KR20210088669A - resist composition - Google Patents

Abstract

(상기 식(1) 중, R₁ 및 R₂는, 각각 독립으로, 수소 원자, 탄소 원자수 1∼9의 지방족 탄화수소기, 알콕시기, 아릴기, 아랄킬기 또는 할로겐 원자를 나타낸다.
m 및 n은, 각각 독립으로, 0∼4의 정수를 나타낸다.
R₁이 복수 있을 경우, 복수의 R₁은 서로 같아도 되고 달라도 된다.
R₂가 복수 있을 경우, 복수의 R₂는 서로 같아도 되고 달라도 된다.
R₃은, 수소 원자, 탄소 원자수 1∼9의 지방족 탄화수소기, 또는 탄화수소기 상에 알콕시기, 할로겐기 및 수산기에서 선택되는 치환기를 1 이상 갖는 구조 부위를 나타낸다)An object of the present invention is to provide a resist composition that has high heat resistance and can be used for lithography using electron beams and extreme ultraviolet rays. Specifically, a resist composition containing a metal salt of a novolak-type phenol resin (C) containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials is used.

(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.
m and n each independently represent the integer of 0-4.
If R ₁ is plural, a plurality of R ₁ are different from each other be the same.
If R ₂ is a plurality, the plurality of R ₂ may be the same or different from each other.
R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group)

Description

resist composition

The present invention relates to a resist composition.

As a resist used for the manufacture of semiconductors such as ICs and LSIs, the manufacture of display devices such as LCDs, and the manufacture of printed originals, positive photoresist using an alkali-soluble resin and a photosensitizer such as a 1,2-naphthoquinonediazide compound is known As the alkali-soluble resin, a positive photoresist composition using a mixture of m-cresol novolak resin and p-cresol novolak resin as alkali-soluble resin has been proposed (for example, refer to Patent Document 1).

The positive photoresist composition described in Patent Document 1 was developed for the purpose of improving developability such as sensitivity. . However, in the positive photoresist composition of patent document 1, there existed a problem that sufficient sensitivity corresponding to thinning was not obtained. Moreover, since various heat treatments are performed in the manufacturing process of a semiconductor etc., high heat resistance is also calculated|required, but there existed a problem that the positive photoresist composition of patent document 1 did not have sufficient heat resistance.

Moreover, especially in the field of semiconductor manufacturing, such as an IC and LSI, fine processing is calculated|required and lithography using an electron beam or extreme ultraviolet (EUV) is examined. With the shortening of the wavelength of the exposure light source, a further improvement in the properties of the resist composition corresponding thereto has been demanded.

Japanese Patent Laid-Open No. 2-55359

The problem to be solved by the present invention is to provide a resist composition that has high heat resistance and can be used for lithography using electron beams and extreme ultraviolet rays.

As a result of intensive studies to solve the above problems, the present inventors have found that a resist composition comprising a metal salt structure of a novolak-type phenolic resin obtained by reacting a carboxylic acid-containing phenolic trinuclear compound having a specific structure with an aliphatic aldehyde, It has high heat resistance and can be used for lithography using electron beams and extreme ultraviolet rays, and the present invention has been completed.

That is, the present invention relates to a resist composition comprising a metal salt of a novolak-type phenolic resin (C) containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials. .

(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.

m and n each independently represent the integer of 0-4.

If R ₁ is plural, a plurality of R ₁ are different from each other be the same.

If R ₂ is a plurality, the plurality of R ₂ may be the same or different from each other.

R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group)

ADVANTAGE OF THE INVENTION According to this invention, it has high heat resistance and can provide the resist composition which can be used for lithography using an electron beam and extreme ultraviolet rays.

1 is a GPC chart of the precursor compound obtained in Synthesis Example 1.
^{2 is a 13} C-NMR chart of the precursor compound obtained in Synthesis Example 1. FIG.
3 is a GPC chart of the precursor compound obtained in Synthesis Example 2.
^{4 is a 13} C-NMR chart of the precursor compound obtained in Synthesis Example 2. FIG.
5 is a GPC chart of the novolak-type phenol resin obtained in Production Example 1.
6 is a GPC chart of the novolak-type phenol resin obtained in Production Example 2.
7 is a GPC chart of the novolak resin obtained in Production Example 3.
8 is a GPC chart of the novolak resin obtained in Production Example 4.

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of this invention is described. This invention is not limited to the following embodiment, The range which does not impair the effect of this invention can add and implement a suitable change.

[resist composition]

The resist composition of this invention contains the metal salt of the novolak-type phenol resin (C) which uses the aromatic compound (A) and the aliphatic aldehyde (B) represented by following formula (1) as essential reaction raw materials.

(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.

m and n each independently represent the integer of 0-4.

If R ₁ is plural, a plurality of R ₁ are different from each other be the same.

If R ₂ is a plurality, the plurality of R ₂ may be the same or different from each other.

R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group)

A resist composition usually contains a resin whose polarity is changed by decomposition by the action of an acid (acid-decomposable resin), and a compound that generates an acid upon irradiation with light (photoacid generator). In such a resist composition, the photo-acid generator generates an acid upon exposure, and the polarity of the resin changes due to the action of the generated acid, thereby forming a desired pattern. However, the resolution of the pattern to be formed may become insufficient because it is accompanied by a mechanism in which dispersion of the acid is liable to occur.

In the resist composition of the present invention, the metal salt structure is decomposed by exposure, the metal ions are desorbed, and the polarity of the novolak-type phenol resin (C) is changed to form a desired pattern. High resolution is obtained in the resist composition of the present invention, which does not involve a mechanism in which acid diffusion tends to cause non-uniformity. In particular, in exposure using light of a short wavelength, such as an electron beam or extreme ultraviolet light, the resolution or pattern shape unevenness tends to become a problem, but the resist composition of the present invention can solve these problems.

As for the metal salt of a novolak-type phenol resin (C), part or all of the functional groups which a novolak-type phenol resin (C) has should just have a metal salt structure.

The metal salt of the novolak-type phenol resin (C) is preferably a carboxylic acid metal salt of the novolac-type phenol resin (C). The carboxylic acid metal salt of the novolak-type phenol resin (C) has a structure preferably represented by the following formula (X).

(in the above formula (X),

_{R 1, R 2, R 3} , m and n are of the formula _{(1) R 1, R 2} , R 3, equal to the m and n.

* is a bonding point with any one of the three aromatic rings of the formula (1), and two * may be bonded to the same aromatic ring or to different aromatic rings, respectively.

Met represents a metal atom.

n represents an integer greater than or equal to 1)

With respect to the structure represented by the formula (X), for example, when the valence of the metal atom is 1, 2, 3 or 4, the following formula (X1), (X2), (X3) or (X4) structure to be displayed.

In the resist composition of the present invention, the metal salt structure may be contained in the novolak-type phenol resin (C), and the content of the metal salt structure is, for example, among all the repeating units of the novolak-type phenol resin (C). For example, it is 1-80 mol%, Preferably it is 10-65 mol%, More preferably, it is 20-50 mol%.

In the resist composition of the present invention, whether or not a metal salt structure of the novolak-type phenol resin (C) is formed is confirmed by the method described in Examples.

Hereinafter, the components contained in the resist composition of the present invention will be described.

[Novolac-type phenolic resin]

A novolak-type phenol resin (C) is resin which uses the aromatic compound (A) represented by following formula (1), and an aliphatic aldehyde (B) as essential reaction raw materials.

(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.

m and n each independently represent the integer of 0-4.

If R ₁ is plural, a plurality of R ₁ are different from each other be the same.

If R ₂ is a plurality, the plurality of R ₂ may be the same or different from each other.

R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group)

In the formula (1), as _{the aliphatic hydrocarbon group having 1 to 9 carbon atoms for R 1} , R ₂ and R ₃ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and a hexyl group , an alkyl group having 1 to 9 carbon atoms, such as a cyclohexyl group, a heptyl group, an octyl group, and a nonyl group, and a cycloalkyl group having 3 to 9 carbon atoms.

In said Formula (1), a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group etc. are mentioned as an alkoxy group of _R<1> and R<_2>.

In said Formula (1), a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group etc. are mentioned as an aryl group of _R<1> and R<_2>.

In said Formula (1), as _{an aralkyl group of R<1>} and R<_2> , a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, etc. are mentioned.

In said Formula (1), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom of _R<1> and R<_2>.

In the formula (1), the "structural moiety having at least one substituent selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group" of _{R 3 is a halogenated alkyl group, halogenated aryl group, or 2-methoxyethoxy group.} , Alkoxyalkoxy groups, such as 2-ethoxyethoxy group, The alkylalkoxy group substituted by the hydroxyl group, etc. are mentioned.

In the formula (1), each of n and m is preferably an integer of 2 or 3.

When n and m are each 2, it _{is preferable that both R 1} and both R ₂ are each independently an alkyl group having 1 to 3 carbon atoms. At this time, _{it is preferable that both R<1>} and both R<_2> are couple|bonded at the 2,5-position of a phenolic hydroxyl group, respectively.

The aromatic compound (A) represented by the formula (1) may be used alone, or a plurality of compounds having different molecular structures may be used.

The aromatic compound (A) represented by the formula (1) can be prepared, for example, by a condensation reaction of an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a carboxyl group.

The aromatic compound (A) represented by the formula (1) can be prepared, for example, by a condensation reaction of an alkyl-substituted phenol (a1) and an aromatic ketone (a3) having a carboxyl group.

The alkyl-substituted phenol (a1) is a phenol substituted with an alkyl group, and examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and a methyl group is preferable.

Specific examples of the alkyl-substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, pt-butylphenol, o-cyclo monoalkylphenols such as hexylphenol, m-cyclohexylphenol and p-cyclohexylphenol; dialkyl phenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, and 2,6-xylenol; and trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol. Among these, dialkylphenol is preferable, and 2,5-xylenol and 2,6-xylenol are more preferable. Alkyl-substituted phenol (a1) may be used individually by 1 type, and may use 2 or more types together.

Aromatic aldehyde (a2) having a carboxyl group is a compound having a formyl group on an aromatic nucleus, such as benzene, naphthalene, phenol, resorcin, naphthol, dihydroxynaphthalene, and an alkyl group, an alkoxy group, a halogen atom, etc. in addition to the formyl group. The compound which has can be mentioned.

Specific examples of the aromatic aldehyde having a carboxyl group (a2) include 4-formylbenzoic acid, 2-formylbenzoic acid, 3-formylbenzoic acid, methyl 4-formylbenzoate, ethyl 4-formylbenzoate, and propyl 4-formylbenzoate. , 4-formyl benzoate isopropyl, 4-formyl benzoate butyl, 4-formyl benzoate isobutyl, 4-formyl benzoate tert-butyl, 4-formyl benzoate cyclohexyl, 4-formyl benzoate tertiary octyl, etc. can be heard Among these, 4-formylbenzoic acid is preferable. The aromatic aldehyde (a2) which has a carboxy group may be used individually by 1 type, and may use 2 or more types together.

The aromatic ketone (a3) having a carboxyl group is a compound having at least one carboxyl group or an ester derivative thereof and a carbonyl group in the aromatic ring.

Specific examples of the aromatic ketone (a3) having a carboxyl group include, for example, 2-acetylbenzoic acid, 3-acetylbenzoic acid, 4-acetylbenzoic acid, methyl 2-acetylbenzoate, ethyl 2-acetylbenzoate, propyl 2-acetylbenzoate; 2-acetylbenzoic acid isopropyl, 2-acetylbenzoic acid butyl, 2-acetylbenzoic acid isobutyl, 2-acetylbenzoic acid tertiary butyl, 2-acetylbenzoic acid cyclohexyl, 2-acetylbenzoic acid tertiary octyl, etc. are mentioned. Of these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferable.

An aromatic ketone (a3) may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the aliphatic aldehyde (B) include formaldehyde, paraformaldehyde, 1,3,5-trioxane, acetaldehyde, propionaldehyde, tetraoxymethylene, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butylaldehyde, caproaldehyde, allylaldehyde, crotonaldehyde, acrolein, and the like. An aliphatic aldehyde compound (B) may be used individually by 1 type, and may use 2 or more types together.

The aliphatic aldehyde (B) is preferably formaldehyde.

When formaldehyde and a fatty aldehyde other than formaldehyde are used as the fatty aldehyde (B), the amount of the fatty aldehyde other than formaldehyde used is preferably in the range of 0.05 to 1 mole per 1 mole of formaldehyde.

The manufacturing method of a novolak-type phenol resin (C), Preferably the following three processes 1-3 are included.

(Process 1)

An aromatic compound (A) is obtained by polycondensing an alkyl-substituted phenol (a1) and an aromatic aldehyde (a2) having a carboxyl group in the presence of an acid catalyst, using a solvent as needed, in a range of 60 to 140°C .

(Process 2)

The aromatic compound (A) obtained in step 1 is isolated from the reaction solution.

(Process 3)

The aromatic compound (A) and the aliphatic aldehyde (B) isolated in step 2 are heated in the presence of an acid catalyst and optionally using a solvent in a range of 60 to 140° C. to polycondensate, whereby a novolak-type phenol resin ( C) is obtained.

Examples of the acid catalyst used in Step 1 and Step 3 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, para-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts may be used alone or in combination of two or more. In addition, among these acid catalysts, sulfuric acid and para-toluenesulfonic acid are preferable in step 1, and sulfuric acid, oxalic acid, and zinc acetate are preferable in step 3 from the viewpoint of excellent activity. Moreover, an acid catalyst may be added before reaction, and it does not matter even if it adds in the middle of reaction.

As a solvent used as needed in the said process 1 and process 3, For example, Monoalcohol, such as methanol, ethanol, and a propanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol polyols such as , 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol mono glycol ethers such as phenyl ether; cyclic ethers such as 1,3-dioxane and 1,4-dioxane; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Aromatic hydrocarbons, such as toluene and xylene, etc. are mentioned. These solvents may be used alone or in combination of two or more. Moreover, the point excellent in the solubility of the compound obtained among these solvents to 2-ethoxyethanol is preferable.

The input ratio [(a1)/(a2)] of the alkyl-substituted phenol (a1) and the aromatic aldehyde having a carboxyl group (a2) in step 1 is the removability of the unreacted alkyl-substituted phenol (a1) and the yield of the product And since the purity of the reaction product is excellent, the molar ratio is preferably in the range of 1/0.2 to 1/0.5, and more preferably in the range of 1/0.25 to 1/3.45.

The input ratio [(A)/(B)] of the aromatic compound (A) and the aliphatic aldehyde (B) in step 3 can suppress excessive high molecular weight (gelation), and is suitable as a phenol resin for resist. Since a molecular weight thing is obtained, the range of 1/0.5 - 1/1.2 is preferable in molar ratio, and the range of 1/0.6 - 1/0.9 is more preferable.

As a method for isolating the aromatic compound (A) from the reaction solution in step 2, for example, the reaction solution is poured into a poor solvent (S1) in which the reaction product is insoluble or sparingly soluble, and a precipitate obtained is filtered. After fractionation, a method of dissolving the reaction product, dissolving in a solvent (S2) that is also miscible with the poor solvent (S1), and filtering the precipitate generated by introducing the reaction product into the poor solvent (S1) is exemplified.

Examples of the poor solvent (S1) used at this time include water; monoalcohols such as methanol, ethanol and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane and cyclohexane; and aromatic hydrocarbons such as toluene and xylene. Among these poor solvents (S1), since the acid catalyst can be efficiently removed simultaneously, water and methanol are preferable. On the other hand, as said solvent (S2), For example, Monoalcohol, such as methanol, ethanol, and a propanol; Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol polyols such as , 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol mono glycol ethers such as phenyl ether; cyclic ethers such as 1,3-dioxane and 1,4-dioxane; glycol esters such as ethylene glycol acetate; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. are mentioned. Moreover, when water is used as said poor solvent (S1), acetone is preferable as said (S2). Moreover, the said poor solvent (S1) and the solvent (S2) may be used individually by only 1 type, respectively, and may use 2 or more types together.

When an aromatic hydrocarbon such as toluene or xylene is used as a solvent in Step 1 and Step 3, when heated to 80° C. or higher, the aromatic compound (A) generated by the reaction dissolves in the solvent, so it is cooled as it is. Since crystals of the aromatic compound (A) are precipitated by doing so, the aromatic compound (A) can be isolated by filtration. In this case, it is not necessary to use the poor solvent (S1) and the solvent (S2).

The aromatic compound (A) represented by the above formula (1) can be obtained by the isolation method of step 2 described above. The purity of the aromatic compound (A) is preferably 90% or more, more preferably 94% or more, particularly preferably 98% or more in terms of the purity calculated from the gel permeation chromatography (GPC) chart. The purity of an aromatic compound (A) can be calculated|required from the area ratio of the chart diagram of GPC, and is measured on the measurement conditions mentioned later.

The range of 2,000-35,000 is preferable and, as for the weight average molecular weight (Mw) of a novolak-type phenol resin (C), the range of 2,000-25,000 is more preferable. The weight average molecular weight (Mw) of a novolak-type phenol resin (C) is measured on the following measurement conditions using gel permeation chromatography (it abbreviates to "GPC" hereafter).

(Measurement conditions for GPC)

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation

Column: Showa Denko Co., Ltd. “Shodex KF802” (8.0 mmФ×300 mm)

+ Showa Denko Co., Ltd. “Shodex KF802” (8.0mmФ×300㎜)

+ Showa Denko Co., Ltd. “Shodex KF803” (8.0mmФ×300㎜)

+ Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ×300 mm)

Column temperature: 40℃

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 model II version 4.30" manufactured by Tosoh Corporation

Developing solvent: tetrahydrofuran

Flow rate: 1.0mL/min

Sample: A 0.5 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a micro filter (100 μl)

Standard sample: the following monodisperse polystyrene

(standard sample: monodisperse polystyrene)

"A-500" made by Tosoh Corporation

"A-2500" made by Tosoh Corporation

"A-5000" made by Tosoh Corporation

"F-1" made by Tosoh Corporation

"F-2" made by Tosoh Corporation

"F-4" made by Tosoh Corporation

"F-10" made by Tosoh Corporation

"F-20" made by Tosoh Corporation

[Metal atoms forming metal salts]

Calcium, zinc, copper, iron, aluminum, zirconium, hafnium, titanium, indium, tin etc. are mentioned as a metal atom which forms a novolak-type phenol resin (C) and a metal salt. Among these, calcium, zinc, copper, iron, zirconium, hafnium and tin are preferable. The said metal atom may be used individually by 1 type, and may use 2 or more types together.

The metal salt of the novolak-type phenolic resin (C) is formed by adding a metal salt such as a hydrochloride, nitrate, and sulfate of a metal atom, and/or a metal oxide while heating a composition containing the novolak-type phenolic resin (C) can do. Of these, nitrates and/or metal oxides are preferable.

The addition amount of the said metal salt and/or a metal oxide is 1-100 mass parts with respect to 100 mass parts of novolak-type phenol resins (C), Preferably it is 10-50 mass parts.

[Alkali-soluble resin]

In the resist composition of the present invention, although the novolak-type phenol resin (C) is an alkali-soluble resin, an alkali-soluble resin (D) other than the novolak-type phenol resin (C) may be included.

Alkali-soluble resin (D) should just be resin soluble in aqueous alkali solution, and cresol novolak resin is preferable. The cresol novolak resin is a novolak-type phenol resin obtained by condensing a phenol-based compound and an aldehyde compound as a reaction raw material, preferably 1 selected from the group consisting of o-cresol, m-cresol and p-cresol. It is a resin which uses the above phenolic compound as an essential reaction raw material.

As a phenolic compound used as a reaction raw material of the said cresol novolak resin, you may use together phenols or phenol derivatives other than cresol. As a phenolic compound other than cresol, For example, phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, etc. Ilenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; butylphenols such as isopropylphenol, butylphenol, and p-t-butylphenol; alkylphenols such as p-pentylphenol, p-octylphenol, p-nonylphenol, and p-cumylphenol; halogenated phenols such as fluorophenol, chlorophenol, bromophenol, and iodophenol; monosubstituted phenols such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, and trinitrophenol; Condensed polycyclic phenols, such as 1-naphthol and 2-naphthol; polyhydric phenols such as resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol S, and dihydroxynaphthaline. can Phenolic compounds other than the said cresol may be used individually by 1 type, and may use 2 or more types together.

When cresol and a phenolic compound other than cresol are used as reaction raw materials in the preparation of the alkali-soluble resin (D), the amount of the phenolic compound other than cresol to be used is preferably in the range of 0.05 to 1.0 mol with respect to 1.0 mol of cresol. .

Examples of the aldehyde compound used as a raw material for the cresol novolak resin include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal. , n-butylaldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, and the like. Among these, formaldehyde is preferable. The said aldehyde compound may be used individually by 1 type, and may use 2 or more types together.

When formaldehyde is used as an aldehyde compound used as a raw material of the cresol novolak resin, an aldehyde compound other than formaldehyde may be used. When formaldehyde and an aldehyde compound other than formaldehyde are used as reaction raw materials in the preparation of the cresol novolak resin, the amount of the aldehyde compound other than formaldehyde used is in the range of 0.05 to 1.0 mol with respect to 1.0 mol of the formaldehyde. desirable.

The condensation reaction of the phenol-based compound and the aldehyde compound is preferably performed in the presence of an acid catalyst. Examples of the acid catalyst include oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. Among these, since it is excellent in catalytic activity, oxalic acid is preferable. The said acid catalyst may be used individually by 1 type, and may use 2 or more types together. The acid catalyst may be put in before the reaction, may be added during the reaction, or either may be used.

When preparing the cresol novolak resin, the charging ratio (molar ratio) of the phenolic compound and the aldehyde compound is preferably in the range of 0.3 to 1.6, and more preferably in the range of 0.5 to 1.3, wherein the aldehyde compound/phenolic compound is in the range of 0.3 to 1.6. Do.

As a specific example of the reaction between the phenolic compound and the aldehyde compound in preparing the cresol novolak resin, the phenolic compound and the aldehyde compound are heated to 60 to 140° C. in the presence of an acid catalyst to advance a polycondensation reaction, and then under reduced pressure. A method of performing dehydration and depilation under conditions is mentioned.

The resist composition of the present invention may or may not contain the photosensitive agent (E). As a photosensitizer (E), the compound which has a quinonediazide group can be used. Examples of the compound having a quinonediazide group include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4 ,4'-tetrahydroxybenzophenone, 2,3',4,4',6-pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2' ,3,4,5-pentahydroxybenzophenone, 2,3',4,4',5',6-hexahydroxybenzophenone, 2,3,3',4,4',5'-hexa polyhydroxybenzophenone compounds such as hydroxybenzophenone; bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(2', 3',4'-trihydroxyphenyl)propane, 4,4'-{1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol, 3,3' bis[(poly)hydroxyphenyl]alkane compounds such as -dimethyl-{1-[4-[2-(3-methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylidene}bisphenol; Tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxy hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis( Tris such as 4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane and bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane (hydroxyphenyl) methane or its methyl substituent; Bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-4 -Hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2 -Methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-3 -Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxy Roxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl) Naphthoquinone-1,2-diazide such as -2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methane or a methyl substituent thereof, etc. A complete ester compound, partial ester compound, amidate or A partial amidide etc. are mentioned. These photosensitizers (E) may be used only by 1 type, and may be used together 2 or more types.

The content of the photosensitive agent (E) in the resist composition of the present invention is 3 with respect to a total of 100 parts by mass of the novolak-type phenol resin (C) and the alkali-soluble resin (D) because good sensitivity is obtained and a desired pattern is obtained. The range of -50 mass parts is preferable, and the range of 5-30 mass parts is more preferable.

The resist composition of the present invention preferably contains a solvent (F). Examples of the solvent (F) include ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; cyclic ethers such as dioxane; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxy and esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. These solvents (F) may be used alone or in combination of two or more.

The content of the solvent (F) in the resist composition of the present invention is 15 to 65 mass %, since a uniform coating film can be obtained by applying the fluidity of the composition to a coating method such as a spin coating method. It is preferable to do so.

The resist composition of the present invention may contain a metal salt of a novolak-type phenolic resin (C), and optionally an alkali-soluble resin (D), a photosensitizer (E), and a solvent (F). metal salt, and optionally alkali-soluble resin (D), photosensitizer (E), solvent (F) and components other than components (C) to (F) (for example, surfactants such as fillers, pigments, leveling agents, etc.; 1 or more selected from a dissolution accelerator) may be included, and an unavoidable impurity may be included in the range which does not impair the effect of this invention.

In the resist composition of the present invention, for example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the solid content from which the solvent (F) is removed, the novolac-type phenolic resin The metal salt of (C) and optionally alkali-soluble resin (D), photosensitizer (E), and components other than components (C) to (F) may consist of.

The resist composition of the present invention is prepared by adding a novolak-type phenolic resin (C), a metal salt, other alkali-soluble resins (D) optionally blended, a photosensitizer (E) and a solvent (F), as well as various additives added as necessary. In this way, it can be prepared by stirring and mixing to obtain a uniform liquid.

When mixing solid substances such as fillers and pigments in the resist composition of the present invention, it is preferable to disperse and mix them using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill. Moreover, in order to remove granulation and impurities, the said composition can also be filtered using a mesh filter, a membrane filter, etc.

[Pattern Forming Method]

The resist composition of the present invention can be used both as a negative photoresist composition and as a positive photoresist. The method for producing a pattern using the resist composition of the present invention includes the steps of forming a resist film using the resist composition of the present invention, exposing the resist film, and developing the exposed resist film using a developer to form a pattern. It includes the process of forming.

Formation of a resist film, exposure of a resist film, and development of the exposed resist film can be performed by a well-known method. Examples of the light source for exposing the resist composition of the present invention include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. Among these light sources, ultraviolet light is preferable, and g-line (wavelength: 436 nm), i-line (wavelength: 365 nm), and EUV laser (wavelength: 13.5 nm) of a high-pressure mercury lamp are preferable.

As an alkali developing solution used for image development after exposure, For example, Inorganic alkaline substances, 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; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; Alkaline aqueous solutions, such as cyclic amines, such as pyrrole and piperidine, can be used. To these alkaline developing solutions, alcohol, surfactant, etc. can also be added and used suitably as needed. As for the alkali concentration of an alkali developing solution, the range of 2-5 mass % is preferable normally, and 2.38 mass % tetramethylammonium hydroxide aqueous solution is generally used.

The pattern formation method of this invention is used suitably in the manufacturing process of an electronic device. Examples of the electronic device include household electrical equipment, office automation equipment, media-related equipment, optical equipment, and communication equipment.

(Example)

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples.

Synthesis Example 1 Synthesis of phenolic trinuclear compound containing carboxylic acid

293.2 g (2.4 mol) of 2,5-xylenol and 150 g (1 mol) of 4-formylbenzoic acid were added to a 2000 ml 4-neck flask equipped with a cooling tube, and dissolved in 500 ml of acetic acid. After adding 5 ml of sulfuric acid while cooling in an ice bath, it was heated to 100°C with a mantle heater, and reacted with stirring for 2 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone and further reprecipitated with water, and then the precipitate was separated by filtration and dried under vacuum to obtain 283 g of a pale pink crystal precursor compound (A-1).

^{As a result of 13} C-NMR measurement of the obtained precursor compound (A-1), it was confirmed that it was a compound represented by the following structural formula. In addition, the purity (GPC purity) computed from a GPC chart figure was 95.3 %. A GPC chart of the precursor compound (A-1) ^{is shown in FIG. 1 , and a 13} C-NMR chart is shown in FIG. 2 .

Synthesis Example 2 Synthesis of phenolic trinuclear compound

293.2 g (2.4 mol) of 2,5-xylenol and 122 g (1 mol) of 2-hydroxybenzaldehyde were added to a 2000 ml 4-neck flask equipped with a cooling tube, and dissolved in 500 ml of 2-ethoxyethanol. After adding 10 ml of sulfuric acid while cooling in an ice bath, the mixture was heated to 100° C. with a mantle heater and reacted with stirring for 2 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was redissolved in acetone and further reprecipitated with water, and then the precipitate was filtered off and dried under vacuum to obtain 283 g of white crystal precursor compound (A'-2).

^{As a result of 13} C-NMR measurement of the obtained precursor compound (A'-2), it was confirmed that it was a compound represented by the following structural formula. In addition, the purity (GPC purity) calculated from the GPC chart was 98.2%. The GPC chart of the precursor compound (A'-2) ^{is shown in FIG. 3, and the 13} C-NMR chart is shown in FIG.

Preparation Example 1 Synthesis of carboxylic acid-containing novolak-type phenol resin

188 g of the precursor compound (A-1) and 16 g of 92% paraformaldehyde were added to a 1000 ml 4-neck flask equipped with a cooling tube, and then dissolved in 500 ml of acetic acid. After adding 10 ml of sulfuric acid while cooling in an ice bath, it was heated to 80° C. in an oil bath, and reacted with stirring for 4 hours. After completion of the reaction, water was added to the obtained solution to reprecipitate the crude product. The crude product was re-dissolved in acetone and further re-precipitated with water, the precipitate was filtered off, and vacuum dried to obtain 182 g of an orange powdery novolak-type phenol resin (C-1). The number average molecular weight (Mn) of the obtained novolak-type phenol resin (C-1) was 3946, the weight average molecular weight (Mw) was 8504, and the polydispersity (Mw/Mn) was 2.16. The GPC chart of a novolak-type phenol resin (C-1) is shown in FIG.

Preparation Example 2 Synthesis of carboxylic acid-containing novolac-type phenol resin

In the same manner as in Production Example 1, except that 9.4 g (0.025 mol) of the precursor compound (A-1) and 8.7 g (0.025 mol) of the precursor compound (A'-2) were used instead of the precursor compound (A-1). 16.8 g of a red powdery novolak-type phenol resin (C-2) was obtained. The number average molecular weight (Mn) of the obtained novolak-type phenol resin (C-2) was 3331, the weight average molecular weight (Mw) was 6738, and the polydispersity (Mw/Mn) was 2.02. The GPC chart of a novolak-type phenol resin (C-2) is shown in FIG.

Preparation Example 3 Synthesis of novolac resin

In a 2L 4-neck flask equipped with a stirrer and a thermometer, 552 g (4 mol) of 2-hydroxybenzoic acid, 498 g (3 mol) of 1,4-bis(methoxymethyl)benzene, 2.5 g of p-toluenesulfonic acid, and 500 g of toluene It injected|threw-in, the temperature was raised to 120 degreeC, and demethanol reaction was performed. It heated up and distilled under reduced pressure, 230 degreeC, vacuum distillation was performed for 6 hours, and 882 g of novolak resins (C'-3) of a pale yellow solid were obtained. The number average molecular weight (Mn) of the novolak resin (C'-3) was 1016, the weight average molecular weight (Mw) was 2782, and the polydispersity (Mw/Mn) was 2.74. The GPC chart of novolac resin (C'-3) is shown in FIG.

Preparation Example 4 Synthesis of novolak resin

In a 2L four-neck flask equipped with a stirrer and a thermometer, 648 g (6 mol) of m-cresol, 432 g (4 mol) of p-cresol, 2.5 g (0.2 mol) of oxalic acid, and 492 g of 42% formaldehyde were added, and the temperature was raised to 100 ° C. , reacted. Dehydration and distillation from normal pressure to 200°C, followed by distillation under reduced pressure at 230°C for 6 hours, gave 736 g of a pale yellow solid novolak resin (C'-4).

GPC of the novolak resin (C'-4) had a number average molecular weight (Mn) of 1450, a weight average molecular weight (Mw) of 10316, and a polydispersity (Mw/Mn) of 7.116. The GPC chart of novolac resin (C'-4) is shown in FIG.

Example 1

[Preparation of resin solution]

The novolak-type phenol resin (C-1) and propylene glycol monomethyl ether acetate (PGMEA) prepared in Production Example 1 were mixed in a mass ratio of novolak-type phenol resin (C-1):PGMEA = 20:80, It was set as the PGMEA solution of the rock-type phenol resin (C-1), this solution was micro-filtered with the disk filter made from a 0.1 micrometer of polytetrafluoroethylene, and the resin solution was prepared.

[Complex evaluation]

5 g of the resin solution obtained in a 30 ml heat-resistant tube and metal nitrate hydrates Ca(NO ₃ ) ₂ .4H ₂ O, Zn(NO ₃ ) ₂ .6H ₂ O, Cu(NO ₃ ) _{2 .3H 2} O and Fe(NO ₃ ) _{0.2g of 3} 9H ₂ O was added, respectively, and it heated to 100 degreeC, shaking-processing. The following reference|standard evaluated the state of the mixture of the resin solution and metal nitrate hydrate after heating. Table 1 shows the results of gelation evaluation.

○: Immovable gelation

△: viscous liquid

×: No change in viscosity

Since floating gelation or viscous liquidization was confirmed by the said evaluation, after adding 1 g of hydrochloric acid aqueous solution further, the shaking process was performed at room temperature for 3 hours. The following reference|standard evaluated the state of the metal nitrate hydrate containing resin solution after agitation process, and the presence or absence of formation of a metal salt structure was confirmed. Table 1 shows the results of the solation evaluation.

○: low viscosity liquid

△: viscous liquid

×: No state change

From the results in Table 1, the novolak-type phenol resin (C-1) of Production Example 1, which was made into a floating gel or viscous liquid by adding a metal nitrate hydrate, and was made into a low-viscosity liquid by further adding an aqueous hydrochloric acid solution, was obtained by addition of a metal nitrate hydrate. It was confirmed that a metal salt structure was formed.

Immovable gelation or viscous liquefaction by adding metal nitrate hydrate and low-viscosity liquefaction by further adding aqueous hydrochloric acid are reversible in the formation of a cross-linked structure due to the coordination bond between the metal and novolac and the decomposition of the cross-linked structure by its dissociation. Since it is a behavior showing that , it shows that the metal salt of a carboxylic acid is formed.

About the prepared resin solution, the following evaluation was performed separately. A result is shown in Table 1.

[Alkali developability evaluation]

The obtained resin solution was applied on a 5-inch silicon wafer with a spin coater so as to have a thickness of about 1 µm, dried on a hot plate at 110°C for 60 seconds, and a resin film was formed on the silicon wafer. The obtained wafer was immersed in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried for 60 seconds on a hot plate at 110°C. The film thickness before and after immersion in a developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability (ADR1 (Å/s)).

Photosensitizer P-200 (manufactured by Toyo Kosei Kogyo Co., Ltd.; 4,4'-[1-[4] so that the obtained resin solution becomes novolak-type phenolic resin/P-200/PGMEA = 20/5/75 (mass ratio)) Condensation product of 1 mole of -[1-(4-hydroxyphenyl)-1methylethyl]phenyl]ethylidene]bisphenol and 2 moles of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride ) was added, and this resin composition was applied on a 5-inch silicon wafer with a spin coater to a thickness of about 1 µm, dried on a hot plate at 110°C for 60 seconds, and a resin film was formed on the silicon wafer. The obtained wafer was immersed in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried for 60 seconds on a hot plate at 110°C. The film thickness before and after immersion in a developer was measured, and the value obtained by dividing the difference by 60 was defined as alkali developability (ADR2 (Å/s)).

[Heat resistance evaluation]

The obtained resin solution was applied on a 5-inch silicon wafer with a spin coater so as to have a thickness of about 1 µm, dried on a hot plate at 110°C for 60 seconds, and a resin film was formed on the silicon wafer. This resin film was scraped off, the glass transition point temperature (it abbreviates hereafter as "Tg") was measured, and the following reference|standard evaluated.

○: Tg is 150°C or higher

×: Tg is 150°C or less

In addition, the measurement of Tg uses a differential thermal scanning calorimeter ("Differential thermal scanning calorimeter (DSC) Q100" manufactured by T.A. Instruments Co., Ltd.) in a nitrogen atmosphere, in a temperature range of -100 to 200°C, and a temperature increase rate of 10°C It was performed under the condition of /min.

Example 2 and Comparative Example 1-2

A resin solution was prepared and evaluated in the same manner as in Example 1 except that the resin shown in Table 1 was used instead of the novolak-type phenol resin (C-1). A result is shown in Table 1. In addition, about the resin solution of novolak resin (C'-3) and novolak resin (C'-4), when there was no viscosity change in gelation evaluation, evaluation of solization was not performed.

[Table 1]

Claims (9)

A resist composition comprising a metal salt of a novolak-type phenol resin (C) comprising an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction raw materials.

(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom.
m and n each independently represent the integer of 0-4.
If R ₁ is plural, a plurality of R ₁ are different from each other be the same.
If R ₂ is a plurality, the plurality of R ₂ may be the same or different from each other.
R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural moiety having one or more substituents selected from an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group) According to claim 1,
The resist composition wherein the metal salt is a carboxylic acid metal salt. 3. The method of claim 1 or 2,
A resist composition wherein the metal valence of the metal salt is at least one selected from a calcium atom, a zinc atom, a copper atom, and an iron atom. 4. The method according to any one of claims 1 to 3,
The resist composition, wherein the aromatic compound (A) is a polycondensate of a phenol compound, an aromatic aldehyde having a carboxy group or a carboxy ester group, and/or an aromatic ketone having a carboxy group or a carboxy ester group. 5. The method of claim 4,
The resist composition wherein the aromatic aldehyde having a carboxyl group is formylbenzoic acid. 6. The method according to any one of claims 1 to 5,
The resist composition wherein the aliphatic aldehyde (B) is formaldehyde and/or paraformaldehyde. A step of forming a resist film using the resist composition according to any one of claims 1 to 6;
exposing the resist film;
and developing the exposed resist film using a developer to form a pattern. 8. The method of claim 7,
The pattern forming method in which the said exposure is exposure by an electron beam or an extreme ultraviolet-ray. The manufacturing method of the electronic device containing the pattern formation method of Claim 7 or 8.

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