferable, and the density dependency can be 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
The surfactant described in No. 8 can be used, and the following commercially available surfactant can be used as it is. Commercially available surfactants that can be used, for example, F-top EF301, EF3
03 (Shin-Akita Chemical Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Ltd.), MegaFac F171, F173, F176, F18
9, R08 (Dainippon Ink Co., Ltd.), Surflon S-382,
SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.),
Fluorinated surfactants such as Troysol S-336 (manufactured by Troy Chemical Co., Ltd.) and silicon-based surfactants can be mentioned. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

Specific examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Ethylene octyl phenol ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; Can be mentioned.

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

The positive photoresist composition of the present invention comprises
As a coating solvent, propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, alkyl lactates such as methyl lactate and ethyl lactate, and propylene such as propylene glycol monomethyl ether and propylene glycol monoethyl ether Ethylene glycol monoalkyl ethers such as glycol monoalkyl ethers, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; 2-heptanone , Γ-butyrolactone, methoxypropyl Selected from alkyl alkoxypropionates such as methyl phosphate and ethyl ethoxypropionate, alkyl pyruvates such as methyl pyruvate and ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. It is applied using at least one solvent.

The positive photoresist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye,
A plasticizer, a surfactant other than the above, a photosensitizer, a compound that promotes solubility in a developer, and the like can be contained.

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 50 nm to 1.5 μm (1500 nm). The composition is applied on a substrate (eg, silicon / silicon dioxide coating) such as that used in the manufacture of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then exposed through a predetermined mask, followed by baking. By performing and developing, a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248n
m), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an electron beam, etc., and particularly an ArF excimer laser (193 nm).
Is preferred.

Examples of the developer for the positive photoresist composition for deep ultraviolet exposure according to the present invention 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.

When a resist of the positive photoresist composition of the present invention is used as an upper resist of a two-layer resist, the lower organic polymer film is etched by oxygen plasma using the upper resist pattern as a protective mask. The upper resist has sufficient resistance to oxygen plasma. Although the oxygen plasma resistance of the positive photoresist composition of the present invention depends on the silicon content of the upper resist, the etching apparatus, and the etching conditions, the etching selectivity (the etching rate ratio between the lower resist and the upper resist) is 10%. It can be taken as a sufficiently large value of ~ 100.

In the pattern forming method using the positive photoresist composition of the present invention, first, an organic polymer film is formed on a substrate to be processed. The organic polymer film may be various known photoresists, and examples thereof include FH series and FHi series manufactured by Fujifilm Olin Co., or OiR series manufactured by Olin Co., and PFI series manufactured by Sumitomo Chemical Co., Ltd. The formation of the organic polymer film is performed by dissolving these in an appropriate solvent and applying the resulting solution by a spin coating method, a spraying method or the like. Next, a film of the positive photoresist composition of the present invention is formed on the first layer of the organic polymer film. This is performed by dissolving the resist material in an appropriate solvent in the same manner as in the first layer, and applying the resulting solution by spin coating, spraying, or the like. The obtained two-layer resist is then subjected to a pattern forming step. As a first step, a pattern forming process is first performed on the second layer, that is, the film of the upper photoresist composition. Perform mask alignment as necessary, and irradiate high-energy radiation through this mask to make the irradiated portion of the photoresist composition soluble in an alkaline aqueous solution,
The pattern is formed by developing with an alkaline aqueous solution.

Next, as a second step, the organic polymer film is etched. This operation is performed by oxygen plasma etching using the film pattern of the resist composition as a mask to form a fine pattern having a high aspect ratio. I do. The etching of the organic polymer film by the oxygen plasma etching is exactly the same technique as the plasma ashing used when the resist film is peeled off after the etching of the substrate is completed by the conventional photoetching operation. This operation can be performed by, for example, a cylindrical plasma etching apparatus or a parallel flat slope plasma etching apparatus using oxygen as a reactive gas, that is, an etching gas. Further, the substrate is processed using this resist pattern as a mask. As a processing method, a dry etching method such as sputter etching, gas plasma etching, or ion beam etching can be used.

The etching treatment by the two-layer resist method including the resist film of the present invention is completed by the operation of removing the resist film. The removal of the resist layer can be carried out simply by dissolving the organic polymer material of the first layer. Since this organic polymer material is an arbitrary photoresist and has not been altered (hardened or the like) at all in the photoetching operation, an organic solvent of each known photoresist itself can be used. Or,
By a process such as plasma etching, separation can be performed without using a solvent.

[0216]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Synthesis Example (1) Synthesis of Resins (1) to (6) 17.5 g of a monomer (A) corresponding to a repeating unit having a partial structure represented by the general formula (I) of the present invention, 10.13 g of a monomer (B) corresponding to the repeating unit represented by the general formula (II) is added to 27 ml of dry THF,
It was completely dissolved under a nitrogen stream. Later, Wako Pure Chemical Co., Ltd.
Initiator V-59 was used in an amount of 2 mol based on the total number of moles of the monomers.
%, And heated to 70 ° C. under a nitrogen stream.

After reacting for 20 hours, the reaction mixture was added dropwise to 400 ml of hexane, and the precipitated white powder was filtered and dried under reduced pressure at room temperature for 1 hour. Thereafter, the white powder was dissolved in 27 ml of dry THF, and 400 ml of hexane was again formed.
After filtration, the precipitated white powder was filtered at 40 ° C.
After drying under reduced pressure for a time, a resin (1) was obtained. As a result of GPC measurement, the molecular weight of the obtained resin (1) was 13,700 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1,000 or less was 3% by GPC area ratio.

Resins (2) to (6) were obtained in the same manner as described above. The molar ratio and the weight average molecular weight of each of the repeating units of the resins (1) to (6) are shown in the following structural formula and Table 1.

Synthesis Example (2) Synthesis of Resin (7) Monomer (A) 12.09 g, methacrylic acid 0.86
g, methyl acrylate 1.72 g, maleic anhydride3.
92 g was added to 19 ml of dry THF and completely dissolved under a nitrogen stream. Thereafter, an initiator V-59 manufactured by Wako Pure Chemical Industries, Ltd.
Was added in an amount of 3 mol% of the total number of moles of the monomer, and a resin (7) was obtained in the same manner as in Synthesis Example (1). As a result of GPC measurement, the molecular weight of the obtained resin (7) was 18,300 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1,000 or less was 4% in GPC area ratio. The molar ratio and the weight average molecular weight of each repeating unit of the resin (7) are shown in the following structural formula and Table 1.

[0221]

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[0222]

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[0223]

[Table 1]

Example 1 2 g of resin (1) as an acid-decomposable resin (A) component, and (2,4,6-trimethylphenyl) diphenylsulfonium-heptadecafluorooctanesulfonate as a compound component that generates an acid upon exposure to light 0.12 g, 0.012 g of DBU, and 0.003 g of the following surfactant W-1 were dissolved in 19.2 g of propylene glycol monomethyl ether acetate, and finely filtered through a 0.1 μm membrane filter.

A silicon wafer was coated with a FHi-028D resist (a resist for i-line, manufactured by Fujifilm Ohlin Co., Ltd.) using a coater CDS-650 manufactured by Canon.
Baking was performed at 0 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.83 μm. When this was further heated at 200 ° C. for 3 minutes, the film thickness became 0.71 μm. The silicon-containing resist composition prepared above was applied thereon, baked at 90 ° C. for 90 seconds, and applied to a thickness of 0.20 μm.

The wafer thus obtained was exposed to an ArF excimer laser stepper while loading a resolving power mask thereon while changing the exposure amount and focus. Then, after heating in a clean room at 120 ° C. for 90 seconds, tetramethylammonium hydroxide developer (2.38%) was used for 60 minutes.
After developing for 2 seconds, rinsing with distilled water and drying were performed to obtain a pattern. Observation with a scanning electron microscope showed that
Were resolved (line resolution). The roughness was evaluated as A.

The roughness was visually evaluated by observing the size of the roughness (irregularity) at the line edge portion in the 0.13 μm line and space pattern with an SEM.
Evaluation was made in three stages of A, B, and C in order from the best one, and A was given when little roughness (roughness) was seen at the line edge, and B was given when little roughness (roughness) was seen at the line edge. Samples in which roughness (roughness) was clearly seen at the line edge were designated C.

To evaluate the number of development defects, a 6-inch Bar was used.
e The resist solution prepared in Example (1) was applied to a thickness of 0.5 μm on an Si substrate,
Dry at 0 ° C. for 60 seconds and then Nikon stepper NSR-150 through a test mask with a 0.35 μm contact hole pattern (Hole Duty ratio = 1.3).
After exposure with 5EX, post-exposure baking is performed at 120 ° C. for 90 minutes.
Seconds. Subsequently, after a battle development with a 2.38% tetramethylammonium hydroxide developing solution (2.38%) for 60 seconds, the resultant was washed with pure water for 30 seconds and spin-dried. The number of development defects of the sample thus obtained was measured with a KLA-2112 machine manufactured by KLA Tencor Co., Ltd., and the obtained primary data value was defined as the number of development defects. The result was 36.

Examples 2 to 6 Positive photoresists were prepared in exactly the same manner as in Example 1 except that the resist compositions in Example 1 were used instead of the resist compositions in Example 1. The composition was prepared, and exposed and developed in the same manner as in Example 1. In addition, resolution, line edge roughness, and number of development defects were evaluated. Table 3 shows the obtained performance.

(Comparative Example 1) A positive photo resist was manufactured in exactly the same manner as in Example 1 except that the resist composition of Example 1 was used instead of the resist composition of Example 1. The resist composition was adjusted, and exposed and developed in the same manner as in Example 1. In addition, resolution, line edge roughness, and number of development defects were evaluated. Table 3 shows the obtained performance.

Examples of the surfactant include W-1: Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3: represents polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the organic basic compound include: DBU: 1,8-diazabicyclo [5.4.0] -7-undecene TPI: 2,4,5-triphenylimidazole DBN: 1,5-diazabicyclo [4.3 .0] -5-Nonene, DMAP: 4-dimethylaminopyridine

[0233]

[Table 2]

[0234]

[Table 3]

The above results show that the positive photoresist composition of the present invention exhibited excellent performance in terms of resolution, evaluation of the number of development defects, and roughness.

[0236]

According to the present invention, it is possible to provide a positive photoresist composition having a high resolution, a small line pattern edge roughness and a small number of development defects in the production of semiconductor devices.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Shoichiro Yasu 4000 Kawajiri, Yoshida-cho, Harihara-gun, Shizuoka Prefecture Fujisha Shin Film Co., Ltd. In-company F-term (reference) 2H025 AA03 AB16 AD03 BE00 BE07 BE10 BF03 BF05 BF11 BF30 BG00 CB43 CC03 CC20 FA17 4J002 BG021 BG072 BK001 EB006 EN136 EQ016 ER027 EU027 EU047 EU077 EU117 EU127 EU137 EU147 EU186 EU206 EU296 237

Claims (6)

[Claims] (A) a repeating unit having a partial structure represented by the following general formula (I) and a repeating unit represented by the following general formula (II); A positive photoresist composition comprising: a resin having increased solubility; and (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation. Embedded image In the formula (I), m1 represents an integer of 1 to 6. R ¹ and R ²
Represents an alkyl group or a cyclic alkyl group,
Alternatively, R ¹ and R ² may combine with each other to form a cyclic alkyl group. R ³ and R ⁴ each represent a hydrogen atom, an alkyl group or a cyclic alkyl group, or R ³ and R ⁴ may combine with each other to form a cyclic alkyl group. R ⁵ to R ⁷ are each an alkyl group, a cyclic alkyl group, an aryl group, an allyl group, trialkylsilyl group or trialkylsilyl group. Embedded image In the formula (II), Y represents a group selected from a hydrogen atom, a methyl group, a cyano group, and a chlorine atom. L ¹ represents a single bond or a divalent linking group. X ¹ is —CO ₂ —, —O—, —CONH
—, Represents a group selected from —CON (R) —. Here, R represents an optionally substituted alkyl or aryl group having 1 to 10 carbon atoms. A is a group containing a lactone structure, a group containing a lactam structure, -OH as a substituent, -OCH _3, -
OCORa, -OCOORa, -OCONHRa, -O
CON (Ra) (Rb), -NHCORa, -NHCOOR
_{a, -NHSO 2 Ra, -N (} R) CORa, -N (R) C
_{OORa, -N (R) SO 2} Ra, -COOR, -CON
_{HRa, -CONHSO 2 Ra, -CON (} R) SO 2 R
a, represents a saturated aliphatic group containing at least one functional group selected from the group of -CON (Ra) (Rb) and -CN.
Here, R, Ra, and Rb each independently represent an alkyl or aryl group having 1 to 10 carbon atoms which may be substituted. 2. The repeating unit having a partial structure represented by the general formula (I) is a repeating unit represented by the following general formula (III) or (IV). The positive photoresist composition as described in the above. Embedded image In the formula (III), Y, R ^{1 to} R ⁷ and m 1 are as defined above.
L ² represents a single bond or a divalent linking group. Embedded image In the formula (IV), R ^{1 to} R ⁷ and m 1 are as defined above. M ¹ represents an atomic group for forming an alicyclic structure which may have a substituent together with the two bonded carbon atoms. L ³
Represents a single bond or a divalent linking group, one of which is linked to a carbon atom forming a ring. m2 represents 1 or 2. 3. The positive photoresist composition according to claim 1, wherein A in the general formula (II) is a group represented by the following general formula (V). Embedded image In the formula (V), X ² represents —CO—O—, —CONH—, —C
Represents a group selected from ON (R)-. R ⁸ is each independently a hydrogen atom, an alkyl group which may have a substituent,
_{OH, -OCH 3, -OCORa, -OCOORa} , -
OCONHRa, -OCON (Ra) (Rb), -NHCO
_{Ra, -NHCOORa, -NHSO 2 Ra,} -N (R)
CORa, -N (R) COORa, -N (R) SO 2 Ra,
-COOR, -CONHRa, -CONHSO ₂ Ra,
_{-CON (R) SO 2 Ra,} -CON (Ra) (Rb), - C
Represents a group selected from the group of N. Here, R, Ra, and Rb are as defined above. m3 represents an integer of 0 to 2; n represents an integer of 0 to 5; 4. The positive-type photo according to claim 3, wherein the group represented by the general formula (V) is a group represented by the following general formula (VI) or (VII). Resist composition. Embedded image Embedded image 5. The resin of (A), the compound of (B) which generates an acid upon irradiation with actinic rays or radiation, and
The positive photoresist composition according to any one of claims 1 to 4, further comprising (C) an organic solvent that dissolves (A) and (B), and (D) an organic basic compound. . 6. The positive photoresist composition according to claim 1, wherein the component (B) is a compound that generates an organic sulfonic acid upon irradiation with actinic rays or radiation. .