TW202031764A - Resist composition - Google Patents

Abstract

The purpose of the present invention is to provide a resist composition which exhibits high heat resistance and can be used in types of lithography that use electron beams and extreme ultraviolet radiation. Specifically, the present invention uses a resist composition that contains a metal salt of a novolac type phenolic resin (C), which is obtained using (A) an aromatic compound represented by formula (1) and (B) an aliphatic aldehyde as essential reaction raw materials. (In formula (1), R1 and R2 each independently denote a hydrogen atom, an aliphatic hydrocarbon group having 1-9 carbon atoms, an alkoxy group, an aryl group, an aralkyl group or a halogen atom. m and n each independently denote an integer between 0 and 4. In cases where a plurality of R1 groups are present, the plurality of R1 groups may be the same as, or different from, each other. In cases where a plurality of R2 groups are present, the plurality of R2 groups may be the same as, or different from, each other. R3 denotes a hydrogen atom, an aliphatic hydrocarbon group having 1-9 carbon atoms, or a structural moiety having one or more substituent groups selected from among alkoxy groups, halogen groups and hydroxyl groups on a hydrocarbon group.).

Description

Resist composition

The present invention relates to resist compositions.

As a resist used in the manufacture of semiconductors such as IC and LSI, the manufacture of LCDs and other display devices, and the manufacture of printing original plates, it is known to use alkali-soluble resins and photosensitive agents such as 1,2-naphthoquinonediazide compounds. Type photoresist. As the alkali-soluble resin, it has been proposed to use a mixture of m-cresol novolak resin and p-cresol novolak resin as a positive photoresist composition of the alkali-soluble resin (for example, refer to Patent Document 1).

The positive photoresist composition described in Patent Document 1 was developed for the purpose of improving the developability of sensitivity, etc. However, in recent years, the high integration of semiconductors has increased, and the pattern tends to be thinner, which requires more excellent的sensitivity. However, in the positive photoresist composition described in Patent Document 1, there is a problem that sufficient sensitivity corresponding to thinning is not obtained. Furthermore, since various heat treatments are applied in the manufacturing process of semiconductors, etc., high heat resistance is also required. However, the positive photoresist composition described in Patent Document 1 has a problem of insufficient heat resistance .

In addition, especially in the field of semiconductor manufacturing such as IC and LSI, finer processing is required, and lithography using electron beams or extreme ultraviolet (EUV) is reviewed. With the shortening of the wavelength of the exposure source, further improvement of the characteristics of the resist composition corresponding to it is required. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-55359

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide a resist composition which has high heat resistance and can be used in lithography using electron beams and extreme ultraviolet rays. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors conducted intensive studies and found a resist composition comprising a phenolic aldehyde obtained by reacting a carboxylic acid-containing phenolic trinuclear compound having a specific structure with an aliphatic aldehyde. The metal salt structure of the varnish-type phenol resin has high heat resistance and can be used in lithography using electron beams and extreme ultraviolet rays to complete the present invention.

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

(前述式(1)中，R₁ 及R₂ 各自獨立地表示氫原子、碳原子數1～9的脂肪族烴基、烷氧基、芳基、芳烷基或鹵素原子； m及n各自獨立地表示0～4之整數； R₁ 為複數時，複數的R₁ 可互相相同，也可相異； R₂ 為複數時，複數的R₂ 可互相相同，也可相異； R₃ 表示氫原子、碳原子數1～9的脂肪族烴基或在烴基上具有1個以上的選自烷氧基、鹵基及羥基之取代基的結構部位)。 [發明之效果]

(In the aforementioned formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, a C 1-9 aliphatic hydrocarbon group, an alkoxy group, an aryl group, an aralkyl group, or a halogen atom; m and n are each independently Ground represents an integer from 0 to 4; when R ₁ is a plural number, the plural R ₁ may be the same as or different from each other; when R ₂ is plural, the plural R ₂ may be the same or different from each other; R ₃ represents hydrogen Atom, an aliphatic hydrocarbon group having 1 to 9 carbon atoms, or a structural site having one or more substituents selected from an alkoxy group, a halogen group, and a hydroxyl group on the hydrocarbon group). [Effects of Invention]

According to the present invention, a resist composition can be provided, which has high heat resistance and can be used in lithography using electron rays and extreme ultraviolet rays.

[Form to implement the invention]

Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate changes within a range that does not impair the effects of the present invention.

[Resist composition] The resist composition of the present invention contains 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 necessary reaction materials.

(前述式(1)中，R₁ 及R₂ 各自獨立地表示氫原子、碳原子數1～9的脂肪族烴基、烷氧基、芳基、芳烷基或鹵素原子； m及n各自獨立地表示0～4之整數； R₁ 為複數時，複數的R₁ 可互相相同，也可相異； R₂ 為複數時，複數的R₂ 可互相相同，也可相異； R₃ 表示氫原子、碳原子數1～9的脂肪族烴基或在烴基上具有1個以上的選自烷氧基、鹵基及羥基之取代基的結構部位)。

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

The resist composition usually contains a resin (acid decomposable resin) whose polarity changes due to decomposition by acid and a compound (photoacid generator) that generates acid due to light irradiation. In such a resist composition, the photoacid generator generates acid by exposure, and the polarity of the resin changes due to the effect of the generated acid to form a desired pattern. However, due to the mechanism that is prone to uneven diffusion of acid, the resolution of the formed pattern may become insufficient.

The resist composition of the present invention decomposes the metal salt structure due to exposure, the metal ions are detached, and the polarity of the novolak-type phenol resin (C) changes to form a desired pattern. In the resist composition of the present invention that does not have a mechanism that easily causes uneven diffusion of acid, high resolution can be obtained. Especially in exposure using short-wavelength light such as electron beams and extreme ultraviolet rays, resolution or pattern shape irregularities are likely to become problems. However, the resist composition system of the present invention can eliminate this problem.

The metal salt of the novolak-type phenol resin (C) only needs to have part or all of the functional groups that the novolak-type phenol resin (C) has a metal salt structure. The metal salt of the novolak type phenol resin (C) is preferably a carboxylic acid metal salt of the novolak type phenol resin (C). The carboxylic acid metal salt of the novolak-type phenol resin (C) preferably has a structure represented by the following formula (X).

(前述式(X)中， R₁ 、R₂ 、R₃ 、m及n係與前述式(1)的R₁ 、R₂ 、R₃ 、m及n相同； ＊係與前述式(1)的3個芳香環之任一個的鍵結點，2個＊可鍵結至相同的芳香環，也可各自鍵結至不同的芳香環； Met表示金屬原子； n表示1以上之整數)。

(In the aforementioned formula (X), R ₁ , R ₂ , R ₃ , m and n are the same as R ₁ , R ₂ , R ₃ , m and n in the aforementioned formula (1); * is the same as the aforementioned formula (1) For the bonding points of any one of the three aromatic rings, 2* can be bonded to the same aromatic ring, or each can be bonded to different aromatic rings; Met represents a metal atom; n represents an integer greater than 1).

Regarding the structure represented by the aforementioned formula (X), for example, when the valence of the aforementioned metal atom is 1, 2, 3, or 4, each is represented by the following formula (X1), (X2), (X3) or (X4) Structure.

In the resist composition of the present invention, as long as the novolak type phenol resin (C) contains a metal salt structure, the content of the metal salt structure is in all the repeating units of the novolak type phenol resin (C) , For example, 1 to 80 mol%, preferably 10 to 65 mol%, more preferably 20 to 50 mol%.

In the resist composition of the present invention, whether the metal salt structure of the novolak type phenol resin (C) is formed can be confirmed by the method described in the examples.

Hereinafter, the components contained in the resist composition of the present invention will be explained. [Novolak type phenol resin] The novolak-type phenol resin (C) is a resin containing an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as essential reaction materials.

(前述式(1)中，R₁ 及R₂ 各自獨立地表示氫原子、碳原子數1～9的脂肪族烴基、烷氧基、芳基、芳烷基或鹵素原子； m及n各自獨立地表示0～4之整數； R₁ 為複數時，複數的R₁ 可互相相同，也可相異； R₂ 為複數時，複數的R₂ 可互相相同，也可相異； R₃ 表示氫原子、碳原子數1～9的脂肪族烴基或在烴基上具有1個以上的選自烷氧基、鹵基及羥基之取代基的結構部位)。

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

In the aforementioned formula (1), examples of the aliphatic hydrocarbon groups having 1 to 9 carbon atoms for R ₁ , R ₂ and R ₃ include methyl, ethyl, propyl, isopropyl, butyl, and tertiary C1-C9 alkyl groups such as hexyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, and C3-9 cycloalkyl group.

In the aforementioned formula (1), examples of the alkoxy group of R ₁ and R ₂ include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, cyclohexyloxy, etc. .

In the aforementioned formula (1), examples of the aryl groups of R ₁ and R ₂ include phenyl, tolyl, xylyl, naphthyl, anthryl and the like.

In the aforementioned formula (1), examples of the aralkyl group of R ₁ and R ₂ include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, and the like.

In the aforementioned formula (1), examples of the halogen atom of R ₁ and R ₂ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the aforementioned formula (1), as "a structural part having one or more substituents selected from the group consisting of an alkoxy group, a halogen group and a hydroxyl group on the hydrocarbon group" of R ₃ , there can be exemplified halogenated alkyl groups, halogenated aryl groups, and 2 -Methoxyethoxy, 2-ethoxyethoxy and other alkoxy alkoxy groups, alkyl alkoxy groups substituted by hydroxy groups, etc.

In the aforementioned formula (1), each of n and m is preferably an integer of 2 or 3. When n and m are each 2, two R ₁ and two R ₂ are each independently preferably an alkyl group having 1 to 3 carbon atoms. In this case, each of the two R ₁ and the two R _{2 is} preferably bonded to the 2,5-position of the phenolic hydroxyl group.

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

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

The alkyl-substituted phenol (a1) is an alkyl-substituted phenol, and the alkyl group includes an alkyl group having 1 to 8 carbon atoms, and a methyl group is preferred.

Specific examples of the alkyl-substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethyl phenol, m-ethyl phenol, p-ethyl phenol, p-octyl phenol, and p-cresol. Monoalkylphenols such as butylphenol, o-cyclohexylphenol, m-cyclohexylphenol, and p-cyclohexylphenol; 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2 , 4-xylenol, 2,6-xylenol and other dialkylphenols; 2,3,5-trimethylphenol, 2,3,6-trimethylphenol and other trialkylphenols. Among these, dialkylphenols are preferred, and 2,5-xylenol and 2,6-xylenol are more preferred. The alkyl-substituted phenol (a1) system may be used individually by 1 type, and may use 2 or more types together.

The aromatic aldehyde (a2) having a carboxyl group can include compounds having a formyl group on the aromatic nucleus of benzene, naphthalene, phenol, resorcinol, naphthol, dihydroxynaphthalene, etc., in addition to formyl group. Compounds having alkyl groups, alkoxy groups, halogen atoms, etc.

Specific examples of the aromatic aldehyde (a2) having a carboxyl group include 4-methanoic acid, 2-methanoic acid, 3-methanoic acid, and methyl 4-methanoic acid. , Ethyl 4-methanyl benzoate, propyl 4-methanyl benzoate, isopropyl 4-methanyl benzoate, butyl 4-methanyl benzoate, isopropyl 4-methanyl benzoate Butyl ester, tertiary butyl 4-methanyl benzoate, cyclohexyl 4-methanyl benzoate, tertiary octyl 4-methanyl benzoate, etc. Among these, 4-methanylbenzoic acid is preferred. The aromatic aldehyde (a2) system which has a carboxyl 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 on 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, and 2-acetylbenzoic acid Methyl ester, ethyl 2-acetyl benzoate, propyl 2-acetyl benzoate, isopropyl 2-acetyl benzoate, butyl 2-acetyl benzoate, 2-acetyl benzene Isobutyl formate, tertiary butyl 2-acetylbenzoate, cyclohexyl 2-acetylbenzoate, tertiary octyl 2-acetylbenzoate, etc. Among these, 2-acetylbenzoic acid and 4-acetylbenzoic acid are preferable. The aromatic ketone (a3) system may be used individually by 1 type, and may use 2 or more types together.

烷、乙醛、丙醛、四甲醛、聚甲醛、三氯乙醛、六亞甲基四胺、糠醛、乙二醛、正丁醛、己醛、烯丙醛、巴豆醛、丙烯醛等。脂肪族醛化合物(B)係可單獨使用1種，也可併用2種以上。Specific examples of aliphatic aldehydes (B) include formaldehyde, paraformaldehyde, 1,3,5-tri

Alkanes, acetaldehyde, propionaldehyde, tetraformaldehyde, polyformaldehyde, chloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, crotonaldehyde, acrolein, etc. The aliphatic aldehyde compound (B) may be used alone or in combination of two or more.

The aliphatic aldehyde (B) is preferably formaldehyde. As the aliphatic aldehyde (B), when formaldehyde and aliphatic aldehydes other than formaldehyde are used, the use amount of the aliphatic aldehydes other than formaldehyde is preferably in the range of 0.05 to 1 mol relative to 1 mol of formaldehyde.

The manufacturing method of the novolak type phenol resin (C) preferably includes the following three steps 1 to 3. (step 1) The alkyl-substituted phenol (a1) and the aromatic aldehyde (a2) having a carboxyl group in the presence of an acid catalyst, optionally using a solvent, are heated in the range of 60 to 140°C, and the aromatic compound is obtained by polycondensation (A). (Step 2) The aromatic compound (A) obtained in step 1 is isolated from the reaction solution. (Step 3) The aromatic compound (A) and the aliphatic aldehyde (B) isolated in step 2 are heated in the range of 60 to 140°C in the presence of an acid catalyst and a solvent as needed to obtain a phenol aldehyde by polycondensation Varnish-type phenol resin (C).

Examples of the acid catalyst used in Step 1 and Step 3 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. Only one type of these acid catalysts may be used, or two or more types may be used in combination. In addition, among these acid catalysts, from the viewpoint of excellent activity, sulfuric acid and p-toluenesulfonic acid are preferred in step 1, and sulfuric acid, oxalic acid, and zinc acetate are preferred in step 3. In addition, the acid catalyst system may be added before the reaction, or may be added during the reaction.

烷、1,4-二

烷等之環狀醚；乙二醇乙酸酯等之二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等之酮；甲苯、二甲苯等之芳香族烴等。此等之溶劑係可僅使用1種，也併用2種以上。又，於此等之溶劑之中，從所得之化合物的溶解性優異之點來看，較佳為2-乙氧基乙醇。As the solvent used as needed in the above step 1 and step 3, for example, monohydric alcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butane Alcohol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethyl Polyols such as glycol, polyethylene glycol, glycerol, etc.; 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 monophenyl ether and other glycol ethers; 1,3-bis

Alkane, 1,4-bis

Cyclic ethers such as alkanes; 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. Only one type of these solvents may be used, or two or more types may be used in combination. In addition, among these solvents, 2-ethoxyethanol is preferred from the viewpoint of excellent solubility of the obtained compound.

The addition ratio of alkyl-substituted phenol (a1) and carboxyl-containing aromatic aldehyde (a2) in step 1 [(a1)/(a2)], the removal and formation of unreacted alkyl-substituted phenol (a1) In view of the excellent yield of the product and the purity of the reaction product, 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 1/0.45.

The addition ratio of aromatic compound (A) and aliphatic aldehyde (B) in step 3 [(A)/(B)] can suppress excessive high molecular weight (gelation) and obtain phenol resin for resist The molar ratio is preferably in the range of 1/0.5 to 1/1.2, more preferably in the range of 1/0.6 to 1/0.9.

As a method of 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 poorly soluble, and the resulting precipitate is separated by filtration After that, the reaction product is dissolved, dissolved in the solvent (S2) that is also mixed with the poor solvent (S1), and then poured into the poor solvent (S1) again, and the resulting precipitate is separated by filtration.

烷、1,4-二

烷等之環狀醚；乙二醇乙酸酯等之二醇酯；丙酮、甲基乙基酮、甲基異丁基酮等之酮等。又，使用水作為前述不良溶劑(S1)時，前述(S2)較佳為丙酮。還有，前述不良溶劑(S1)及溶劑(S2)係可各自僅1種使用，也可併用2種以上。Examples of the poor solvent (S1) used at this time include water; monohydric alcohols such as methanol, ethanol, and propanol; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and cyclohexane; and toluene , Xylene and other aromatic hydrocarbons. Among these poor solvents (S1), water and methanol are preferable in terms of efficiently removing the acid catalyst at the same time. On the other hand, as the aforementioned solvent (S2), for example, monohydric alcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol , Polyethylene glycol, glycerol and other polyols; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl Ethylene glycol ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether and other glycol ethers; 1,3-bis

Alkane, 1,4-bis

Cyclic ethers such as alkanes; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. In addition, when water is used as the poor solvent (S1), the (S2) is preferably acetone. In addition, the aforementioned poor solvent (S1) and solvent (S2) may be used only one type each, or two or more types may be used in combination.

When aromatic hydrocarbons such as toluene and xylene are used as the solvent in the above steps 1 and 3, if heating at 80°C or higher, the aromatic compound (A) produced by the reaction is dissolved in the solvent, so Direct cooling, since the crystals of the aforementioned aromatic compound (A) are precipitated, by separating them by filtration, the aforementioned aromatic compound (A) can be isolated. In this case, the aforementioned poor solvent (S1) and solvent (S2) may not be used.

The aromatic compound (A) represented by the aforementioned formula (1) can be obtained by the single ionization method of the above step 2. The purity of the aromatic compound (A) is calculated from a gel permeation chromatography (GPC) chart, and is preferably 90% or more, more preferably 94% or more, and particularly preferably 98% or more. The purity of the aromatic compound (A) can be obtained from the area ratio of the GPC chart, and is measured under the measurement conditions described later.

The weight average molecular weight (Mw) of the novolak-type phenol resin (C) is preferably in the range of 2,000 to 35,000, more preferably in the range of 2,000 to 25,000. The weight average molecular weight (Mw) of the novolak type phenol resin (C) is measured using a gel permeation chromatography (hereinafter referred to as "GPC") under the following measurement conditions.

(GPC measurement conditions) Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation Pillar: "Shodex KF802" (8.0mmФ×300mm) manufactured by Showa Denko Co., Ltd. + "Shodex KF802" made by Showa Denko Corporation (8.0mmФ×300mm) + "Shodex KF803" made by Showa Denko Corporation (8.0mmФ×300mm) + "Shodex KF804" made by Showa Denko Corporation (8.0mmФ×300mm) 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% by mass tetrahydrofuran solution (100μl) in terms of the solid content of the resin filtered by a microfilter Standard sample: the following monodisperse polystyrene

(Standard sample: monodisperse polystyrene) Tosoh Corporation "A-500" Tosoh Corporation "A-2500" "A-5000" manufactured by Tosoh Corporation Tosoh Corporation "F-1" Tosoh Corporation "F-2" "F-4" manufactured by Tosoh Corporation Tosoh Corporation "F-10" Tosoh Corporation "F-20"

[Metal atoms forming metal salts] Examples of the metal atom forming a metal salt with the novolak type phenol resin (C) include calcium, zinc, copper, iron, aluminum, zirconium, hafnium, titanium, indium, tin, and the like. Among these, calcium, zinc, copper, iron, zirconium, hafnium, and tin are preferred. The aforementioned metal atom system may be used singly or in combination of two or more kinds.

The metal salt of the novolak type phenol resin (C) can be heated by heating the composition containing the novolak type phenol resin (C), while adding metal salts such as hydrochloride, nitrate, and sulfate of metal atoms and or Metal oxide is formed. Among these, nitrates and or metal oxides are preferred.

The addition amount of the aforementioned metal salt and or metal oxide is, for example, 1 to 100 parts by mass, and preferably 10 to 50 parts by mass, relative to 100 parts by mass of the novolak-type phenol resin (C).

[Alkali-soluble resin] In the resist composition of the present invention, the novolak-type phenol resin (C) is an alkali-soluble resin, but it may also contain an alkali-soluble resin (D) other than the novolak-type phenol resin (C).

The alkali-soluble resin (D) may be any resin soluble in an aqueous alkali solution, and a cresol novolak resin is preferred. The aforementioned cresol novolak resin is a novolak type phenol resin formed by condensation of phenolic compounds and aldehyde compounds as raw materials, preferably selected from the group consisting of o-cresol, m-cresol and p-cresol One or more phenolic compounds in the group are the necessary reaction raw materials for the resin.

As the phenolic compound used as the reaction raw material of the aforementioned cresol novolak resin, a phenol or a phenol derivative other than cresol may be used in combination. Examples of phenolic compounds other than cresol include phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -Xylenol such as xylenol and 3,5-xylenol; ethyl phenol such as o-ethyl phenol, m-ethyl phenol and p-ethyl phenol; isopropyl phenol, butyl phenol, p-tertiary Butyl phenol such as butyl phenol; alkyl phenol such as p-pentyl phenol, p-octyl phenol, p-nonyl phenol, p-cumyl phenol; halogenation of fluorophenol, chlorophenol, bromophenol, iodophenol, etc. Phenol; 1-substituted phenol such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol, etc.; 1-naphthol, 2-naphthol, etc., condensation polycyclic phenol; resorcinol Phenol, alkyl resorcinol, gallic phenol, catechol, alkyl catechol, hydroquinone, alkyl hydroquinone, phlotriol, bisphenol A, bisphenol F, bisphenol S, dihydroxy naphthalene And other polyphenols. The phenolic compound system other than the aforementioned cresol may be used alone or in combination of two or more kinds.

In the preparation of alkali-soluble resin (D), when cresol and phenolic compound other than cresol are used as the reaction raw material, the usage amount of the aforementioned phenolic compound other than cresol is preferably 0.05 to 1.0 mol relative to cresol. 1.0 mol range.

烷、乙醛、丙醛、聚甲醛、三氯乙醛、六亞甲基四胺、糠醛、乙二醛、正丁醛、己醛、烯丙醛、苯甲醛、巴豆醛、丙烯醛、四甲醛、苯基乙醛、鄰甲苯甲醛、水楊醛等。於此等之中，較佳為甲醛。前述醛化合物係可單獨1種使用，也可併用2種以上。As the aldehyde compound used as the raw material of the aforementioned cresol novolak resin, for example, formaldehyde, paraformaldehyde, three

Alkane, acetaldehyde, propionaldehyde, polyformaldehyde, chloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, hexanal, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetra Formaldehyde, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, etc. Among these, formaldehyde is preferred. The above-mentioned aldehyde compound system may be used individually by 1 type, and may use 2 or more types together.

As the aldehyde compound used as the raw material of the aforementioned cresol novolak resin, when formaldehyde is used, an aldehyde compound other than formaldehyde may also be used. In the preparation of the cresol novolak resin, when formaldehyde and an aldehyde compound other than formaldehyde are used as raw materials for the reaction, the amount of the aldehyde compound other than formaldehyde is preferably in the range of 0.05 to 1.0 mol relative to 1.0 mol of the aforementioned formaldehyde .

The condensation reaction of the aforementioned phenolic compound and aldehyde compound is preferably carried out in the presence of an acid catalyst. Examples of the acid catalyst include oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. Among these, oxalic acid is preferred in terms of excellent catalytic activity. The aforementioned acid catalyst system may be used singly or in combination of two or more kinds. The acid catalyst system can be added before or during the reaction, either.

The addition ratio (molar ratio) of the phenolic compound and the aldehyde compound when preparing the aforementioned cresol novolak resin is preferably the aldehyde compound/phenolic compound in the range of 0.3 to 1.6, more preferably in the range of 0.5 to 1.3 .

As a specific example of the reaction between the phenolic compound and the aldehyde compound when preparing the aforementioned 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 the polycondensation reaction. , And then carry out the method of dehydration and monomer removal under reduced pressure.

The resist composition of the present invention may or may not contain the photosensitizer (E). As the photosensitizer (E), a compound having a quinonediazide group can be used. As the compound having a quinonediazide group, for example, 2,3,4-trihydroxydiphenyl ketone, 2,4,4'-trihydroxydiphenyl ketone, 2,4,6-trihydroxy Diphenylketone, 2,3,6-trihydroxydiphenylketone, 2,3,4-trihydroxy-2'-methyldiphenylketone, 2,3,4,4'-tetrahydroxydiphenyl Ketone, 2,2',4,4'-tetrahydroxydiphenyl ketone, 2,3',4,4',6-pentahydroxydiphenyl ketone, 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'-hexahydroxydiphenyl ketone and other polyhydroxydiphenyl ketone compounds; 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]ethylene}bisphenol, 3,3'-dimethyl-{1-[4-[2-(3 -Methyl-4-hydroxyphenyl)-2-propyl]phenyl]ethylene}bisphenol and other bis[(poly)hydroxyphenyl]alkane compounds; see (4-hydroxyphenyl)methane, Bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis( 4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4- Hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, etc. The ginseng (hydroxyphenyl) methanes or their methyl substituents; 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-hydroxy Phenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, 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-2-hydroxy-4-methylphenyl)- Bis(cyclohexylhydroxyphenyl)(hydroxyphenyl)methanes such as 4-hydroxyphenylmethane or its methyl substituents and naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone- Complete ester compounds, partial ester compounds, amides or partial amides of sulfonic acids with quinonediazide groups such as 1,2-diazide-4-sulfonic acid, o-anthraquinonediazide sulfonic acid, etc. . These photosensitizers (E) may be used only one type, or two or more types may be used in combination.

The content of the photosensitizer (E) in the resist composition of the present invention is 100 relative to the total of the novolak-type phenol resin (C) and the alkali-soluble resin (D) in terms of obtaining good sensitivity and obtaining the desired pattern. Parts by mass are preferably in the range of 3-50 parts by mass, more preferably in the range of 5-30 parts by mass.

烷等的環式醚；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙醯乙酸甲酯、乙醯乙酸乙酯等之酯等。此等之溶劑(F)係可僅1種使用，也可併用2種以上。The resist composition of the present invention preferably contains a solvent (F). As the aforementioned solvent (F), for example, ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. ; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.; methyl race Ethylene glycol alkyl ether acetate such as loxoacetate, ethyl siloxe acetate, etc.; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ethyl Propylene glycol alkyl ether acetate such as acid esters; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl amyl ketone, etc.; two

Cyclic ethers such as alkane; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2- Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, Esters such as methyl acetylacetate and ethyl acetylacetate. Only one type of these solvents (F) may be used, or two or more types may be used in combination.

The content of the solvent (F) in the resist composition of the present invention, in view of the fluidity of the composition and obtaining a uniform coating film by coating methods such as spin coating, is preferably such that the resist composition of the present invention The solid content concentration in the bismuth is 15 to 65% by mass.

The resist composition of the present invention only needs to contain the metal salt of the novolak type phenol resin (C) and optionally the alkali-soluble resin (D), the photosensitizer (E) and the solvent (F), and may also contain the novolak type The metal salt of the phenol resin (C) and the optional alkali-soluble resin (D), photosensitizer (E), solvent (F), and components other than components (C) to (F) (such as fillers, pigments, and One or more selected from surfactants, adhesion promoters, and dissolution promoters, such as leveling agents, may also contain unavoidable impurities within the range that does not impair the effects of the present invention.

The resist composition of the present invention is, 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 solid components other than the solvent (F), but it may also contain novolac type phenol The metal salt of the resin (C) and the arbitrarily included alkali-soluble resin (D), photosensitizer (E), and components other than the components (C) to (F).

The resist composition of the present invention can be mixed with novolak type phenol resin (C), metal salt, optional other alkali-soluble resin (D), photosensitizer (E) and solvent (F) by a usual method. , According to the need to add various additives, become a uniform liquid and prepare.

When solids such as fillers and pigments are blended into the resist composition of the present invention, it is preferable to use a dispersing device such as a dissolver, a homogenizer, or a three-roll mill for dispersion and mixing. In addition, in order to remove coarse particles or impurities, a mesh filter, a membrane filter, etc. may be used to filter the composition.

[Pattern Formation Method] The resist composition of the present invention can be used as a negative photoresist composition, and can also be used as a positive photoresist. The manufacturing method of the pattern using the resist composition of the present invention includes the step of forming a resist film using the resist composition of the present invention, the step of exposing the aforementioned resist film, and the use of a developer to expose the aforementioned exposed The resist film is developed to form a pattern.

The formation of the resist film, the exposure of the resist film, and the development of the exposed resist film can be implemented by well-known methods. As a light source for exposing the resist composition of the present invention, for example, infrared light, visible light, ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc. can be cited. Among these light sources, ultraviolet light is preferable, and g-line (wavelength: 436nm), i-line (wavelength: 365nm), EUV laser (wavelength: 13.5nm) of a high-pressure mercury lamp.

As the alkaline developer used in the development after exposure, for example, inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc. can be used; among others, ethylamine, n-propylamine, etc. Primary amines; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; hydroxide Quaternary ammonium salts of tetramethylammonium and tetraethylammonium hydroxide; alkaline aqueous solutions of cyclic amines such as pyrrole and piperidine. In these alkaline developers, alcohol, surfactant, etc. can be suitably added and used as needed. The alkali concentration of the alkali developer is generally preferably in the range of 2 to 5% by mass, and a 2.38% by mass tetramethylammonium hydroxide aqueous solution is generally used.

The pattern forming method of the present invention is applicable to the manufacturing process of electronic devices. Examples of the above-mentioned electronic devices include household electrical equipment, office automation equipment, media-related equipment, optical equipment, and communication equipment. [Example]

Hereinafter, the present invention will be explained concretely with examples and comparative examples.

Synthesis Example 1 "Synthesis of phenolic trinuclear compound containing carboxylic acid In a 2000 ml 4-necked flask equipped with a cooling tube, 293.2 g (2.4 mol) of 2,5-xylenol and 150 g (1 mol) of 4-methanyl benzoic acid were added 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 heating bag, and the reaction was allowed to react while stirring for 2 hours. After the completion of the reaction, water was added to the resulting solution to re-precipitate the crude product. The crude product was re-dissolved in acetone, and after reprecipitating with water, the precipitate was separated by filtration and vacuum dried to obtain 283 g of the precursor compound (A-1) of pale pink crystals.

The obtained precursor compound (A-1) was subjected to ¹³ C-NMR measurement, and as a result, it was confirmed to be a compound represented by the following structural formula. In addition, the purity (GPC purity) calculated from the GPC chart was 95.3%. Fig. 1 shows a GPC chart of the precursor compound (A-1), and Fig. 2 shows a ¹³ C-NMR chart.

Synthesis Example 2" Synthesis of Phenolic Trinuclear Compound Add 293.2g (2.4mol) of 2,5-xylenol and 122g (1mol) of 2-hydroxybenzaldehyde in a 2000ml 4-necked flask equipped with a cooling tube, and dissolve in 500ml of 2-ethoxyethanol in. After adding 10 ml of sulfuric acid while cooling in an ice bath, it was heated to 100°C with a heating bag, and the reaction was allowed to react while stirring for 2 hours. After the completion of the reaction, water was added to the resulting solution to re-precipitate the crude product. The crude product was re-dissolved in acetone and reprecipitated with water, and the precipitate was separated by filtration and vacuum-dried to obtain 283 g of a white crystal precursor compound (A'-2).

The obtained precursor compound (A'-2) was subjected to ¹³ C-NMR measurement, and as a result, it was confirmed to be a compound represented by the following structural formula. In addition, the purity (GPC purity) calculated from the GPC chart was 98.2%. Fig. 3 shows the GPC chart of the precursor compound (A'-2), and Fig. 4 shows the ¹³ C-NMR chart.

Production Example 1 "Synthesis of carboxylic acid-containing novolac type phenol resin In a 1000 ml 4-necked flask equipped with a cooling tube, 188 g of the precursor compound (A-1) and 16 g of 92% paraformaldehyde were added and 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 while stirring for 4 hours. After the completion of the reaction, water was added to the resulting solution to re-precipitate the crude product. The crude product was re-dissolved in acetone, and after reprecipitating with water, the precipitate was separated by filtration and vacuum dried to obtain 182 g of orange powder 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. Fig. 5 shows the GPC chart of the novolak type phenol resin (C-1).

Production Example 2 "Synthesis of carboxylic acid-containing novolac type phenol resin Except that instead of the precursor compound (A-1), 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, the same as in Production Example 1 Similarly, 16.8 g of a light red powder 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. Fig. 6 shows the GPC chart of the novolak type phenol resin (C-2).

Production Example 3 "Synthesis of novolac resin In a 2L 4-neck flask equipped with a stirrer and a thermometer, add 552g (4mol) of 2-hydroxybenzoic acid, 498g (3mol) of 1,4-bis(methoxymethyl)benzene, and 2.5g of p-toluenesulfonate Acid and 500 g of toluene were heated up to 120°C to perform a methanol removal reaction. The temperature was increased under reduced pressure, distillation was performed, and vacuum distillation was performed at 230°C for 6 hours to obtain 882 g of light yellow solid novolak resin (C'-3). The number average molecular weight (Mn) of the novolak resin (C'-3) is 1016, the weight average molecular weight (Mw) is 2782, and the polydispersity (Mw/Mn) is 2.74. Fig. 7 shows the GPC chart of the novolak resin (C'-3).

Production Example 4 "Synthesis of novolac resin In a 2L 4-neck flask equipped with a stirrer and a thermometer, add 648g (6mol) of m-cresol, 432g (4mol) of p-cresol, 2.5g (0.2mol) of oxalic acid, and 492g of 42% formaldehyde, and heat to 100 It is allowed to react up to °C. It was dehydrated and distilled to 200°C under normal pressure, and distilled under reduced pressure at 230°C for 6 hours to obtain 736 g of light yellow solid novolak resin (C'-4). The GPC of the novolak resin (C'-4) is that the number average molecular weight (Mn) is 1450, the weight average molecular weight (Mw) is 10316, and the polydispersity (Mw/Mn) is 7.116. Fig. 8 shows the GPC chart of the novolak resin (C'-4).

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 are used in a mass ratio of novolak-type phenol resin (C-1):PGMEA=20:80 The mixture was mixed to form a PGMEA solution of novolak-type phenol resin (C-1), and this solution was subjected to precision filtration with a 0.1 μm polytetrafluoroethylene disc filter to prepare a resin solution.

[Composite Evaluation] 5g of the resulting resin was added a solution of 0.2g with a metal nitrate hydrate in 30ml tube heat _{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 ) ₃ ·9H ₂ O are heated to 100°C while shaking. The state of the mixture of the heated resin solution and the metal nitrate hydrate was evaluated using the following criteria. Table 1 shows the results of the gelation evaluation. ○: Immobile gelation △: Viscous liquefaction ×: No viscosity change

According to the above evaluation, after confirming that it does not gel or viscous liquid, 1g of hydrochloric acid aqueous solution is added, and shaking treatment is performed at room temperature for 3 hours. Evaluate the state of the metal nitrate hydrate-containing resin solution after shaking treatment with the following criteria to confirm whether a metal salt structure is formed. Table 1 shows the results of the solization evaluation. ○: Low viscosity liquefaction △: viscous liquid ×: No state change

From the results in Table 1, it can be confirmed that the novolak-type phenol resin of Production Example 1 (C-1) does not gel or become viscous liquefied due to the addition of metal nitrate hydrate, and is liquefied with low viscosity due to the addition of hydrochloric acid aqueous solution. ), the metal salt structure is formed by adding metal nitrate hydrate.

Those that do not gel or viscous liquefaction due to the addition of metal nitrate hydrate, and low-viscosity liquefaction due to the addition of hydrochloric acid aqueous solution, are due to the following behavior: coordination bond between metal and novolak The formation of the cross-linked structure, and the decomposition of the cross-linked structure caused by its dissociation is reversible, so it means that the metal salt of carboxylic acid has been formed.

For the prepared resin solution, the following evaluation was additionally performed. The results are shown in Table 1. [Evaluation of alkali developability] The resulting resin solution was applied with a spin coater to a thickness of about 1 μm on a 5-inch silicon wafer, and dried on a hot plate at 110°C for 60 seconds to form a resin film on the silicon wafer. The resulting wafer was immersed in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110°C for 60 seconds. The film thickness before and after immersion in the developer was measured, and the difference was divided by 60 as the alkali developability (ADR1 (Å/s)).

To the obtained resin solution, add the photosensitizer P-200 (manufactured by Toyo Gosei Kogyo Co., Ltd.; 1mol) so that it becomes a novolak type phenol resin/P-200/PGMEA=20/5/75 (mass ratio) 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1methylethyl]phenyl]ethylene] bisphenol and 2 moles of 1,2-naphthoquinone Condensate of -2-diazide-5-sulfonyl chloride), to a thickness of about 1μm on a 5-inch silicon wafer, apply the resin composition with a spin coater and place it on a hot plate at 110°C Dry for 60 seconds to form a resin film on the silicon wafer. The resulting wafer was immersed in a developing solution (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds, and then dried on a hot plate at 110°C for 60 seconds. The film thickness before and after immersion in the developer was measured, and the difference was divided by 60 as the alkali developability (ADR2 (Å/s)).

[Evaluation of heat resistance] The resulting resin solution was applied with a spin coater to a thickness of about 1 μm on a 5-inch silicon wafer, and dried on a hot plate at 110°C for 60 seconds to form a resin film on the silicon wafer. This resin film was scraped off, the glass transition point temperature (hereinafter referred to as "Tg") was measured, and the evaluation was performed using the following criteria. ○: Tg is above 150℃ ×: Tg is below 150℃ In addition, Tg was measured using a differential scanning calorimeter ("Differential Scanning Calorimeter (DSC) Q100" manufactured by TA Instruments Co., Ltd.) in a nitrogen atmosphere, with a temperature range of -100 to 200°C, and a heating rate of 10°C /Min.

Example 2 and Comparative Example 1-2 Except having used the resin shown in Table 1 instead of the novolak-type phenol resin (C-1), it carried out similarly to Example 1, and prepared the resin solution, and evaluated. The results are shown in Table 1. In addition, regarding the resin solutions of the novolak resin (C'-3) and the novolak resin (C'-4), when there is no change in viscosity in the gelation evaluation, the evaluation of solization is not performed.

[Table 1] Example 1 Example 2 Comparative example 1 Comparative example 2 Resin C-1 C-2 C'-3 C'-4 Alkali developability ADR1 [Å/s] 15000 10000 3500 110 ADR2 [Å/s] 80 56 2900 15 Heat resistance Tg [℃] 270 220 52 110 determination ○ ○ × × Composite Ca(NO ₃ ) ₂ ･4H ₂ O Gelation △ △ × × Solization ○ ○ - - Zn(NO ₃ ) ₂ ･6H ₂ O Gelation △ △ × × Solization ○ ○ - - Cu(NO ₃ ) ₂ ･3H ₂ O Gelation ○ ○ △ × Solization ○ ○ × - Fe(NO ₃ ) ₃ ･9H ₂ O Gelation ○ ○ △ × Solization ○ ○ △ -

no.

Figure 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. 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. FIG. Fig. 6 is a GPC chart of the novolak-type phenol resin obtained in Production Example 2. FIG. 7 is a GPC chart of the novolak resin obtained in Production Example 3. FIG. Fig. 8 is a GPC chart of the novolak resin obtained in Production Example 4.

no.

Claims (9)

A resist composition comprising a metal salt of a novolac type phenol resin (C) with an aromatic compound (A) represented by the following formula (1) and an aliphatic aldehyde (B) as necessary reaction materials;

(In 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 are each independently Represents an integer from 0 to 4; when R ₁ is a plural number, the plural R ₁ may be the same or different from each other; when R ₂ is plural, the plural 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 site having one or more substituents selected from the group consisting of an alkoxy group, a halogen group, and a hydroxyl group on the hydrocarbon group). The resist composition of claim 1, wherein the metal salt is a metal carboxylate. The resist composition of claim 1 or 2, wherein the metal atom of the metal salt is one or more selected from calcium atoms, zinc atoms, copper atoms, and iron atoms. The resist composition according to any one of claims 1 to 3, wherein the aromatic compound (A) is a phenol compound and an aromatic aldehyde having a carboxyl group or a carboxyl ester group and/or an aromatic having a carboxyl group or a carboxyl ester group Polycondensate of ketone. The resist composition of claim 4, wherein the aromatic aldehyde having a carboxyl group is methanoic acid. The resist composition according to any one of claims 1 to 5, wherein the aliphatic aldehyde (B) is formaldehyde and/or paraformaldehyde. A pattern forming method, which includes: The step of forming a resist film using the resist composition of any one of claims 1 to 6, The step of exposing the resist film, and The step of developing the exposed resist film to form a pattern using a developing solution. The pattern forming method of claim 7, wherein the exposure is exposure by electron beams or extreme ultraviolet rays. A method of manufacturing an electronic device, which includes the pattern forming method of claim 7 or 8.

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