WO2021230185A1

WO2021230185A1 - Compound, production method therefor, composition, resist film, and pattern formation method

Info

Publication number: WO2021230185A1
Application number: PCT/JP2021/017657
Authority: WO
Inventors: 宏人工藤; 隆佐藤; 禎大松; 雅敏越後
Original assignee: 学校法人関西大学; 三菱瓦斯化学株式会社
Priority date: 2020-05-11
Filing date: 2021-05-10
Publication date: 2021-11-18
Also published as: JPWO2021230185A1; TW202201127A

Abstract

Provided is a compound in which the hydroxy groups of a polyphenol are crosslinked within each molecule by a group containing a degradable bond that is degraded under acidic or alkaline conditions. The polyphenol is preferably a calixarene.

Description

Compounds and methods for producing them, compositions, resist films, and pattern forming methods.

The present invention relates to a compound and a method for producing the same, a composition, a resist film, a pattern forming method, and a lower layer film for lithography and an optical article formed by the composition.

In the manufacture of semiconductor devices, microfabrication is performed by lithography using photoresist materials, but in recent years, with the increasing integration and speed of LSIs (large-scale integrated circuits), further miniaturization by pattern rules has been performed. Is required.

The general resist material so far is a polymer-based resist material capable of forming an amorphous thin film. Examples thereof include polymer-based resist materials such as polymethylmethacrylate and polyhydroxystyrene or polyalkylmethacrylate having a dissociative reactive group. Then, ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays (Extreme UltraViolet: hereinafter, appropriately referred to as "EUV") are applied to the resist thin film prepared by applying a solution of such a polymer-based resist material on the substrate. By irradiating with X-rays or the like, a line pattern of about 45 to 100 nm is formed (see, for example, Non-Patent Document 1).

However, the polymer-based resist material has a large molecular weight of about 10,000 to 100,000 and has a wide molecular weight distribution. For this reason, in lithography using a polymer-based resist material, roughness occurs on the surface of a fine pattern, it becomes difficult to control the pattern size, and the yield decreases. Therefore, there is a limit to miniaturization in lithography using a conventional polymer-based resist material. Various low molecular weight resist materials have been proposed to produce finer patterns.

For example, an alkali-developed negative-type radiation-sensitive composition using a low molecular weight polynuclear polyphenol compound as a main component has been proposed (see, for example, Patent Documents 1 and 2). Further, as a candidate for a low molecular weight resist material having high heat resistance, an alkali-developed negative-type negative radiation-sensitive composition using a low molecular weight cyclic polyphenol compound as a main component has been proposed (for example, Patent Document 3 and non-patent). See Document 2). Further, it is known that as a base compound of a resist material, a polyphenol compound can impart high heat resistance while having a low molecular weight and is useful for improving the resolution and roughness of a resist pattern (see, for example, Non-Patent Document 3). ). Further, Patent Document 4 discloses a resist material in which calixarene is cross-linked between molecules.

In addition, the reaction mechanism of lithography using electron beam or extreme ultraviolet (EUV) is different from that of ordinary optical lithography. Furthermore, in lithography using an electron beam or EUV, the goal is to form a fine pattern of several tens of nm. As the resist pattern size becomes smaller as described above, a resist material having higher sensitivity to the exposure light source is required. Particularly in EUV lithography, it is necessary to increase the sensitivity of the resist composition in terms of throughput.

As a resist material for improving these, for example, an inorganic resist material having titanium, hafnium or zirconium has been proposed (see, for example, Patent Documents 5 and 6).

Japanese Unexamined Patent Publication No. 2005-326838 Japanese Unexamined Patent Publication No. 2008-145539 Japanese Unexamined Patent Publication No. 2009-173623 Japanese Unexamined Patent Publication No. 2017-88847 Japanese Patent Application Laid-Open No. 2015-75500 Japanese Unexamined Patent Publication No. 2015-108781

However, the inorganic resist material has low sensitivity, and it is required to further improve the resolution in terms of resolution. Further, in an optical article, a composition having high sensitivity and high resolution is desired. In view of such circumstances, it is an object of the present invention to provide a compound and a composition that provide a resist material having high sensitivity and high resolution.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that a specific compound can solve the above-mentioned problems, and have completed the present invention. That is, the present invention is as follows.
[1]
A compound having a polyphenol moiety, wherein the hydroxyl group of the polyphenol is intramolecularly crosslinked with a group containing a dissociative bond that dissociates under acid or alkaline conditions.
[2]
The compound according to [1], wherein the polyphenol is calixarene.
[3]
The compound according to [1] or [2], which is a compound represented by the formula (P-0C) or (P-1C) described later.
[4]
The compound according to [1] to [3] represented by the formula (P-0A) or (P-1A) described later.
[5]
The compound according to any one of [1] to [4], wherein the dissociative bond is an ester bond.
[6]
The compound according to any one of [1] to [5], wherein the intramolecular crosslinking group is represented by the formula (C-0) described later.
[7]
The compound according to any one of [1] to [6], wherein the intramolecular cross-linking group in the formula (P-0C) is represented by the formula (C-0A) described later.
[8]
The compound according to any one of [1] to [7], which is represented by the formula (M-0) described later.
[9]
The compound according to [8], which is represented by the formula (M-0A) described later.
[10]
The compound according to any one of [1] to [6], wherein the intramolecular cross-linking group in the formula (P-1C) is represented by the formula (C-1A) described later.
[11]
The compound according to any one of [1] to [6] or [10], which is represented by the formula (M-1) described later.
[12]
The compound according to [11], which is represented by the formula (M-1A) described later.
[13]
[1]-[. 12] The method for producing a compound according to any one of.
[14]
The production method according to [13], wherein the cross-linking agent is represented by the formula (C-hal) described later.
[15]
The production method according to [14], wherein the cross-linking agent is represented by the formula (C-0hal) or (C-1hal) described later.
[16]
A composition for forming a resist film containing the compound according to any one of [1] to [12] or a derivative thereof.
[17]
The composition for forming a resist film according to [16], further containing a component selected from the group consisting of a solvent, an acid generator, an acid cross-linking agent, and a combination thereof.
[18]
A resist film formed from the composition according to [16] or [17].
[19]
A film forming step of forming a film on a substrate using the resist film forming composition according to [16] or [17], and a film forming step.
The exposure process for exposing the film and
A developing step of developing a film exposed in the exposure step to form a pattern, and a developing step of forming a pattern.
Pattern forming method including.
[20]
A curable composition containing the compound according to any one of [1] to [12] or a derivative thereof.
[21]
The curable composition according to [20], further containing a silicon-containing compound.
[22]
The curable composition according to [21], wherein the silicon-containing compound is a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzed condensate thereof.
[23]
The curable composition according to any one of [20] to [22], further containing a component selected from the group consisting of a solvent, an acid generator, an acid cross-linking agent, and a combination thereof.
[24]
An underlayer film formed from the curable composition according to any one of [20] to [23].
[25]
A step of forming a resist underlayer film using the curable composition according to any one of [20] to [23], and
A step of forming at least one photoresist layer on the resist underlayer film and
A step of irradiating a predetermined area of the photoresist layer with radiation to develop the photoresist layer,
A pattern forming method.
[26]
An optical article formed from the curable composition according to any one of [20] to [23].
[27]
A step of dissolving the compound according to any one of [1] to [12] or a derivative thereof in a solvent containing an organic solvent that is not miscible with water to obtain a solution (B).
The first extraction step of bringing the obtained solution (B) into contact with an acidic aqueous solution to extract impurities in the compound or its derivative.
Purification method including.
[28]
The acidic aqueous solution is one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and tartrate acid. The purification method according to [27], which is one or more organic acid aqueous solutions selected from the group consisting of citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid.
[29]
The organic solvent that is not miscible with water is one or more organic solvents selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate []. 27] or [28].
[30]
Any of [27] to [29], which comprises a second extraction step of contacting the solution phase containing the compound or derivative with water after the first extraction step to extract impurities in the compound or derivative. The purification method described in.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a compound and a composition that provide a resist material having high sensitivity and high resolution.

¹ H-NMR spectrum of BAB-DMHDO IR spectrum of BAB-DMHDO ¹ H-NMR spectrum of BCA [4] -co-BAB-DMHDO IR spectrum of BCA [4] -co-BAB-DMHDO

Hereinafter, embodiments of the present invention will be described (hereinafter, may be referred to as "the present embodiment"). The present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.

[Compound]
In the compound according to this embodiment, the hydroxyl group of the polyphenol is intramolecularly crosslinked with a group containing a dissociative bond that dissociates under acid or alkaline conditions. That is, the compound has a group having a structure of —AO— that crosslinks two hydroxyl groups with each other in one embodiment. In this case, A is a divalent organic group that dissociates under acid or alkaline conditions. In another embodiment, the compound has three or more hydroxyl groups intramolecularly crosslinked.

The dissociative bond that dissociates under acid or alkaline conditions is not limited as long as it is a bond that dissociates under the conditions, and examples thereof include ester bonds and amide bonds.

Polyphenol is a compound having two or more phenolic hydroxyl groups, preferably calixarene. In this embodiment, calixarene refers to a cyclic compound obtained by a condensation reaction between a phenolic compound and an aldehyde.

The compound according to this embodiment is preferably represented by the following formula (P-0C).

^{^{1) L 1 ~ L 4 L}} 1 ~ L 4 For each independently a single bond, a straight-chain alkylene group of having 1 to 20 carbon atoms have a substituent, substituted A branched alkylene group having 3 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent, and an arylene group having 6 to 24 carbon atoms which may have a substituent may be used. , -O-, -OC (= O)-, -OC (= O) O-, -O-R ^2- C (= O) O-, -N (R ²⁰ ) -C (= O)-, A divalent organic group selected from the group consisting of -N (R ²⁰ ) -C (= O) O-, -S-, -SO-, -SO _{2- and any combination thereof.}

As the linear alkylene group, an alkylene group having 1 to 4 carbon atoms is preferable. Examples of the branched alkylene group include an alkylene group having 3 to 6 carbon atoms. As the cycloalkylene group, a cycloalkylene group having 5 to 7 carbon atoms is preferable. Examples of the arylene group include a phenylene group and a naphthylene group. R ² is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group. R ²⁰ is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent, and is preferably a hydrogen atom or a methyl group.

In one embodiment, two or more ^L 1 ~ ^{L 4} is ^{-O-R 2 -C (= O} ) O group, it can be involved in intramolecular bridge. When two or more L ¹ to L ⁴ are involved in the ^{intramolecular cross-linking, it is preferable that some R 16} to R ¹⁹ are involved in the intramolecular cross-linking as a divalent group. Further, R ² is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group.

R ¹⁶ ~ ^{R 19} for ²⁾ ^R 16 ^~ R ^19, when not involved in intramolecular bridge, independently, a group selected from the following.
A linear alkyl group having 1 to 20 carbon atoms which may have a substituent;
A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent;
An aryl group having 6 to 20 carbon atoms which may have a substituent;
An alkoxyl group having 1 to 20 carbon atoms which may have a substituent;
Cyano group;
Nitro group;
Hydroxy group;
Heterocyclic group;
Halogen atom;
Carboxyl group;
Alkylsilyl group with 1 to 20 carbon atoms;
Substituent methyl group having 2 to 20 carbon atoms, 1-substituted ethyl group having 3 to 20 carbon atoms, 1-substituted-n-propyl group having 4 to 20 carbon atoms, and 3 to 20 carbon atoms having the property of being dissociated by an acid. 1-branched alkyl group, silyl group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, cyclic ether group having 2 to 20 carbon atoms, carbon number of carbon atoms. A group selected from the group consisting of 2 to 20 alkoxycarbonyl groups and alkoxycarbonylalkyl groups;
Hydrogen atom.
When R ¹⁶ to R ¹⁹ are involved in intramolecular cross-linking, they may be divalent groups independently derived from the groups selected from the above.

Examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms, and more preferably a t-butyl group. As the cycloalkyl group, a cycloalkyl group having 5 to 7 carbon atoms is preferable. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkoxyl group include an alkoxyl group having 1 to 4 carbon atoms.

Examples of the heterocyclic group include a heterocyclic group having 4 to 20 carbon atoms and containing O, S, or N as a heteroatom, preferably a furanyl group, a thiophenyl group, an imidazolyl group, a pyrrolyl group, and pyridyl. The group etc. can be mentioned. Examples of the alkylsilyl group include an alkylsilyl group having 1 to 20 carbon atoms.

Examples of the halogen atom include F, Cl, Br, and I, but F or Cl is preferable.

As the substituted methyl group having 2 to 20 carbon atoms having the property of being dissociated by an acid, a substituted methyl group having 4 to 18 carbon atoms is preferable, and a substituted methyl group having 6 to 16 carbon atoms is more preferable. Specific examples of the substituted methyl group include, but are not limited to, a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an n-propoxymethyl group, an isopropoxymethyl group, an n-butoxymethyl group, and a t-butoxymethyl group. 2-Methylpropoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, phenyloxymethyl group, 1-cyclopentyloxymethyl group, 1-cyclohexyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4 -Methylphenacyl group, piperonyl group, substituent group represented by the following formula (1) and the like can be mentioned. In the following formula (1), R ^2A is an alkyl group having 1 to 4 carbon atoms. Specific examples of R ^2A include, but are not limited to, a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a t-butyl group, an n-butyl group and the like.

As the 1-substituted ethyl group having 3 to 20 carbon atoms having the property of being dissociated by an acid, a 1-substituted ethyl group having 5 to 18 carbon atoms is preferable, and a substituted ethyl group having 7 to 16 carbon atoms is more preferable. Specific examples of the 1-substituted ethyl group include, but are not limited to, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, t-butoxyethyl group, 2-methylpropoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl Group, 1,1-diphenoxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, and substitution represented by the following formula (2). The base group and the like can be mentioned. In the following formula (2), R ^2A is as defined by the above formula (1).

As the 1-substituted-n-propyl group having 4 to 20 carbon atoms which has the property of being dissociated by an acid, the 1-substituted-n-propyl group having 6 to 18 carbon atoms is preferable, and the 1-substituted-n-propyl group having 8 to 16 carbon atoms is preferable. The -n-propyl group is more preferred. Specific examples of the 1-substituted-n-propyl group include, but are not limited to, 1-methoxy-n-propyl group and 1-ethoxy-n-propyl group.

As the 1-branched alkyl group having 3 to 20 carbon atoms which has the property of being dissociated by an acid, a 1-branched alkyl group having 5 to 18 carbon atoms is preferable, and a branched alkyl group having 7 to 16 carbon atoms is more preferable. Specific examples of the 1-branched alkyl group are not limited to the following, but are limited to an isopropyl group, a sec-butyl group, a t-butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group and a 1,1-dimethylbutyl group. , 2-Methyl adamantyl group, 2-ethyl adamantyl group and the like.

As the silyl group having 1 to 20 carbon atoms having the property of being dissociated by an acid, a silyl group having 3 to 18 carbon atoms is preferable, and a silyl group having 5 to 16 carbon atoms is more preferable. Specific examples of the silyl group include, but are not limited to, a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiethylsilyl group, and a t-butyldiphenylsilyl. Examples include a group, a tri-t-butylsilyl group, a triphenylsilyl group and the like.

As the acyl group having 2 to 20 carbon atoms having the property of being dissociated by an acid, an acyl group having 4 to 18 carbon atoms is preferable, and an acyl group having 6 to 16 carbon atoms is more preferable. Specific examples of the acyl group include, but are not limited to, an acetyl group, a phenoxyacetyl group, a propionyl group, a butyryl group, a heptanoyle group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a laurylloyl group, an adamantyl carbonyl group and a benzoyl group. Examples include groups and naphthoyl groups.

As the 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms which has the property of being dissociated by an acid, a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms is preferable, and a 1-substituted alkoxymethyl group having 4 to 18 carbon atoms is preferable. More preferably, a 1-substituted alkoxymethyl group having 6 to 16 carbon atoms is further preferable. Specific examples of the 1-substituted alkoxymethyl group are not limited to the following, but are limited to 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group and 1-cyclooctyl. Examples thereof include a methoxymethyl group and a 1-adamantyl methoxymethyl group.

As the cyclic ether group having 2 to 20 carbon atoms which has the property of being dissociated by an acid, a cyclic ether group having 4 to 18 carbon atoms is preferable, and a cyclic ether group having 6 to 16 carbon atoms is more preferable. Specific examples of the cyclic ether group include, but are not limited to, a tetrahydropyranyl group, a tetrahydropyranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 4-methoxytetrahydropyranyl group and a 4-methoxytetrahydrothiopyrani. Lu groups and the like can be mentioned.

As the alkoxycarbonyl group having 2 to 20 carbon atoms which has the property of being dissociated by an acid, an alkoxycarbonyl group having 4 to 18 carbon atoms is preferable, and an alkoxycarbonyl group having 6 to 16 carbon atoms is more preferable. Specific examples of the alkoxycarbonyl group include, but are not limited to, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group, and the following formula (3). ) Can be mentioned as a group represented by n = 0.

As the alkoxycarbonylalkyl group having the property of being dissociated by an acid, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms is preferable, an alkoxycarbonylalkyl group having 4 to 18 carbon atoms is more preferable, and an alkoxycarbonylalkyl group having 6 to 16 carbon atoms is more preferable. Groups are even more preferred. Specific examples of the alkoxycarbonylalkyl group include, but are not limited to, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and the following formula (3). ) N = 1 to 4, and the like can be mentioned.

In the formula (3), R ^3A is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 4.

3) About L ¹ R ¹⁶ to L ⁴ R ¹⁹ groups m ^{7 to 10} represent the number of these groups, respectively, and are independently integers of 1 to 4. If m ^{7 to 10} is large, the compound may become unstable, so m ^{7 to 10} is preferably 1 to 2, more preferably 1.

At ^{least two of the L 1} R ¹⁶ to L ⁴ R ¹⁹ groups are ether-bonded to the benzene ring and form an intramolecular cross-linking group. In one embodiment, two of the L ¹ R ¹⁶ to L ⁴ R ¹⁹ groups form an intramolecular cross-linking group represented by the formula (C-0).

In the above formula, A is a divalent group derived from ^{R 16} to R ^19. Specifically, A is derived from the above-mentioned alkyl group; cycloalkyl group; aryl group; alkoxyl group; heterocyclic group; carboxyl group; alkylsilyl group having 1 to 20 carbon atoms; a group having a property of being dissociated by an acid 2 It is the basis of the price. Considering the ease of producing the compound and the like, A is preferably an alkylene group having 4 to 10 carbon atoms. Therefore, two of the L ¹ R ¹⁶ to L ⁴ R ¹⁹ groups more preferably form an intramolecular cross-linking group represented by the formula (C-0A).

⁴⁾ ^R ¹² ~ R ¹⁵ for R 12 ^{~ R 15} are independently hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or aryl of the formula (P-0C-1) 6 to 24 carbon atoms represented by A group or a group derived from these. The alkyl group having 1 to 20 carbon ^atoms, may be mentioned those described in ^R 16 ^~ R ^19. R ¹² to R ¹⁵ are preferably hydrogen atoms.

In the formula (P-0C-1), R ²¹ is selected from the following.
Alkyl group having 1 to 20 carbon atoms which may have a substituent;
A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent;
An aryl group having 6 to 20 carbon atoms which may have a substituent;
An alkoxy group having 1 to 20 carbon atoms, which may have a substituent,
Cyano group;
Nitro group;
Heterocyclic group;
Halogen atom;
Carboxyl group;
Alkylsilyl group with 1 to 20 carbon atoms;
Substituent methyl group having 2 to 20 carbon atoms, 1-substituted ethyl group having 3 to 20 carbon atoms, 1-substituted-n-propyl group having 4 to 20 carbon atoms, and 3 to 20 carbon atoms having the property of being dissociated by an acid. 1-branched alkyl group, silyl group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, cyclic ether group having 2 to 20 carbon atoms, carbon number of carbon atoms. A group selected from the group consisting of 2 to 20 alkoxycarbonyl groups and alkoxycarbonylalkyl groups.

Specific examples of these groups ^are as described in ^R 16 ^~ R ^19. Further, p ⁷ indicates the number of R ²¹ and is an independent integer of 0 to 5. p ⁷ is 0 to 1, more preferably preferably 0.

The compound of this embodiment is preferably represented by the formula (P-0A). In the formula, ^RA is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and is preferably a t-butyl group. In the compound, in the formula (P-0C), R ¹² to R ¹⁵ are hydrogen atoms, and m ^{7 to 10} are 2. And of the two L ¹ R ¹⁶ existing in one benzene ring, one is ^RA (for example, ^{a linear alkylene group in which L 1} has 1 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms, R ¹⁶ is a hydrogen atom), and the other is D. The same applies ^{to L 2} R ¹⁷ to L ⁴ R ¹⁹ existing in other benzene rings. However, ^{two or more groups of D 1} to D ⁴ are intramolecular cross-linking groups that are ether-bonded to the benzene ring, and groups of D ¹ to D ⁴ that are not involved in the cross-linking are OH groups. Above all, ^{it is preferable that D 1} and D ⁴ or D ² and D ³ form an intramolecular cross-linking group. The intramolecular crosslinking group is represented by, for example, the above-mentioned formula (C-0) or formula (C-0A).

The compound of this embodiment is more preferably represented by the formula (P-0B).

The compound of this embodiment is particularly preferably represented by the formula (M-0). X ⁰ is a group represented by the formula (X-0). A is defined as described above.

The compound of this embodiment is particularly preferably represented by the formula (M-0A). X ⁰ is a group represented by the formula (X-0A).

In the present invention, "substitution" means that one or more hydrogen atoms in a functional group are substituted with a substituent unless otherwise defined. The "substituted group" is not particularly limited, but for example, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, and the like. Branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxyl group having 1 to 20 carbon atoms, 0 to 20 carbon atoms. Amino group, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, alkiloyloxy having 1 to 20 carbon atoms. Examples thereof include a group, an allyloyloxy group having 7 to 30 carbon atoms or an alkylsilyl group having 1 to 20 carbon atoms.

The compound according to this embodiment is preferably represented by the following formula (P-1C).

^{^{1) L 5 ~ L 12 L}} 5 ~ L 12 For each independently a single bond, a straight-chain alkylene group of having 1 to 20 carbon atoms have a substituent, substituted A branched alkylene group having 3 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent, and an arylene group having 6 to 24 carbon atoms which may have a substituent may be used. , -O-, -OC (= O)-, -OC (= O) O-, -O-R ^2- C (= O) O-, -N (R ²⁰ ) -C (= O)-, A divalent organic group selected from the group consisting of -N (R ²⁰ ) -C (= O) O-, -S-, -SO-, -SO _{2- and any combination thereof.}

Examples of the linear alkylene group, the branched alkylene group, the cycloalkylene group, and the arylene group include those described by the formula (P-0C). Is as described in Formula (P-0C) also R ² and ^{R 20.}

In one embodiment, 2 or more ^L 5 ^{~ L 12} is ^{-O-R 2 -C (= O} ) O group, can be involved in intramolecular bridge. When two or more L ⁵ to L ¹² are involved in the ^{intramolecular cross-linking, it is preferable that some R 30} to R ³⁷ are involved in the intramolecular cross-linking as a divalent group. For R ² is as described in Formula (P-0C).

^{^{^{2) R 30 ~ R 30 ~}}} R 37 for ^{R 37,} when not involved in intramolecular bridge, independently, a group selected from the following.
A linear alkyl group having 1 to 20 carbon atoms which may have a substituent;
A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent;
An aryl group having 6 to 20 carbon atoms which may have a substituent;
An alkoxyl group having 1 to 20 carbon atoms which may have a substituent;
Cyano group;
Nitro group;
Hydroxy group;
Heterocyclic group;
Halogen atom;
Carboxyl group;
Alkylsilyl group with 1 to 20 carbon atoms;
Substituent methyl group having 2 to 20 carbon atoms, 1-substituted ethyl group having 3 to 20 carbon atoms, 1-substituted-n-propyl group having 4 to 20 carbon atoms, and 3 to 20 carbon atoms having the property of being dissociated by an acid. 1-branched alkyl group, silyl group with 1 to 20 carbon atoms, acyl group with 2 to 20 carbon atoms, 2 to 20 carbon atoms
A group selected from the group consisting of a 1-substituted alkoxyalkyl group, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group;
Hydrogen atom.
When R ³⁰ to R ³⁷ are involved in intramolecular cross-linking, they may be divalent groups independently derived from the groups selected from the above.

Examples of the alkyl group, the cycloalkyl group, the aryl group, and the alkoxyl include those described by the formula (P-0C). Examples of the heterocyclic group, the alkylsilyl group, the halogen atom, and the group having the property of being dissociated by the acid include those described by the formula (P-0C).

3) About L ⁵ R ³⁰ to L ¹² R ³⁷ m ^{11 to 18} represent the number of these groups, respectively, and are independently integers of 1 to 4. If m ^{11 to 18} is large, the compound may become unstable, so m ^{11 to 18} is preferably 1 to 2, more preferably 1.

At ^{least two of the L 5} R ³⁰ to L ¹² R ³⁷ groups are ether-bonded to the benzene ring and form an intramolecular cross-linking group. In one embodiment, two of the L ⁵ R ³⁰ to L ¹² R ³⁷ groups form an intramolecular cross-linking group represented by the above formula (C-0). However, in this case, A in the formula (C-0) is a divalent group derived from ^{R 30} to R ^37. The specific A is also as described above. Two of R ³⁰ to R ³⁷ preferably form an intramolecular cross-linking group represented by the formula (C-1A).

⁴⁾ ^R ²² ~ R ²⁹ for R 22 ^{~ R 29} are independently hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or aryl of the formula (P-0C-1) 6 to 24 carbon atoms represented by A group or a group derived from these. The alkyl group having 1 to 20 carbon ^atoms, may be mentioned those described in ^R 16 ^~ R ^19. R ²² to R ²⁹ are preferably hydrogen atoms.

The compound of this embodiment is preferably represented by the formula (P-1A). Wherein, R ^B is a linear alkyl group or branched alkyl group having 3 to 10 carbon atoms having 1 to 10 carbon atoms, preferably a t- butyl group. In the compound, in the formula (P-1C), R ²² to R ²⁹ are hydrogen atoms, and m ^{11 to 18} are 2. And out of one benzene ring into two ^L 5 ^{R 30} present, one ^{R B} (e.g. ^{which L 5} linear alkylene group or branched alkylene group having 3 to 10 carbon atoms having 1 to 10 carbon atoms, R ³⁰ is a hydrogen atom) and the other is D. The same applies ^{to L 6} R ³¹ to L ¹² R ³⁷ existing in other benzene rings. However, ^{two or more groups of D 5} to D ¹² are intramolecular cross-linking groups that are ether-bonded to the benzene ring, and groups of D ⁵ to D ¹² that are not involved in the cross-linking are OH groups. Above all, ^{it is preferable that D 5} and D ¹¹ or D ⁹ and D ¹³ form an intramolecular cross-linking group. The intramolecular cross-linking group is, for example, as described above.

The compound of this embodiment is more preferably represented by the formula (P-1B).

The compound of this embodiment is particularly preferably represented by the formula (M-1). X ⁰ is a group represented by the formula (X-1). A is a divalent group derived from ^{R 30} to R ^37.

The compound of this embodiment is particularly preferably represented by the formula (M-1A). X ¹ is a group represented by the formula (X-1A).

[Method for producing compounds]
In the method for producing a compound according to the present embodiment, a polyphenol is reacted with a cross-linking agent containing a dissociative bond that dissociates under acidic or alkaline conditions, and two or more hydroxyl groups of the polyphenol are intramolecularly generated by the compound. A step of cross-linking is provided.

The above-mentioned polyphenols can be used. Examples of the cross-linking agent include compounds having an ester bond or an amide bond. The cross-linking agent is preferably represented by the formula (C-hal), more preferably the formula (C-0hal) or the formula (C-1hal). In the formula, A is defined as described above. X is a halogen atom, preferably F, Cl, or Br, and more preferably Br.

The reaction temperature and time are appropriately determined from the viewpoint of reaction rate and reduction of by-products, but can be carried out at, for example, about -10 to 30 ° C. Further, the solvent is not limited, but halogenated hydrocarbons and the like can be used. Further, a basic compound may be used in combination to trap the generated hydrogen halide. Examples of the compound include amines such as pyridine.

[Composition]
The compound according to this embodiment is suitable as a material for lithography. The lithography material is a material that can be used in lithography technology, and is not particularly limited as long as it contains the compound according to the present embodiment, and can be used for resist applications (that is, resist compositions) and the like. Further, the compound according to this embodiment is a curable composition. The curable composition can be, for example, a composition for forming an underlayer film for lithography, a composition for forming an optical article, and the like, but is not limited thereto. The curable composition may be either radiation-curable or thermosetting, but is more preferably radiation-curable. Further, the composition according to the present embodiment is produced through the steps of preparing the compound according to the above-mentioned present embodiment. For example, it can be produced by mixing the compound according to the present embodiment with other components such as a solvent by a known method.

1) Material Composition for Lithography The material composition for lithography according to the present embodiment contains the material for lithography according to the present embodiment and a solvent. Since the material composition for lithography has high sensitivity and high resolution, a good resist pattern can be formed. Further, since the molecule of the compound according to the present embodiment has an appropriate diffusion rate, it exhibits high resolution while maintaining high sensitivity. Further, since the compound has an appropriate molecular weight, it is difficult to volatilize, and the film loss during curing is relatively small, so that the composition can form a highly flat film.

<Characteristics of resist film forming composition>
The lithography material of the present embodiment can be used for resist applications as described above, and an amorphous film can be formed by a known method such as spin coating. Further, depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be produced separately. Hereinafter, the composition for forming a resist film will be described.

When the resist film-forming composition in the present embodiment has a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the composition in a developing solution at 23 ° C. is preferably 5 Å / sec or less, and 0. 05 to 5 Å / sec is more preferable, and 0.0005 to 5 Å / sec is even more preferable. When the dissolution rate is 5 Å / sec or less, a resist insoluble in a developing solution can be obtained. Further, when the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. It is presumed that this is because the change in solubility of the compound according to the present embodiment before and after exposure increases the contrast between the exposed portion that dissolves in the developing solution and the unexposed portion that does not dissolve in the developing solution. It also has the effect of reducing line edge roughness and reducing defects.

When the resist film forming composition in the present embodiment is a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the composition in a developing solution at 23 ° C. is preferably 10 Å / sec or more. .. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developing solution and is more suitable for a resist. Further, if the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface portion of the compound according to the present embodiment is dissolved and the line edge roughness is reduced. It also has the effect of reducing defects. The dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 ° C. and measuring the film thickness before and after the immersion by a known method such as visual inspection, ellipsometer or QCM method.

When the resist film-forming composition of the present embodiment has a positive resist pattern, a portion of the amorphous film formed by spin-coating the composition exposed to radiation such as KrF excimer laser, extreme ultraviolet rays, electron beam or X-ray. The dissolution rate of the above in a developing solution at 23 ° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, it is easily dissolved in a developing solution and is more suitable for a resist. Further, if the dissolution rate is 10 Å / sec or more, the resolution may be improved. It is presumed that this is because the micro surface portion of the compound according to the present embodiment is dissolved and the line edge roughness is reduced. It also has the effect of reducing defects.

When the resist film-forming composition of the present embodiment is a negative resist pattern, a portion of the amorphous film formed by spin-coating the composition exposed to radiation such as KrF excimer laser, extreme ultraviolet rays, electron beams or X-rays. The dissolution rate of the above in a developing solution at 23 ° C. is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, still more preferably 0.0005 to 5 Å / sec. When the dissolution rate is 5 Å / sec or less, a resist insoluble in a developing solution can be obtained. Further, when the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. It is presumed that this is because the change in solubility of the compound according to the present embodiment before and after exposure increases the contrast between the unexposed portion that dissolves in the developing solution and the exposed portion that does not dissolve in the developing solution. It also has the effect of reducing line edge roughness and reducing defects.

<Other components of the resist film forming composition>
The resist film forming composition of the present embodiment contains the compound according to the present embodiment as a solid component. The composition for forming a resist film of the present embodiment further contains a solvent in addition to the compound according to the present embodiment.

The solvent used in the composition for forming a resist film of the present embodiment is not particularly limited, but for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono. Ethethylene glycol monoalkyl ether acetates such as -n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (PGMEA), Propropylene glycol monoalkyl ether acetates such as propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-acetate Aliphatic carboxylic acid esters such as hexyl, methyl propionate, ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy- Methyl 2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, pyruvate Other esters such as methyl and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN) and the like. Ketones; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactones such as γ-lactone and the like can be mentioned. These solvents can be used alone or in combination of two or more.

The solvent used in the composition for forming a resist film of the present embodiment is preferably a safe solvent, and more preferably an ester such as PGMEA, butyl acetate, ethyl propionate, and ethyl lactate; a polyvalent value such as PGME. Alcohol ether; at least one selected from aprotic polar solvents such as CHN, CPN, 2-heptanone, anisole, and more preferably at least one selected from PGMEA, PGME and CHN.

In the composition for forming a resist film of the present embodiment, the relationship between the amount of the solid component and the amount of the solvent is not particularly limited, but the solid component is 1 to 80% by mass with respect to 100% by mass of the total mass of the solid component and the solvent. % And 20 to 99% by mass of the solvent, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, still more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent. Yes, particularly preferably 2 to 10% by mass of the solid component and 90 to 98% by mass of the solvent.

The composition for forming a resist film of the present embodiment comprises a group consisting of an acid generator (C), an acid cross-linking agent (G), an acid diffusion control agent (E) and other components (F) as other solid components. It may contain at least one selected.

In the composition for forming a resist film of the present embodiment, the content of the compound according to the present embodiment is not particularly limited, but the total mass of the solid component (compound according to the present embodiment, acid generator (C), acid cross-linking). The total amount of solid components arbitrarily used such as the agent (G), the acid diffusion control agent (E) and the other component (F), the same applies hereinafter) is preferably 50 to 99.4% by mass, more preferably. Is 55 to 90% by mass, more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. In the case of the above content, the resolution is further improved and the line edge roughness (LER) is further reduced.

<Acid generator (C)>
The composition for forming a resist film of the present embodiment is directly or indirectly irradiated with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam. It is preferable to contain at least one acid generator (C) that generates an acid.

In this case, in the resist film forming composition of the present embodiment, the content of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, based on the total mass of the solid components. 3 to 30% by mass is more preferable, and 10 to 25% by mass is particularly preferable. By using the acid generator (C) within the above content range, a pattern profile with higher sensitivity and lower edge roughness can be obtained.

In the resist film forming composition of the present embodiment, if an acid is generated in the system, the method of generating the acid is not limited. Finer processing is possible by using an excimer laser instead of ultraviolet rays such as g-rays and i-rays, and further fine processing is possible by using electron beams, extreme ultraviolet rays, X-rays, and ion beams as high-energy rays. Is possible.

The acid generator (C) is not particularly limited, and examples thereof include compounds disclosed in International Publication No. 2017/033943. As the acid generator (C), an acid generator having an aromatic ring is preferable, an acid generator having a sulfonic acid ion having an aryl group is more preferable, and diphenyltrimethylphenylsulfonium p-toluenesulfonate and triphenylsulfonium p-toluene are more preferable. Sulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoromethanesulfonate are particularly preferable. By using the acid generator, line edge roughness can be reduced.

Further, it is preferable that the resist film forming composition of the present embodiment further contains a diazonaphthoquinone photoactive compound as an acid generator. The diazonaphthoquinone photoactive compound is a diazonaphthoquinone substance containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound, and is particularly limited as long as it is generally used as a photosensitive component in a positive resist composition. However, one type or two or more types can be arbitrarily selected and used. Among these, from the viewpoint of low roughness and solubility, a non-polymeric diazonaphthoquinone photoactive compound is preferable, a low molecular weight compound having a molecular weight of 1500 or less is more preferable, and a molecular weight of 1200 or less is particularly preferable, and a molecular weight is particularly preferable. It is 1000 or less. Preferred specific examples of such a non-polymeric diazonaphthoquinone photoactive compound include the non-polymeric diazonaphthoquinone photoactive compound disclosed in International Publication No. 2016/158881. The acid generator (C) may be used alone or in combination of two or more.

<Acid cross-linking agent (G)>
The resist film forming composition of the present embodiment contains one or more acid cross-linking agents (G) when used as a negative resist material or as an additive for increasing the strength of a pattern even in a positive resist material. It is preferable to include it. The acid cross-linking agent (G) is a compound capable of intramolecularly or intermolecularly cross-linking the compound according to the present embodiment in the presence of the acid generated from the acid generator (C). Such an acid cross-linking agent (G) is not particularly limited, and examples thereof include compounds having one or more cross-linking groups capable of cross-linking the compound according to the present embodiment.

Specific examples of such a crosslinkable group are not particularly limited, but are, for example, (i) -R-OH (where R is an alkylene group having 1 to 6 carbon atoms) and -R-OR'(here). R is an alkylene group having 1 to 6 carbon atoms, R'is an alkyl group having 1 to 6 carbon atoms), -R-OCOMe (where R is an alkylene group having 1 to 6 carbon atoms) and other hydroxyalkyl groups. Or a group derived from them; a carbonyl group such as (ii) formyl group, -R-COOH (where R is an alkylene group having 1 to 6 carbon atoms) or a group derived from them; (iii) dimethylamino. Nitrogen-containing group-containing group such as methyl group, diethylaminomethyl group, dimethylolaminomethyl group, dietylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing group such as glycidyl ether group, glycidyl ester group and glycidylamino group. (V) Allyloxy having 1 to 6 carbon atoms (alkyl group having 1 to 6 carbon atoms) such as benzyloxymethyl group and benzoyloxymethyl group, and aralkyloxy having 1 to 6 carbon atoms (alkyl having 1 to 6 carbon atoms). Groups derived from aromatic groups such as (group); (vi) polymerizable multiple bond-containing groups such as vinyl groups and isopropenyl groups can be mentioned. As the crosslinkable group of the acid cross-linking agent (G), a hydroxyalkyl group, an alkoxyalkyl group and the like are preferable, and an alkoxymethyl group is particularly preferable.

The acid cross-linking agent (G) having a cross-linking group is not particularly limited. Methylol group-containing compounds such as group-containing phenol compounds; (ii) alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycol uryl compounds, alkoxyalkyl group-containing phenol compounds, etc. Alkoxyalkyl group-containing compounds; (iii) Carboxymethyl groups such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycol uryl compounds, and carboxymethyl group-containing phenol compounds. Containing compounds; (iv) bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolak resin-based epoxy compounds, resole resin-based epoxy compounds, poly (hydroxystyrene) -based epoxy compounds and other epoxy compounds. Can be mentioned.

As the acid cross-linking agent (G), a compound having a phenolic hydroxyl group and a compound and a resin obtained by introducing the cross-linking group into an acidic functional group in an alkali-soluble resin and imparting cross-linking property can be used. .. In that case, the introduction rate of the crosslinkable group is not particularly limited, and is, for example, 5 to 100 mol%, preferably 10 to 60, based on the total acidic functional group in the compound having a phenolic hydroxyl group and the alkali-soluble resin. It is adjusted to mol%, more preferably 15-40 mol%. Within the above range, a cross-linking reaction occurs sufficiently, and a decrease in the residual film ratio, a pattern swelling phenomenon, meandering, and the like can be avoided, which is preferable.

In the composition for forming a resist film of the present embodiment, the acid cross-linking agent (G) is an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycol uryl compound or a resin thereof (acid cross-linking agent (G1)) in the molecule. A phenol derivative (acid) having 1 to 6 benzene rings, 2 or more hydroxyalkyl groups or alkoxyalkyl groups in the entire molecule, and the hydroxyalkyl group or alkoxyalkyl group bonded to any of the benzene rings. A cross-linking agent (G2)), a compound having at least one α-hydroxyisopropyl group (acid cross-linking agent (G3)) is preferable. For example, the compounds disclosed in International Publication No. 2017/033943 may be mentioned.

In the resist film forming composition of the present embodiment, the content of the acid cross-linking agent (G) is preferably 0.5 to 49% by mass, more preferably 0.5 to 40% by mass, based on the total mass of the solid components. 1 to 30% by mass is more preferable, and 2 to 20% by mass is particularly preferable. When the content ratio of the acid cross-linking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the resist film in the alkaline developer is improved, the residual film ratio is lowered, and the pattern is swollen or tortuous. It is preferable because it can suppress the occurrence, and on the other hand, when it is 49% by mass or less, it is preferable because the decrease in heat resistance as a resist can be suppressed.

Further, the content of at least one compound selected from the acid cross-linking agent (G1), the acid cross-linking agent (G2), and the acid cross-linking agent (G3) in the acid cross-linking agent (G) is not particularly limited. , The range can be various depending on the type of the substrate used when forming the resist pattern and the like.

<Acid diffusion control agent (E)>
The resist film-forming composition of the present embodiment is an acid having an action of controlling diffusion of an acid generated from an acid generator by irradiation in the resist film and preventing an unfavorable chemical reaction in an unexposed region. A diffusion control agent (E) may be contained. By using such an acid diffusion control agent (E), the storage stability of the resist film forming composition is improved. In addition, the resolution is further improved, and changes in the line width of the resist pattern due to fluctuations in the leaving time before irradiation and the leaving time after irradiation can be suppressed, resulting in extremely excellent process stability.

Such an acid diffusion control agent (E) is not particularly limited, and examples thereof include radiolytic basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds. Examples of the acid diffusion control agent (E) include compounds disclosed in International Publication No. 2017/033943. The acid diffusion control agent (E) may be used alone or in combination of two or more.

The content of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass, based on the total mass of the solid component. 0.01 to 3% by mass is particularly preferable. When the content of the acid diffusion control agent (E) is within the above range, deterioration of resolution, pattern shape, dimensional fidelity and the like can be further suppressed. Further, even if the leaving time from the electron beam irradiation to the heating after the irradiation is long, the shape of the upper layer portion of the pattern does not deteriorate. Further, when the content of the acid diffusion control agent (E) is 10% by mass or less, it is possible to prevent deterioration of sensitivity, developability of the unexposed portion and the like. Further, by using such an acid diffusion control agent, the storage stability of the resist film forming composition is improved, the resolution is improved, and the retention time before irradiation and the retention time after irradiation are improved. It is possible to suppress the change in the line width of the resist pattern due to the fluctuation of the resist pattern, and the process stability is extremely excellent.

<Other ingredients (F)>
The composition for forming a resist film of the present embodiment contains a dissolution accelerator, a dissolution control agent, a sensitizer, and a surfactant as other components (F), if necessary, as long as the object of the present embodiment is not impaired. One or two or more kinds of additives such as an activator and an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be added. Examples of the other component (F) include compounds disclosed in International Publication No. 2017/033943.

The total content of the other component (F) is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, further preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid component. ..

In the composition for forming a resist film of the present embodiment, the content of the compound according to the present embodiment, the acid generator (C), the acid diffusion control agent (E), and other components (F) (the compound according to the present embodiment). / Acid generator (C) / Acid diffusion control agent (E) / Other component (F)) is the mass% based on the solid matter, preferably 50 to 99.4 / 0.001 to 49 / 0.001. ~ 49/0 to 49, more preferably 55 to 90/1 to 40/0.01 to 10/0 to 5, still more preferably 60 to 80/3 to 30/0.01 to 5/0 to 1, in particular. It is preferably 60 to 70/10 to 25/0.01 to 3/0.

The content ratio of each component is selected from each range so that the total is 100% by mass. With the above content ratio, the performance such as sensitivity, resolution, and developability is further excellent.

The method for preparing the resist film-forming composition of the present embodiment is not particularly limited, and for example, each component is dissolved in a solvent at the time of use to form a uniform solution, and then, if necessary, for example, a pore size of about 0.2 μm. Examples thereof include a method of filtering with a filter or the like.

The resist film forming composition of the present embodiment may contain a resin as long as the object of the present invention is not impaired. The resin is not particularly limited, and is, for example, a novolak resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and a polymer containing acrylic acid, vinyl alcohol, or vinylphenol as a monomer unit. Alternatively, these derivatives and the like can be mentioned. The content of the resin is not particularly limited and is appropriately adjusted according to the type of the compound according to the present embodiment to be used, but is preferably 30 parts by mass or less, more preferably 10 parts by mass, per 100 parts by mass of the compound. Parts or less, more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.

<Pattern formation method>
When a pattern is formed on a substrate using a lithography material, for example, a lithography material according to the present embodiment and a composition containing the same (hereinafter, these may be collectively referred to as "lithographic material or the like"). A pattern forming method including a film forming step of forming a film on a substrate, an exposure step of exposing the film, and a developing step of developing the exposed film in the exposure step to form a pattern is used. be able to.

For example, when a resist pattern is formed using the lithography material or the like of the present embodiment, the method for forming the pattern (resist pattern) is not particularly limited, and as a suitable method, a resist film containing the above-mentioned lithography material or the like is used. A film forming step of applying the forming composition onto a substrate to form a film (resist film), an exposure step of exposing the formed film (resist film), and a film (resist film) exposed in the exposure step. ) Is developed to form a pattern (resist pattern). The resist pattern of this embodiment can also be formed as an upper resist in a multilayer process.

The method for forming a specific resist pattern is not particularly limited, and examples thereof include the following methods. First, a resist film is formed by applying the composition on a conventionally known substrate by a coating means such as rotary coating, cast coating, and roll coating. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, the present invention is not particularly limited, and examples thereof include a silicon wafer, a metal substrate such as copper, chromium, iron, and aluminum, and a glass substrate. The material of the wiring pattern is not particularly limited, and examples thereof include copper, aluminum, nickel, and gold. Further, if necessary, an inorganic film or an organic film may be provided on the above-mentioned substrate. The inorganic film is not particularly limited, and examples thereof include an inorganic antireflection film (inorganic BARC). The organic film is not particularly limited, and examples thereof include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

Next, if necessary, heat the applied substrate. The heating conditions vary depending on the composition contained in the composition and the like, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C. By heating, the adhesion of the resist to the substrate may be improved, which is preferable. The resist film is then exposed to the desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer lasers, electron beams, extreme ultraviolet rays (EUV), X-rays, and ion beams. The exposure conditions and the like are appropriately selected according to the compounding composition and the like of the resist composition.

In the resist pattern forming method of the present embodiment, it is preferable to heat after irradiation in order to stably form a fine pattern with high accuracy in exposure. The heating conditions vary depending on the composition of the composition and the like, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C.

Next, the exposed resist film is developed with a developing solution to form a predetermined resist pattern. As the developing solution, it is preferable to select a solvent having a solubility parameter (SP value) close to that of the compound according to the present embodiment to be used, and a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether. A polar solvent such as a system solvent, a hydrocarbon solvent or an alkaline aqueous solution can be used. A positive resist pattern or a negative resist pattern can be produced according to the type of the developing solution, but generally, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, or an ether solvent is used. In the case of a hydrocarbon solvent, a negative resist pattern can be obtained, and in the case of an alkaline aqueous solution, a positive resist pattern can be obtained. Examples of the ketone solvent, ester solvent, alcohol solvent, amide solvent, ether solvent, hydrocarbon solvent, and alkaline aqueous solution include those disclosed in International Publication No. 2017/033943.

A plurality of the solvents may be mixed, or they may be mixed with a solvent other than the above or water as long as they have performance. However, in order to fully exert the effect of the present invention, the water content of the developer as a whole is preferably less than 70% by mass, more preferably less than 50% by mass, and more preferably less than 30% by mass. It is preferable that it is less than 10% by mass, and it is particularly preferable that it contains substantially no water. That is, the content of the organic solvent in the developing solution is not particularly limited, and is preferably 30% by mass or more and 100% by mass or less, and more preferably 50% by mass or more and 100% by mass or less with respect to the total amount of the developing solution. It is more preferably 70% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

In particular, the developing solution contains at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent, and the developing solution contains the resolution and roughness of the resist pattern. It is preferable because it improves the resist performance of the solvent.

The vapor pressure of the developer is not particularly limited, and is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less, for example, at 20 ° C. By reducing the vapor pressure of the developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity in the wafer surface is improved. To improve. Examples of the developer having such a vapor pressure include the developer disclosed in International Publication No. 2017/033943.

An appropriate amount of surfactant can be added to the developer as needed. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based or silicon-based surfactant can be used. Examples of these fluorine- or silicon-based surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, and Japanese Patent Application Laid-Open No. 62-170950. Kaisho 63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, JP-A-5360692. The surfactants described in No. 5529881, No. 5296330, No. 5436098, No. 5576143, No. 5294511, and No. 5824451 can be mentioned. Preferably, it is a nonionic surfactant. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.

The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developing solution.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), and a method of developing by raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle). Method), a method of spraying the developer on the surface of the substrate (spray method), a method of continuously spraying the developer on the substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispense method). ) Etc. can be applied. The time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.

Further, after the step of performing the development, a step of stopping the development may be carried out while substituting with another solvent.

After development, it is preferable to include a step of washing with a rinsing solution containing an organic solvent.

The rinsing solution used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution containing a general organic solvent or water can be used. As the rinsing solution, it is preferable to use a rinsing solution containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent. .. More preferably, after the development, a washing step is performed using a rinsing solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent. More preferably, after development, a step of washing with a rinsing solution containing an alcohol-based solvent or an ester-based solvent is performed. Even more preferably, after development, a step of washing with a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after development, a step of washing with a rinsing solution containing a monohydric alcohol having 5 or more carbon atoms is performed. The time for rinsing the pattern is not particularly limited, but is preferably 10 to 90 seconds.

Here, the monohydric alcohol used in the rinsing step after development is not particularly limited, and examples thereof include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol and 2 -Butanol, 3-methyl-1-butanol, t-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol , Cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and a particularly preferable monohydric alcohol having 5 or more carbon atoms is 1-. Hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like can be used.

Each of the above components may be mixed in a plurality or mixed with an organic solvent other than the above.

The water content in the rinse liquid is not particularly limited, and is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

The vapor pressure of the rinse solution used after development is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and further preferably 0.12 kPa or more and 3 kPa or less at 20 ° C. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and the swelling caused by the infiltration of the rinsing liquid is further suppressed, and the dimensions in the wafer surface are further suppressed. The uniformity is improved.

An appropriate amount of surfactant can be added to the rinse solution before use.

In the rinsing process, the developed wafer is washed with the rinsing liquid containing the above-mentioned organic solvent. The method of cleaning treatment is not particularly limited, but for example, a method of continuously applying a rinse solution onto a substrate rotating at a constant speed (rotational coating method), or a method of immersing the substrate in a tank filled with the rinse solution for a certain period of time. A method (dip method), a method of spraying a rinse solution on the surface of the substrate (spray method), etc. can be applied. Among them, the cleaning treatment is performed by the rotation coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.

A pattern wiring board can be obtained by etching after forming a resist pattern. The etching method can be performed by a known method such as dry etching using plasma gas and wet etching with an alkaline solution, a ferric chloride solution, a ferric chloride solution or the like.

It is also possible to perform plating after forming a resist pattern. The plating method is not particularly limited, and examples thereof include copper plating, solder plating, nickel plating, and gold plating.

The residual resist pattern after etching can be peeled off with an organic solvent. The organic solvent is not particularly limited, and examples thereof include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). The peeling method is not particularly limited, and examples thereof include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small-diameter through hole.

In the present embodiment, the wiring board can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

2) Composition for forming an underlayer film for lithography, an underlayer film for lithography, and a pattern forming method [first embodiment]
<Composition for forming an underlayer film for lithography>
The composition for forming an underlayer film for lithography according to the first embodiment of the present invention comprises the compound according to the present embodiment and a silicon-containing compound (for example, a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzed condensate thereof). ) And. The composition for forming a lower layer film for lithography of the present embodiment can form a lower layer film for lithography such as a resist underlayer film, has high heat resistance, and has high solvent solubility. Therefore, the rectangularity of the pattern is excellent. In addition, it is possible to reduce film defects (thin film formation), have high adhesion, have good storage stability, have high sensitivity, long-term light resistance, and can impart a good resist pattern shape. Further, since the molecule of the compound according to the present embodiment has an appropriate diffusion rate, it exhibits high resolution while maintaining high sensitivity. Further, since the compound has an appropriate molecular weight, it is difficult to volatilize, and the film loss during curing is relatively small, so that the composition for forming a lower layer film for lithography can form a lower layer film for lithography with high flatness.

The composition for forming a lower layer film for lithography of the present embodiment is suitably used for, for example, a multilayer resist method in which a resist lower layer film is further provided between an upper layer resist (photoresist or the like) and a hard mask, an organic lower layer film, or the like. Can be done. In such a multilayer resist method, for example, a resist underlayer film is formed on an organic underlayer film or a hard mask on a substrate by a coating method or the like, and an upper layer resist (for example, photoresist, etc.) is formed on the resist underlayer film. An electron beam resist, an EUV resist) is formed. Then, a resist pattern is formed by exposure and development, the resist underlayer film is dry-etched using the resist pattern to transfer the pattern, and the pattern is transferred by etching the organic underlayer film, and the organic underlayer film is used. Process the substrate.

That is, the lithography lower layer film (resist lower layer film) formed by using the lithography lower layer film forming composition of the present embodiment is less likely to cause intermixing with the upper layer resist and has heat resistance, for example. Since the etching rate for the halogen-based (fluorine-based) etching gas is higher than that of the patterned upper-layer resist used as a mask, a good pattern can be obtained with a rectangular shape. Further, since the lithography underlayer film (resist underlayer film) formed by using the lithography underlayer film forming composition of the present embodiment has high resistance to oxygen-based etching gas, it is provided on a substrate such as a hard mask. It can function as a good mask when patterning layers. The composition for forming an underlayer film for lithography of the present embodiment can also be used in an embodiment in which a plurality of underlayer films for resist are laminated. In this case, the position of the resist lower layer film (how many layers are laminated) formed by using the composition for forming the lower layer film for lithography of the present embodiment is not particularly limited, and even if it is directly under the upper layer resist. Often, the layer may be located closest to the substrate, or may be sandwiched between resist underlayer films.

In forming a fine pattern, the resist film thickness tends to be thin in order to prevent the pattern from collapsing. Dry etching for transferring a pattern to a film existing in the lower layer by thinning the resist cannot transfer the pattern unless the etching rate is higher than that of the upper film. In the present embodiment, the substrate is coated with the resist underlayer film (containing a silicon-based compound) of the present embodiment via the organic underlayer film, and further coated with the resist film (organic resist film). Can be done. The dry etching rate differs greatly depending on the selection of the etching gas between the organic component film and the inorganic component film. The organic component film has an oxygen-based gas and the dry etching rate increases, and the inorganic component film contains halogen. The dry etching rate increases with gas.

For example, using a pattern-transferred resist underlayer film, the underlying organic underlayer film is dry-etched with an oxygen-based gas to perform pattern transfer to the organic underlayer film, and the pattern-transferred organic underlayer film is a halogen-containing gas. Can be used for substrate processing. Since the lithography underlayer film (resist underlayer film) formed by using the lithography underlayer film forming composition of the present embodiment has good adhesion, the transfer pattern can be suppressed from collapsing.

Further, the resist underlayer film formed by the composition for forming the underlayer film for lithography of the present embodiment contains the compound according to the present embodiment having excellent absorption ability to active light and a silicon-containing compound (for example, hydrolyzable organosilane and its water addition). By including (decomposed product or a hydrolyzed condensate thereof), the sensitivity of the upper layer resist is improved, intermixing with the upper layer resist does not occur, and the shape of the pattern of the resist undercoat forming film after exposure and development becomes rectangular. Become. This enables substrate processing with a fine pattern.

Further, since the resist underlayer film by the composition for forming the underlayer film for lithography of the present embodiment has high heat resistance, it can be used even under high temperature baking conditions. Furthermore, since it has a relatively low molecular weight and low viscosity, it is easy to uniformly fill every corner even with a substrate having a step (particularly, a fine space, a hole pattern, etc.), and as a result. , Flatness and embedding properties tend to be relatively favorably enhanced.

The composition for forming an underlayer film for lithography can further contain a solvent, an acid generator, an acid cross-linking agent, or a combination thereof. In addition to this, an organic polymer compound, a surfactant, water, alcohol, a curing catalyst and the like can be included as optional components. From the viewpoint of coatability and quality stability, the content of the compound according to the present embodiment in the composition for forming an underlayer film for lithography is preferably 0.1 to 70% by mass, preferably 0.5 to 50% by mass. % Is more preferable, and 3.0 to 40% by mass is particularly preferable.

<Solvent>
As the solvent used in the present embodiment, a known solvent can be appropriately used as long as the compound portion according to the present embodiment is at least soluble. For example, a solvent that can be contained in the composition for forming an underlayer film for lithography disclosed in International Publication No. 2017/188450 can be mentioned. The solvent is preferably a safe solvent, more preferably an ester such as PGMEA, butyl acetate, ethyl propionate, and ethyl lactate; a polyhydric alcohol ether such as PGME; CHN, CPN, 2-heptanone, anisole and the like. At least one selected from the aprotic polar solvents of, and more preferably at least one selected from PGMEA, PGME and CHN.

The content of the solvent is not particularly limited, but is 100 to 10,000 parts by mass with respect to 100 parts by mass of the total solid content of the composition for forming a lower layer film for lithography from the viewpoint of solubility and film formation. It is preferably 200 to 8,000 parts by mass, more preferably 200 to 5,000 parts by mass.

<Acid cross-linking agent>
The composition for forming an underlayer film for lithography may contain one or more acid cross-linking agents when used as a negative resist material or as an additive for increasing the strength of a pattern even in a positive resist material. .. Examples of the acid-crosslinking agent include compounds having one or more groups (hereinafter, referred to as “crosslinkable groups”) capable of forming a crosslink in the presence of an acid. For example, an acid cross-linking agent which may be contained in the composition for forming an underlayer film for lithography disclosed in International Publication No. 2017/188450 can be mentioned. Further, for example, the one described in International Publication WO2013 / 024779 can be mentioned as a specific example of the acid cross-linking agent.

The content of the acid cross-linking agent is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the composition for forming an underlayer film for lithography from the viewpoint of solubility and shape stability of the coating film. It is preferably 30 parts by mass, more preferably 0.05 to 20 parts by mass, and even more preferably 0.1 to 10 parts by mass.

<Silicon-containing compound>
The silicon-containing compound may be either an organic silicon-containing compound or an inorganic silicon-containing compound, but is preferably an organic silicon-containing compound. Examples of the inorganic silicon-containing compound include a silicon oxide, a silicon nitride, and a polysilazane compound composed of silicon oxide nitride, which can be formed into a film by a coating method at a low temperature. Examples of the organosilicon-containing compound include polysilsesquioxane-based compounds, hydrolyzable organosilanes, hydrolyzates thereof, and hydrolyzed condensates thereof. The specific material of the polysilsesquioxane base is not limited to the following, and for example, those described in JP-A-2007-226170 and JP-A-2007-226204 can be used. The hydrolyzable organosilane, its hydrolyzate, or its hydrolyzed condensate is at least one selected from the group consisting of the hydrolyzable organosilane of the following formula (D1) and the following formula (D2). Hydrolyzable organosilanes, their hydrolysates, or their hydrolyzed condensates (hereinafter, these are simply at least one organic silicon compound selected from the group consisting of formulas (D1) and (D2). May be referred to). When the composition for forming an underlayer film for lithography contains at least one organosilicon compound selected from the group consisting of the formulas (D1) and (D2), the Si—O bond is controlled by adjusting the curing conditions. It is easy to use, is advantageous in terms of cost, and is suitable for introducing organic components. Therefore, the composition for forming the underlayer film for lithography is formed by using the composition for forming the underlayer film for lithography containing at least one organosilicon compound selected from the group consisting of the formula (D1) and the formula (D2). The resulting layer is useful as an intermediate layer of the resist layer (a layer between the upper resist layer and the organic lower layer film provided on the substrate).

Equation (D1): (R ³ ) _a Si (R ⁴ ) _4-a
(In the formula (D1), R ³ is an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, and the like. An "organic group" having an alkoxyaryl group, an acyloxyaryl group, an isocyanurate group, a hydroxy group, a cyclic amino group, or a cyano group; or a combination thereof, which is bonded to a silicon atom by a Si—C bond. are those, R ⁴ represents an alkoxy group, an acyloxy group or a halogen group, a is an integer of 0-3.)

Equation (D2): [(R ⁵ ) _c Si (R ⁶ ) _4-c ] ₂ Y _b
(In the formula (D2), R ⁵ represents an alkyl group, R ⁶ represents an alkoxy group, an acyloxy group or a halogen group, Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, and c. Represents an integer of 0 or 1.)

In the composition, the ratio of the compound according to the present embodiment to the silicon-containing compound (for example, at least one organosilicon compound selected from the group consisting of the formulas (D1) and (D2)) is a molar ratio. It can be used in the range of 1: 2 to 1: 200. In order to obtain a good resist shape, for example, it can be used in the range of 1: 2 to 1: 100 in the molar ratio. At least one organosilicon compound selected from the group consisting of the formula (D1) and the formula (D2) is preferably used as a hydrolysis condensate (polymer of polyorganosiloxane).

^{R 3} in the hydrolyzable organosilane represented by the formula (D1) is an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkenyl group, an epoxy group or an acryloyl. An "organic group" having a group, a methacryloyl group, a mercapto group, an alkoxyaryl group, an acyloxyaryl group, an isocyanurate group, a hydroxy group, a cyclic amino group, or a cyano group, or a combination thereof, and a Si—C bond. R ⁴ represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 0 to 3.

In the hydrolyzable organosilane of the formula (D2), R ⁵ represents an alkyl group, R ⁶ represents an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group or an arylene group, and b represents 0 or 1. It represents an integer and c represents an integer of 0 or 1.

The hydrolyzable organosilanes represented by the formulas (D1) and (D2) are, for example, hydrolyzable organosilanes which may be contained in the composition for forming an underlayer film for lithography disclosed in International Publication No. 2017/188450. Silane can be mentioned.

In the present embodiment, a film may be formed as a mixture without reacting the compound according to the present embodiment with hydrolyzable organosilane or the like, but the present in the composition for forming a lower layer film for lithography may be formed. The compound according to the embodiment and the above-mentioned hydrolyzable organosilane are hydrolyzed and condensed using one or more compounds selected from inorganic acids, aliphatic sulfonic acids and aromatic sulfonic acids as an acid catalyst. May be good.

Examples of the acid catalyst used at this time include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid and the like. ^{The amount of the catalyst used is preferably 10 to 6} to 10 mol, more preferably 10 to ⁵ to 5 mol, and further preferably 10 to 5 to 5 mol, based on 1 mol of the monomer (total amount of the compound according to the present embodiment and the hydrolyzable organosilane, etc.). It is preferably 10 ^-4 to 1 mol.

The amount of water for hydrolyzing and condensing these monomers is 0.01 to 100 mol per mol of the hydrolyzable substituent bonded to the monomer (compound according to the present embodiment, hydrolyzable organosilane, etc.). It is preferable to add 0.05 to 50 mol, more preferably 0.1 to 30 mol, more preferably. If the addition is 100 mol or less, the equipment used for the reaction does not become excessive, which is economical.

As an operation method, for example, a monomer is added to an aqueous catalyst solution to initiate a hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, the monomer may be diluted with the organic solvent, or both may be performed. The reaction temperature is preferably 0 to 100 ° C, more preferably 40 to 100 ° C. A method in which the temperature is maintained at 5 to 80 ° C. when the monomer is added dropwise and then aged at 40 to 100 ° C. is preferable.

Examples of the organic solvent that can be added to the aqueous catalyst solution or that can dilute the monomer include the organic solvent disclosed in International Publication No. 2017/188450.

The amount of the organic solvent used is preferably 0 to 1,000 ml, particularly preferably 0 to 500 ml, per 1 mol of the monomer (total amount of the compound according to the present embodiment and the hydrolyzable organosilane, etc.). If the amount of the organic solvent used is 1,000 ml or less, the reaction vessel does not become excessive, which is economical.

After that, if necessary, a neutralization reaction of the catalyst is carried out, and the alcohol produced by the hydrolysis condensation reaction is removed under reduced pressure to obtain an aqueous reaction mixture solution. At this time, the amount of the alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents with respect to the acid used in the catalyst. This alkaline substance may be any substance as long as it is alkaline in water.

Subsequently, it is preferable to remove by-products such as alcohol produced by the hydrolysis condensation reaction from the reaction mixture. At this time, the temperature at which the reaction mixture is heated depends on the type of the added organic solvent and the alcohol generated by the reaction, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, still more preferably 15 to 80 ° C. .. The degree of decompression at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less in absolute pressure, and even more preferably absolute. The pressure is 50 kPa or less. Although it is difficult to know exactly the amount of alcohol removed at this time, it is desirable that about 80% by mass or more of the produced alcohol or the like is removed.

Next, the acid catalyst used for hydrolysis condensation may be removed from the reaction mixture. As a method for removing the acid catalyst, a method of mixing water and a reaction mixture and extracting the product with an organic solvent can be exemplified. The organic solvent used at this time is preferably one that can dissolve the product and separates into two layers when mixed with water. For example, the organic solvent disclosed in International Publication No. 2017/188450.

Further, when removing the acid catalyst used for hydrolysis condensation from the reaction mixture, it is also possible to use a mixture of a water-soluble organic solvent and a poorly water-soluble organic solvent. For example, the mixture disclosed in International Publication No. 2017/188450.

The mixing ratio of the water-soluble organic solvent and the water-soluble organic solvent is appropriately selected, but 0.1 to 1,000 parts by mass of the water-soluble organic solvent is preferable and more preferable with respect to 100 parts by mass of the water-soluble organic solvent. Is 1 to 500 parts by mass, more preferably 2 to 100 parts by mass.

In either case, the product in which the acid catalyst remains or the product in which the acid catalyst is removed can be obtained by adding the final solvent and exchanging the solvent under reduced pressure to obtain a solution of the product. The temperature of the solvent exchange at this time depends on the type of the reaction solvent to be removed and the extraction solvent, but is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and further preferably 15 to 80 ° C. The degree of decompression at this time varies depending on the type of extraction solvent to be removed, the exhaust device, the condensing device, and the heating temperature, but is preferably atmospheric pressure or less, more preferably 80 kPa or less in absolute pressure, and still more preferably 50 kPa in absolute pressure. It is as follows.

<Other optional ingredients>
In addition to the above components, the composition may contain an organic polymer compound, a cross-linking agent, a surfactant and the like, if necessary.

By using the organic polymer compound, the dry etching rate (decrease in film thickness per unit time), attenuation coefficient, refractive index, etc. of the resist underlayer film formed from the composition for forming the underlayer film for lithography is adjusted. be able to. The organic polymer compound is not particularly limited, and various organic polymers can be used. A polycondensation polymer, an addition polymerization polymer and the like can be used. For example, the organic polymer compound disclosed in International Publication No. 2017/188450 can be used.

By using a cross-linking agent, it is possible to adjust the dry etching rate (decrease in film thickness per unit time) of the resist underlayer film formed from the composition for forming the underlayer film for lithography. The cross-linking agent is not particularly limited, and various cross-linking agents can be used. Specific examples of the cross-linking agent that can be used in the present embodiment include double bonds such as a melamine compound, a guanamine compound, a glycol uryl compound, a urea compound, an epoxy compound, a thioepoxy compound, an isocyanate compound, an azide compound, and an alkenyl ether group. Examples of the compound containing the above include, but are not limited to, a compound having at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group as a substituent (crosslinkable group). For example, the cross-linking agent disclosed in International Publication No. 2017/188450.

In the composition for forming an underlayer film for lithography, the content of the cross-linking agent is not particularly limited, but is preferably 1 to 10 parts by mass, more preferably 1 part by mass, based on 100 parts by mass of the compound according to the present embodiment. It is 1 to 5 parts by mass. By setting the above-mentioned preferable range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect is enhanced, and the film forming property after crosslinking tends to be enhanced.

The surfactant is effective in suppressing the occurrence of surface defects and the like when the composition for forming an underlayer film for lithography is applied to a substrate. Examples of the surfactant contained in the composition for forming an underlayer film for lithography include the surfactant disclosed in International Publication No. 2017/188450. When a surfactant is used, the ratio thereof is, for example, 0.0001 part to 5 parts by mass or 0.001 part to 1 part by mass with respect to 100 parts by mass of the compound according to the present embodiment. Or 0.01 parts by mass to 0.5 parts by mass.

<Underlayer film for lithography and pattern formation method>
The lithography underlayer film according to the first embodiment of the present invention can be formed by using the lithography underlayer film forming composition according to the first embodiment of the present invention. The lower layer film for lithography of the present embodiment can be suitably used as the lower layer (resist lower layer film) of the photoresist (upper layer) used in the multilayer resist method.

In the present embodiment, for example, a resist underlayer film is formed using a composition for forming an underlayer film for lithography, and at least one photoresist layer is formed on the resist underlayer film, and then the photoresist layer is formed. A pattern can be formed by irradiating a predetermined area with radiation and performing development.

Further, as one aspect of the pattern forming method according to the first embodiment of the present invention using the composition for forming a lower layer film for lithography according to the first embodiment of the present invention prepared as described above. An organic underlayer film is formed on the substrate by using a coating type organic underlayer film material, and a resist underlayer film is formed on the organic underlayer film by using the composition for forming a lower layer film for lithography according to the first embodiment of the present invention. The resist film is formed, an upper resist film is formed on the resist lower layer film using the upper resist film composition, an upper resist pattern is formed on the upper resist film, and the upper resist pattern is used as a mask to etch the resist lower layer film. The pattern is transferred with A pattern forming method in which a pattern is transferred to a body) by etching can be mentioned.

As another aspect of the pattern forming method according to the first embodiment of the present invention, an organic hard mask containing carbon as a main component is formed on a substrate by a CVD method, and the first aspect of the present invention is formed on the organic hard mask. A resist lower layer film is formed using the composition for forming a lower layer film for lithography of the embodiment, an upper layer resist film is formed on the resist lower layer film using the upper layer resist film composition, and an upper layer resist pattern is formed on the upper layer resist film. The upper resist pattern is used as a mask to transfer the pattern to the resist lower layer film by etching, and the resist lower layer film to which the pattern is transferred is used as a mask to transfer the pattern to the organic hard mask by etching. Examples thereof include a pattern forming method in which the pattern is transferred to the substrate (workpiece) by etching using the organic hard mask on which the pattern is transferred as a mask.

As the base material, for example, a semiconductor substrate can be used. As the semiconductor substrate, a silicon substrate can be generally used, but the present invention is not particularly limited, and Si, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN, Al and the like can be used. It is possible to use a material different from that of the layer to be processed.

The metals constituting the base material (workpiece; including the semiconductor substrate) include silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, and iron. , Tantalum, iridium, or molybdenum, or alloys thereof.

Further, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film is formed on a semiconductor substrate as a layer to be processed (processed portion). Etc. can be used. Examples of the layer to be processed containing such a metal include Si, SiO ₂ , SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, W. , W—Si, Al, Cu, Al—Si and the like, various low dielectric films and etching stopper films thereof are used, and can be usually formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.

In the pattern forming method of the present embodiment, an organic underlayer film or an organic hard mask can be formed on the substrate. Of these, the organic underlayer film can be formed from the coating type organic underlayer film material by the rotary coating method or the like, and the organic hard mask is formed from the material of the organic hard mask containing carbon as a main component by the CVD method. be able to. The types of such an organic lower layer film and an organic hard mask are not particularly limited, but when the upper layer resist film forms a pattern by exposure, it is preferable that the upper layer resist film exhibits a sufficient antireflection film function. By forming such an organic underlayer film or an organic hard mask, the pattern formed by the upper layer resist film can be transferred onto the substrate (workpiece) without causing a size conversion difference. The "carbon-based" hard mask is composed of a carbon-based material such as amorphous hydride carbon in which 50% by mass or more of the solid content is also called amorphous carbon and is labeled as a-C: H. Means a hard mask that is. A-C: H films can be deposited by a variety of techniques, but plasma chemical vapor deposition (PECVD) is widely used for cost efficiency and film quality adjustability. As an example of the hard mask, for example, those described in Japanese Patent Application Laid-Open No. 2013-526783 can be referred to.

The resist underlayer film using the resist underlayer film forming composition of the present embodiment used in the pattern forming method of the present embodiment is obtained from the composition for forming the underlayer film for lithography by an organic underlayer film or the like by a spin coating method or the like. It can be manufactured on the provided workpiece. When the resist undercoat is formed by the spin coating method, it is desirable to evaporate the solvent after spin coating and bake in order to promote the crosslinking reaction for the purpose of preventing mixing with the upper resist film. The bake temperature is preferably in the range of 50 to 500 ° C. At this time, although it depends on the structure of the manufactured device, the baking temperature is particularly preferably 400 ° C. or lower in order to reduce heat damage to the device. The baking time is preferably in the range of 10 seconds to 300 seconds.

Further, in the pattern forming method of the present embodiment, as a method of forming a pattern on the upper resist film, a lithography method using light having a wavelength of 300 nm or less or EUV light; an electron beam direct drawing method and an induced self-organization method. Either method can be preferably used. By using such a method, a fine pattern can be formed on the resist upper layer film.

The upper-layer resist film composition can be appropriately selected depending on the method for forming a pattern on the above-mentioned upper-layer resist film. For example, when performing lithography using light of 300 nm or less or EUV light, a chemically amplified photoresist film material can be used as the upper resist film composition. As such a photoresist film material, a photoresist film is formed and exposed, and then a positive pattern is formed by dissolving an exposed portion with an alkaline developer, or a development made of an organic solvent. An example thereof is one in which a negative pattern is formed by dissolving an unexposed portion with a liquid.

The resist underlayer film formed from the lithography underlayer film forming composition of the present embodiment may absorb the light depending on the wavelength of the light used in the lithography process. Then, in such a case, it can function as an antireflection film having an effect of preventing the reflected light from the substrate.

In addition to the function as a hard mask, the EUV resist underlayer film can also be used for the following purposes. EUV that can prevent the reflection of unfavorable exposure light, for example, the above-mentioned UV or DUV (ArF light, KrF light) from the substrate or interface during EUV exposure (wavelength 13.5 nm) without intermixing with the EUV resist. As the lower layer antireflection film of the resist, the composition for forming the lower layer film for lithography according to the present embodiment can be used. Reflection can be efficiently prevented in the lower layer of the EUV resist. Further, since the composition for forming the lower layer film is excellent in the ability to absorb EUV, it is possible to exhibit the sensitizing effect of the upper layer resist composition, which contributes to the improvement of sensitivity. When used as an EUV resist underlayer, the process can be carried out in the same manner as the photoresist underlayer.

[Second embodiment]
<Composition for forming an underlayer film for lithography>
The composition for forming an underlayer film for lithography according to a second embodiment of the present invention is a composition for forming an underlayer film for lithography containing a compound according to the present embodiment. The composition for forming an underlayer film for lithography of the present embodiment is capable of reducing film defects (thin film formation), has good storage stability, is highly sensitive, has long-term light resistance, and has a good resist pattern shape. Can be granted. The composition for forming an underlayer film for lithography of the present embodiment may not contain a silicon-containing compound.

The composition for forming an underlayer film for lithography of the present embodiment is applicable to a wet process, and is useful for forming a photoresist underlayer film excellent in heat resistance, adhesion, step embedding characteristics, and particularly flatness. A composition for forming a lower layer film can be realized. Since this composition for forming an underlayer film for lithography uses a compound having a specific structure, which can have a relatively high crosslink density and high solvent solubility, deterioration of the film during baking is suppressed. Therefore, it is possible to form an underlayer film having excellent etching resistance to fluorine gas-based plasma etching and the like. Furthermore, since it has excellent adhesion to the resist layer, an excellent resist pattern can be formed. Since the composition for forming a lower layer film for lithography of the present embodiment is particularly excellent in heat resistance, step embedding characteristics and flatness, for example, as a composition for forming a lower layer film of a resist provided in the lowermost layer among a plurality of resist layers. Can be used. However, the resist underlayer film formed by using the composition for forming the underlayer film for lithography of the present embodiment may further include another resist underlayer between the substrate and the resist underlayer.

The composition for forming an underlayer film for lithography according to the present embodiment may further contain a solvent, an acid generator, an acid cross-linking agent and the like in addition to the compound according to the present embodiment. Further, as an optional component, a basic compound, other substances, water, alcohol, a curing catalyst and the like can be included. From the viewpoint of coatability and quality stability, the content of the compound according to the present embodiment in the composition for forming an underlayer film for lithography is preferably 0.1 to 70% by mass, preferably 0.5 to 50% by mass. % Is more preferable, and 3.0 to 40% by mass is particularly preferable.

<Solvent>
Examples of the solvent used in the present embodiment include those described in the first embodiment. The amount is also as described in the first embodiment.

<Acid cross-linking agent>
As described above, the composition for forming an underlayer film for lithography of the present embodiment may contain an acid cross-linking agent, if necessary, from the viewpoint of suppressing intermixing and the like. Examples of the acid cross-linking agent that can be used in the present embodiment include double bonds such as a melamine compound, an epoxy compound, a guanamine compound, a glycoluril compound, a urea compound, a thioepoxy compound, an isocyanate compound, an azido compound, and an alkenyl ether group. Examples of the compound include those having at least one group selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group as a substituent (crosslinkable group), but the compound is not particularly limited thereto. In addition, these acid cross-linking agents can be used individually by 1 type or in combination of 2 or more types. Moreover, these may be used as an additive. Further, a compound containing a hydroxy group can also be used as a cross-linking agent. Specific examples of the acid cross-linking agent include those described in International Publication No. 2013/024779.

In the composition for forming an underlayer film for lithography of the present embodiment, the content of the acid cross-linking agent is not particularly limited, but is 5 to 50 mass with respect to 100 mass by mass of the total solid content of the composition for forming an underlayer film for lithography. The amount is preferably 10 to 40 parts by mass, more preferably 10 to 40 parts by mass. By setting the above-mentioned preferable range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect is enhanced, and the film forming property after crosslinking tends to be enhanced.

<Acid generator>
The composition for forming an underlayer film for lithography of the present embodiment may contain an acid generator, if necessary, from the viewpoint of further promoting the cross-linking reaction by heat. As the acid generator, those that generate acid by thermal decomposition, those that generate acid by light irradiation, and the like are known, but any of them can be used. As the acid generator, for example, the one described in International Publication No. WO2013 / 024779 can be used.

In the composition for forming an underlayer film for lithography of the present embodiment, the content of the acid generator is not particularly limited, but is 0.1 with respect to 100 parts by mass of the total solid content of the composition for forming an underlayer film for lithography. It is preferably about 50 parts by mass, more preferably 0.5 to 40 parts by mass. By setting the above-mentioned preferable range, the amount of acid generated tends to increase and the crosslinking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.

<Basic compound>
Further, the composition for forming an underlayer film for lithography of the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.

The basic compound acts as a quencher for the acid to prevent the acid generated in a smaller amount than the acid generator from advancing the cross-linking reaction. Examples of such basic compounds include primary, secondary or tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, and nitrogen-containing compounds having a carboxyl group. Examples thereof include a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and the like, but the present invention is not particularly limited thereto. Specific examples of the basic compound include those described in International Publication No. 2013/024779.

In the composition for forming an underlayer film for lithography of the present embodiment, the content of the basic compound is not particularly limited, but is 0.001 with respect to 100 parts by mass of the total solid content of the composition for forming an underlayer film for lithography. It is preferably about 2 parts by mass, more preferably 0.01 to 1 part by mass. By setting the above-mentioned preferable range, the storage stability tends to be enhanced without excessively impairing the crosslinking reaction.

Further, the composition for forming an underlayer film for lithography of the present embodiment may contain another resin or compound for the purpose of imparting thermosetting property and controlling the absorbance. Examples of such other resins or compounds include naphthalene resin, xylene resin, naphthalene-modified resin, phenol-modified resin of naphthalene resin, polyhydroxystyrene, dicyclopentadiene resin, (meth) acrylate, dimethacrylate, trimethacrylate, and tetramethacrylate. Resins containing naphthalene rings such as vinylnaphthalene and polyacenaphthalene, biphenyl rings such as phenanthrenquinone and fluorene, and heterocycles having heteroatoms such as thiophene and indene, and resins not containing aromatic rings; rosin-based resins and cyclodextrin. , Adamantane (poly) all, tricyclodecane (poly) all and resins or compounds containing an alicyclic structure such as derivatives thereof, but are not particularly limited thereto. Further, the composition for forming an underlayer film for lithography of the present embodiment may contain a known additive. Examples of the known additives include, but are not limited to, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.

<Resist underlayer film for lithography and pattern formation method>
The resist underlayer film for lithography according to the second embodiment of the present invention is formed by using the composition for forming the underlayer film for lithography according to the second embodiment of the present invention. The pattern formed in this embodiment can be used, for example, as a resist pattern or a circuit pattern.

Further, the pattern forming method according to the second embodiment of the present invention is a step of forming a resist underlayer film on a substrate using the composition for forming a underlayer film for lithography according to the second embodiment of the present invention (A). -1 step), a step of forming at least one photoresist layer on the resist underlayer film (step A-2), and a step of forming at least one photoresist layer in the A-2 step. It has a step (A-3 step) of irradiating a predetermined region of the photoresist layer with radiation to develop the photoresist layer. The "photoresist layer" means the outermost layer of the resist layer, that is, the layer provided on the outermost side (opposite side of the substrate) of the resist layer.

Further, another pattern forming method of the second embodiment of the present invention is a step of forming a resist underlayer film on a substrate by using the composition for forming a underlayer film for lithography according to the second embodiment of the present invention. B-1 step), a step of forming a resist intermediate layer film on the lower layer film using a resist intermediate layer film material (for example, a resist layer containing silicon) (step B-2), and the resist intermediate layer film. After forming at least one photoresist layer on the surface (step B-3) and forming at least one photoresist layer in the step B-3, radiation is applied to a predetermined region of the photoresist layer. After the resist pattern was formed in the step of forming a resist pattern by irradiating and developing the resist (step B-4) and the step B-4, the resist intermediate layer film was etched using the resist pattern as a mask. A step (B-5 step) of etching the lower layer film using the obtained intermediate layer film pattern as an etching mask and etching the substrate using the obtained lower layer film pattern as an etching mask to form a pattern on the substrate. Have.

As long as the resist underlayer film for lithography of the present embodiment is formed from the composition for forming the underlayer film for lithography of the present embodiment, the forming method thereof is not particularly limited, and a known method can be applied. .. For example, the composition for forming an underlayer film for lithography of the present embodiment is applied onto a substrate by a known coating method such as spin coating or screen printing or a printing method, and then removed by volatilizing an organic solvent. , A resist underlayer film can be formed.

When forming the resist lower layer film, it is preferable to perform a baking treatment in order to suppress the occurrence of a mixing phenomenon with an upper layer resist (for example, a photoresist layer or a resist intermediate layer film) and promote a crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C, more preferably 200 to 400 ° C. The baking time is also not particularly limited, but is preferably in the range of 10 seconds to 300 seconds. The thickness of the resist underlayer film can be appropriately selected according to the required performance and is not particularly limited, but is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm. It is preferable to do so.

After forming the resist underlayer film on the substrate, the resist intermediate layer film can be provided between the photoresist layer and the resist underlayer film. For example, in the case of a two-layer process, a silicon-containing resist layer, a single-layer resist made of ordinary hydrocarbons, or the like can be provided as a resist intermediate layer film on the resist underlayer film. Further, for example, in the case of a three-layer process, it is preferable to prepare a silicon-containing intermediate layer between the resist intermediate layer film and the photoresist layer, and a silicon-free single-layer resist layer on the silicon-containing intermediate layer. Known photoresist materials can be used for forming the photoresist layer, the resist intermediate layer film, and the resist layer provided between these layers.

For example, as the silicon-containing resist material for the two-layer process, a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as the base polymer from the viewpoint of oxygen gas etching resistance, and an organic solvent is used, if necessary. A positive photoresist material containing a basic compound or the like is preferably used. Here, as the silicon atom-containing polymer, a known polymer used in this type of resist material can be used.

Further, for example, a polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer for the three-layer process. By giving the resist intermediate layer film an effect as an antireflection film, it tends to be possible to effectively suppress reflection. For example, in the process for 193 nm exposure, if a material containing a large amount of aromatic groups and having high substrate etching resistance is used as the resist underlayer film, the k value tends to be high and the substrate reflection tends to be high, but the resist intermediate layer film reflects. By suppressing the above, the substrate reflection can be reduced to 0.5% or less. The intermediate layer having such an antireflection effect is not limited to the following, but for 193 nm exposure, a phenyl group or an absorbent group having a silicon-silicon bond is introduced, and the polysilseskioki crosslinked with an acid or heat. Sun is preferably used.

Further, a resist intermediate layer film formed by the Chemical Vapor Deposition (CVD) method can also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, and for example, a SiON film is known. In general, the formation of a resist intermediate layer film by a wet process such as a spin coating method or screen printing is simpler and more cost effective than the CVD method. The upper layer resist in the three-layer process may be either a positive type or a negative type, and the same single-layer resist as normally used can be used.

Further, the resist underlayer film of the present embodiment can also be used as an antireflection film for a normal single-layer resist or a base material for suppressing pattern collapse. Since the resist underlayer film of the present embodiment has excellent etching resistance for base processing, it can be expected to function as a hard mask for base processing.

When the resist layer is formed from the above-mentioned known photoresist material, a wet process such as a spin coating method or screen printing is preferably used as in the case of forming the resist underlayer film. Further, after applying the resist material by a spin coating method or the like, prebaking is usually performed, and this prebaking is preferably performed in a range of a baking temperature of 80 to 180 ° C. and a baking time of 10 seconds to 300 seconds. After that, a resist pattern can be obtained by performing exposure, post-exposure baking (PEB), and development according to a conventional method. The thickness of each resist film is not particularly limited, but is generally preferably 30 nm to 500 nm, more preferably 50 nm to 400 nm.

Further, the exposure light may be appropriately selected and used according to the photoresist material used. In general, high-energy rays having a wavelength of 300 nm or less, specifically, excimer lasers having a wavelength of 248 nm, 193 nm, and 157 nm, soft X-rays having a wavelength of 3 to 20 nm, electron beams, X-rays, and the like can be mentioned.

The resist pattern formed by the above method is such that the pattern collapse is suppressed by the resist underlayer film of the present embodiment. Therefore, by using the resist underlayer film of the present embodiment, a finer pattern can be obtained, and the exposure amount required to obtain the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used as the etching of the resist underlayer film in the two-layer process. As the gas etching, etching using oxygen gas is preferable. In addition to oxygen gas, it is also possible to add an inert gas such as He or Ar, or CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ , or H _{2 gas.} It is also possible to perform gas etching using only _{CO, CO 2} , NH ₃ , N ₂ , NO ₂ , and H ₂ gases without using oxygen gas. In particular, the latter gas is preferably used to protect the side wall to prevent undercutting of the side wall of the pattern.

On the other hand, gas etching is also preferably used for etching the intermediate layer (the layer located between the photoresist layer and the resist underlayer film) in the three-layer process. As the gas etching, the same one as described in the above-mentioned two-layer process can be applied. In particular, the processing of the intermediate layer in the three-layer process is preferably performed by using a fluorocarbon-based gas and using the resist pattern as a mask. After that, the resist underlayer film can be processed by, for example, performing oxygen gas etching using the intermediate layer pattern as a mask as described above.

Here, when an inorganic hard mask intermediate layer film is formed as an intermediate layer, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film (SiON film) are formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following, and for example, the method described in JP-A-2002-334869 and WO2004 / 0666377 can be used. A photoresist film can be formed directly on such an intermediate layer film, but an organic antireflection film (BARC) is formed on the intermediate layer film by spin coating, and a photoresist film is formed on the organic antireflection film (BARC). You may.

As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. By giving the resist interlayer film an effect as an antireflection film, it tends to be possible to effectively suppress reflection. The specific material of the polysilsesquioxane-based intermediate layer is not limited to the following, and for example, those described in JP-A-2007-226170 and JP-A-2007-226204 can be used. ..

Etching of the substrate can also be performed by a conventional method. For example, if the substrate is SiO ₂ or SiN, etching mainly composed of chlorofluorocarbons, and if the substrate is p—Si, Al, or W, chlorine-based or bromine-based gas is used. Mainly etching can be performed. When the substrate is etched with a fluorocarbon-based gas, the silicon-containing resist in the two-layer resist process and the silicon-containing intermediate layer in the three-layer process are peeled off at the same time as the substrate is processed. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled off, and generally, dry etching peeling is performed with a fluorocarbon-based gas after the substrate is processed. ..

The resist underlayer film of the present embodiment is excellent in etching resistance of these substrates. As the substrate, a known substrate can be appropriately selected and used, and the present invention is not particularly limited, and examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, and Al. Be done. Further, the substrate may be a laminated body having a film to be processed (substrate to be processed) on a base material (support). As such a film to be processed, _{various Low-k films such as Si, SiO 2} , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si and their stopper films and stopper films thereof. Etc., and usually, a material different from the base material (support) is used. The thickness of the substrate or the film to be processed is not particularly limited, but is usually preferably about 50 nm to 10,000 nm, and more preferably 75 nm to 5,000 nm.

The resist underlayer film of the present embodiment is excellent in embedding flatness in a substrate having a step. As a method for evaluating the embedding flatness, a known method can be appropriately selected and used, and is not particularly limited. For example, a solution of each compound adjusted to a predetermined concentration is placed on a silicon substrate having a step. It is applied by spin coating, and the solvent is removed and dried at 110 ° C. for 90 seconds to form an underlayer film having a predetermined thickness, and then the line & space area is baked at a temperature of about 240 to 300 ° C. for a predetermined time. By measuring the difference (ΔT) between the thickness of the lower layer film and the open region without the pattern with an ellipsometer, the embedding flatness with respect to the stepped substrate can be evaluated.

3) Optical article forming composition and optical article The optical component forming composition according to the present embodiment is an optical component forming composition containing the compound according to the present embodiment. The composition for forming an optical component is usefully used for forming an optical article. By containing the compound according to the present embodiment, the composition for forming an optical component of the present embodiment can be expected to have a high refractive index and high transparency of the obtained optical article, and further, storage stability and structure forming ability. (Film forming ability) and heat resistance are expected.

The refractive index of the optical article is preferably 1.65 or more, more preferably 1.70 or more, still more preferably 1.75 or more, from the viewpoint of miniaturization of optical components and improvement of light collection rate. From the viewpoint of improving the light collection rate, the transparency of the optical article is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more.

The method for measuring the refractive index is not particularly limited, and a known method is used. For example, spectroscopic ellipsometry method, minimum declination method, critical angle method (Abbe method, Prurich method), V-block method, prism coupler method and immersion method (Becke line method) can be mentioned. The method for measuring transparency is not particularly limited, and a known method is used. For example, spectrophotometers and spectroscopic ellipsometry methods can be mentioned.

Further, the cured product according to the present embodiment for forming an optical article obtained by curing the composition for forming an optical component can be a three-dimensional crosslinked product, and can be colored by a wide range of heat treatment from low temperature to high temperature. It is suppressed, and high refractive index and high transparency can be expected.

The composition for forming an optical component of the present embodiment may further contain a solvent in addition to the compound according to the present embodiment. The solvent can be the same as the solvent used in the composition for forming the underlayer film for lithography of the present embodiment described above.

In the composition for forming an optical component of the present embodiment, the relationship between the amount of the solid component and the amount of the solvent is not particularly limited, but the solid component is 1 to 80% by mass with respect to the total of 100% by mass of the solid component and the solvent. And the solvent is preferably 20 to 99% by mass, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, still more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent. Particularly preferably, the solid component is 2 to 10% by mass and the solvent is 90 to 98% by mass. The composition for forming an optical component of the present embodiment may not contain a solvent.

The composition for forming an optical component of the present embodiment contains at least one selected from the group consisting of an acid cross-linking agent (G), an acid diffusion control agent (E) and another component (F) as other solid components. You may.

In the composition for forming an optical component of the present embodiment, the content of the compound according to the present embodiment is not particularly limited, but the total mass of the solid component (compound according to the present embodiment, acid cross-linking agent (G), acid diffusion). It is preferably 50 to 99.4% by mass, more preferably 55 to 90% by mass, based on the total of the solid components arbitrarily used such as the control agent (E) and the other component (F), the same applies hereinafter). It is more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass.

<Acid generator (C)>
The composition for forming an optical component of the present embodiment preferably contains at least one acid generator (C) that directly or indirectly generates an acid by heat. The acid generator (C) is not particularly limited, and can be, for example, the same as the acid generator (C) that can be contained in the composition for forming an underlayer film for lithography of the present embodiment described above.

In the composition for forming an optical component of the present embodiment, the content of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, or 3 to 40% by mass of the total mass of the solid components. 30% by mass is more preferable, and 10 to 25% by mass is particularly preferable. By using the acid generator (C) within the range of the content, a higher refractive index can be obtained.

<Acid cross-linking agent (G)>
The composition for forming an optical component of the present embodiment preferably contains one or more acid cross-linking agents (G) when used as an additive for increasing the strength of the structure. The acid cross-linking agent (G) is not particularly limited, and can be, for example, the same as the acid cross-linking agent (G) that can be contained in the composition for forming an underlayer film for lithography of the present embodiment described above.

In the composition for forming an optical component of the present embodiment, the content of the acid cross-linking agent (G) is preferably 0.5 to 49% by mass, more preferably 0.5 to 40% by mass, based on the total mass of the solid components. 1 to 30% by mass is more preferable, and 2 to 20% by mass is particularly preferable. When the content ratio of the acid cross-linking agent (G) is 0.5% by mass or more, it is preferable because the effect of suppressing the solubility of the composition for forming an optical component in an organic solvent can be improved, while 49% by mass or less. This is preferable because it can suppress a decrease in heat resistance as a composition for forming an optical component.

Further, the content of at least one compound selected from the acid cross-linking agent (G1), the acid cross-linking agent (G2), and the acid cross-linking agent (G3) in the acid cross-linking agent (G) is not particularly limited. , The range can be various depending on the type of the substrate used when forming the composition for forming an optical component.

<Acid diffusion control agent (E)>
The composition for forming an optical component of the present embodiment is an acid diffusion control agent having an action of controlling diffusion of an acid generated from an acid generator in the composition for forming an optical component to prevent an unfavorable chemical reaction ( E) may be contained. By using such an acid diffusion control agent (E), the storage stability of the composition for forming an optical component is improved. In addition, the resolution is further improved, and changes in the line width of the structure due to fluctuations in the leaving time after heating can be suppressed, resulting in extremely excellent process stability. The acid diffusion control agent (E) is not particularly limited, and can be, for example, the same as the acid diffusion control agent (E) that can be contained in the composition for forming a lower layer film for lithography of the present embodiment described above.

The content of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass, based on the total mass of the solid component. 0.01 to 3% by mass is particularly preferable. When the content of the acid diffusion control agent (E) is within the above range, deterioration of resolution, pattern shape, dimensional fidelity and the like can be further suppressed. Further, even if the leaving time from the electron beam irradiation to the heating after the irradiation is long, the shape of the upper layer portion of the pattern does not deteriorate. Further, when the content of the acid diffusion control agent (E) is 10% by mass or less, it is possible to prevent deterioration of sensitivity, developability of the unexposed portion and the like. Further, by using such an acid diffusion control agent, the storage stability of the composition for forming an optical component is improved, the resolution is improved, and the retention time before irradiation and the retention time after irradiation are improved. It is possible to suppress the change in the line width of the composition for forming an optical component due to the fluctuation of the above, and the process stability is extremely excellent.

<Other ingredients (F)>
The composition for forming an optical component of the present embodiment contains a dissolution accelerator, a dissolution control agent, a sensitizer, and a surfactant as other components (F), if necessary, as long as the object of the present embodiment is not impaired. One or two or more kinds of additives such as an activator and an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be added. The other component (F) can be, for example, the same as the other component (F) that can be contained in the composition for forming a lower layer film for lithography of the present embodiment described above.

In the composition for forming an optical component of the present embodiment, the content of the compound, the acid diffusion control agent (E), and the other component (F) according to the present embodiment (compound / acid diffusion control agent (E) according to the present embodiment). ) / Other components (F)) are in mass% based on solid matter, preferably 50 to 99.4 / 0.001 to 49 / 0.001 to 49/0 to 49, and more preferably 55 to 90 /. 1 to 40/0.01 to 10/0 to 5, more preferably 60 to 80/3 to 30/0.01 to 5/0 to 1, particularly preferably 60 to 70/10 to 25/0.01 to It is 3/0. The content ratio of each component is selected from each range so that the total is 100% by mass. With the above content ratio, the performance such as sensitivity, resolution, and developability is further excellent.

The method for preparing the composition for forming an optical component of the present embodiment is not particularly limited, and for example, each component is dissolved in a solvent at the time of use to form a uniform solution, and then, if necessary, for example, a pore size of about 0.2 μm. Examples thereof include a method of filtering with a filter or the like.

The composition for forming an optical component of the present embodiment may contain other resins as long as the object of the present invention is not impaired. Other resins are not particularly limited and include, for example, novolak resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinylphenol as a monomer unit. Examples thereof include polymers and derivatives thereof. The content of the resin is not particularly limited, and is appropriately adjusted according to the type of the compound according to the present embodiment to be used.

Further, the cured product of the present embodiment is obtained by curing the composition for forming an optical component, and can be used as various resins. These cured products can be used for various purposes as highly versatile materials imparting various properties such as high melting point, high refractive index and high transparency. The cured product can be obtained by irradiating the composition with a known method corresponding to each composition such as light irradiation and heating.

These cured products can be used as various synthetic resins such as epoxy resin, polycarbonate resin, and acrylic resin, and further, by utilizing their functionality, as optical parts such as lenses and optical sheets.

[Purification method]
The method for purifying a compound according to this embodiment is a step of dissolving the compound or a derivative thereof in a solvent containing an organic solvent that is not arbitrarily mixed with water to obtain a solution (B), and the obtained solution (B) and acidity. The present invention comprises a first extraction step of contacting the compound with an aqueous solution of the above to extract impurities in the compound or a derivative thereof.

Specifically, the compound is dissolved in an organic solvent that is arbitrarily immiscible with water, and the solution is brought into contact with an acidic aqueous solution for extraction treatment to transfer the metal content contained in the compound to the aqueous phase. The organic phase and the aqueous phase are separated and purified. By this method, the content of various metals in the compound or its derivative can be significantly reduced. Examples of the derivative of the compound include a resin obtained by reacting the compounds with each other or with the compound and another compound. Hereinafter, the compound of the present embodiment or a derivative thereof is also collectively referred to as "the compound of the present embodiment".

The organic solvent that is not miscible with water means an organic solvent having a solubility in water of less than 50% by mass at any temperature of 20 to 90 ° C. From the viewpoint of productivity, the solubility is preferably less than 25% by mass. The organic solvent that is arbitrarily immiscible with water is not limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable. The amount of the organic solvent used is usually about 1 to 100 times by mass with respect to the compound of the present invention.

Specific examples of the solvent used in the purification method include those described in International Publication WO2015 / 080240. These solvents may be used alone or in combination of two or more. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, and cyclohexanone and propylene glycol monomethyl ether acetate are particularly preferable.

The acidic aqueous solution is appropriately selected from the generally known aqueous solutions of organic and inorganic compounds dissolved in water. For example, those described in International Publication WO2015 / 080240 can be mentioned. These acidic aqueous solutions may be used alone or in combination of two or more. Among these, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid and citrus. One or more organic acid aqueous solutions selected from the group consisting of acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid are preferable. As the water used at this time, for the purpose of the present invention, water having a low metal content, for example, ion-exchanged water or the like is preferably used.

The pH of the acidic aqueous solution is not limited, but an aqueous solution with excessively high acidity may adversely affect the compound of the present invention, which is not preferable. Usually, the pH range is about 0 to 5, and more preferably about pH 0 to 3.

The amount of the acidic aqueous solution used is not limited, but if the amount is too small, it is necessary to increase the number of extractions for removing the metal, and conversely, if the amount is too large, the total amount of the liquid increases and the workability may decrease. be. The amount of the aqueous solution used is usually 10 to 200% by mass, preferably 20 to 100% by mass, based on the solution containing the compound and the like of the present embodiment and the organic solvent.

The temperature at which the extraction process is performed is usually 20 to 90 ° C, preferably 30 to 80 ° C. The extraction operation is performed, for example, by stirring or the like to mix the two well, and then allowing the mixture to stand. As a result, the metal content contained in the compound or the like of the present embodiment is transferred to the aqueous phase. Further, since the acidity of the solution is lowered by this treatment, deterioration of the compound of the present invention can be suppressed.

The oil phase containing the compound and the like of this embodiment is recovered from the mixture after the treatment by decantation or the like. The standing time is not limited, but it is not preferable if the standing time of the mixture is excessively short because the separation between the oil phase containing the organic solvent and the aqueous phase becomes insufficient. The standing time is usually 1 minute or more, more preferably 10 minutes or more, still more preferably 30 minutes or more. The extraction process may be performed once or more than once.

It is preferable that the recovered oil phase is subjected to a washing treatment with water, that is, an extraction treatment using water (second extraction step). The process can be performed as described above. The oil phase after washing thus obtained may contain water, and the water can be easily removed by vacuum distillation or the like. If necessary, an organic solvent can be added to the oil phase to adjust the concentration of the compound of the present invention. The target compound can be isolated by subjecting the oil phase to a known treatment such as vacuum distillation or reprecipitation.

Hereinafter, this embodiment will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
1) Synthesis of BCA [4] -co-BAB-DMHDO In a 100 ml eggplant flask, 2,5-dimethyl-2,5-hexanediol (17 mmol, 2.49 g), pyridine (40 mmol, 3.22 ml), CCl ₄ ( 40 ml) was added, the mixture was cooled to 0 ° C., bromoacetyl bromide (40 mmol, 8.07 g) was slowly added, and the mixture was stirred for 1 hour. Then, the reaction was carried out by stirring at room temperature for 24 hours. After completion of the reaction, the salt was removed by gravity filtration, the filtrate was diluted with diethyl ether, and washed with 1N aqueous HCl solution and saturated aqueous sodium hydrogen carbonate solution in this order. The solution was dried and then concentrated to give a pale yellow solid. The resulting product ^{was analyzed by 1} H-NMR and IR. These spectra are shown in FIGS. 1 and 2. The yield was 5.14 g and the yield was 82%.

_BCA _[4] in a test tube (0.4mmol, 0.26g), K 2 CO 3 (2mmol, 0.276g), TBAB (0.1mmol, 0.032g), NMP and (12 ml) was added, at 80 ° C. Stirring for 2 hours produced phenoxide. Then, BAB-DMHDO (0.8 mmol, 0.310 g) synthesized as described above was carefully added, and the reaction was carried out for 24 hours. After completion of the reaction, the mixture was re-submerged in a 0.5 N aqueous HCl solution and filtered using Kiriyama Rohto (registered trademark). It was thoroughly washed with water and dried under reduced pressure at 60 ° C. for at least one day to obtain a milky brown solid. The resulting product ^{was analyzed by 1} H-NMR, IR, GPC. The yield was 0.344 g and the yield was 60%. Thermal analysis was also performed. These spectra are shown in FIGS. 3 and 4, and the analysis results are shown in Table 1.

2) Evaluation of BCA [4] -co-BAB-DMHDO PGMEA is used as a solvent, and BCA [4] -co-BAB-DMHDO and a photoacid generator (PAG) are dissolved therein to form a resist film. The thing was prepared. The solid content concentration was 5% by mass, and the mass ratio of BCA [4] -co-BAB-DMHDO: PAG was 100:10. A thin film (film thickness: about 60 nm) was formed using a spin coater, and exposure, development, and rinsing were performed to create a sensitivity curve. The film formation conditions, exposure amount, and development conditions are shown below. As a result of the sensitivity evaluation, it was clarified that it has a very high sensitivity characteristic of _{E 0} = 0.8 mJ / cm ^2.

Film formation conditions Slope 30s, 4000 RPM
Prebake 110 ℃ 1min
Development conditions PEB 110 ℃ 1min
Immerse in 2.38 mass% TMAH aqueous solution for 30s Immersion in pure water for 15s

[Example 2]
Using 2,7-dimethyl-2,7-octanediol (17 mmol, 2.73 g) instead of 2,5-dimethyl-2,5-hexanediol (17 mmol, 2.49 g), BCA [4] ( BCA [8] -co-BAB-DMODO, 0.2 g in the same manner as in Example 1 except that BCA [8] (0.2 mmol, 0.26 g) was used instead of 0.4 mmol (0.26 g). Got As a result of sensitivity evaluation of the obtained BCA [8] -co-BAB-DMODO in the same manner as in Example 1, the sensitivity was as high as _{E 0} = 1.0 mJ / cm ^2.

[Comparative Example 1] Evaluation result of a composition using AC-1 as a resist material 2-methyl-2-methacryloyloxyadamantane 4.15 g, methacrylloyloxy-γ-butyrolactone 3.00 g, 3-hydroxy-1-adamantyl 2.08 g of methacrylate and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare a reaction solution. The reaction solution was polymerized under a nitrogen atmosphere at a reaction temperature of 63 ° C. for 22 hours, and then the reaction solution was added dropwise to 400 mL of n-hexane. The obtained produced resin was coagulated and purified, and the produced white powder was filtered and then dried under reduced pressure at 40 ° C. overnight to obtain AC-1 represented by the following formula. When the sensitivity was evaluated in the same manner as in Example 1 except that AC-1 was used, BCA [4] -co-BAB-DMHDO and BCA [8] -co-BAB-DMODO, which are the compounds of this embodiment, were evaluated. It turned out to be inferior to.

Claims

A compound having a polyphenol moiety, in which the hydroxyl group of the polyphenol is intramolecularly crosslinked with a group containing a dissociative bond that dissociates under acid or alkaline conditions.
The compound according to claim 1, wherein the polyphenol is calixarene.
The compound according to claim 1 or 2, which is a compound represented by the following formula (P-0C) or (P-1C).

(During the ceremony,
L 1 to L 4 are independently single-bonded; a linear alkylene group having 1 to 20 carbon atoms which may have a substituent; and 3 to 20 carbon atoms which may have a substituent. Branched alkylene group; cycloalkylene group having 3 to 20 carbon atoms which may have a substituent; arylene group having 6 to 24 carbon atoms which may have a substituent; -O-; -OC (= O)-; -OC (= O) O-; -OR 2- C (= O) O-; -N (R 20 ) -C (= O)-; -N (R 20 ) -C ( = O) O-; -S-; -SO-; -SO 2-, a divalent organic group selected from the group consisting of any combination thereof.
R 2 is an alkylene group having 1 to 10 carbon atoms,
R 20 is an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent.
Each of R 16 to R 19 is an independent linear alkyl group having 1 to 20 carbon atoms which may have a substituent; and a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent. An aryl group having 6 to 20 carbon atoms which may have a substituent; an alkoxy group having 1 to 20 carbon atoms which may have a substituent; a cyano group; a nitro group; a hydroxyl group; a heterocyclic group; a halogen. Atomic; carboxyl group; alkylsilyl group having 1 to 20 carbon atoms; substituted methyl group having 2 to 20 carbon atoms, 1-substituted ethyl group having 3 to 20 carbon atoms, and 4 to 20 carbon atoms having the property of being dissociated by an acid. 1-substituted-n-propyl group, 1-branched alkyl group with 3 to 20 carbon atoms, silyl group with 1 to 20 carbon atoms, acyl group with 2 to 20 carbon atoms, 1-substituted alkoxy with 2 to 20 carbon atoms An alkyl group, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkoxycarbonylalkyl group; or a hydrogen atom.
R 12 to R 15 are independent hydrogen atoms, alkyl groups having 2 to 20 carbon atoms, or groups represented by the following formula (P-0C-1).

Each of R 21 independently has an alkyl group having 1 to 20 carbon atoms which may have a substituent; a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent; and a substituent. It may have an aryl group having 6 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms which may have a substituent; a cyano group; a nitro group; a heterocyclic group; a halogen atom; a carboxyl group; a carbon number of 1 carbon group. Alkylsilyl group to 20; substituted methyl group having 2 to 20 carbon atoms, 1-substituted ethyl group having 3 to 20 carbon atoms, 1-substituted-n-propyl group having 4 to 20 carbon atoms, which have the property of being dissociated by an acid. Group, 1-branched alkyl group with 3 to 20 carbon atoms, silyl group with 1 to 20 carbon atoms, acyl group with 2 to 20 carbon atoms, 1-substituted alkoxyalkyl group with 2 to 20 carbon atoms, 2 to 20 carbon atoms A cyclic ether group, an alkoxycarbonyl group having 2 to 20 carbon atoms, or an alkoxycarbonylalkyl group.
m 7 to 10 are independently integers of 1 to 4,
p 7 is an integer of 0 to 5 independently.
However, at least two groups of L 1 R 16 to L 4 R 19 are ether-bonded to the benzene ring to form an intramolecular cross-linking group. )

(During the ceremony,
L 5 to L 12 are independently divalent organic groups, respectively.
R 30 to R 37 are independent groups defined by the above R 16 to R 19.
R 22 to R 29 are independent groups defined by the above R 12 to R 15, respectively.
m 11 to 18 are independently integers of 1 to 4,
However, at least two groups of L 5 R 30 to L 12 R 37 are ether-bonded to the benzene ring to form an intramolecular cross-linking group. )
The compound according to claim 1 to 3, which is represented by the following formula (P-0A) or (P-1A).

(In the formula, RA is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms.
At least two or more groups of D 1 to D 4 form an intramolecular cross-linking group that ether-bonds to the benzene ring, and the group that does not participate in the cross-linking is an OH group. )

(Wherein, R B is a linear alkyl group or branched alkyl group having 3 to 10 carbon atoms having 1 to 10 carbon atoms,
At least two or more groups of D 5 to D 12 form an intramolecular cross-linking group that ether-bonds to the benzene ring, and the group that does not participate in the cross-linking is an OH group. )
The compound according to any one of claims 1 to 4, wherein the dissociative bond is an ester bond.
The compound according to any one of claims 1 to 5, wherein the intramolecular cross-linking group is represented by the following formula (C-0).

(In formula (C-0), A is a divalent group derived from R 16 to R 19 , or A is a divalent group derived from R 30 to R 37).
The compound according to any one of claims 1 to 6, wherein the intramolecular cross-linking group in the formula (P-0C) is represented by the following formula (C-0A).
The compound according to any one of claims 1 to 7, which is represented by the following formula (M-0).

(In the formula (M-0), X 0 is a group represented by the following formula (X-0).)

(In formula (X-0), A is a divalent group derived from R 16 to R 19.)
The compound according to claim 8, which is represented by the following formula (M-0A).

(In the formula (M-0A), X 0 is a group represented by the following formula (X-0A).)
The compound according to any one of claims 1 to 6, wherein the intramolecular cross-linking group in the formula (P-1C) is represented by the following formula (C-1A).
The compound according to any one of claims 1 to 6 or 10, represented by the following formula (M-1).

(In the formula (M-1), X 1 is a group represented by the following formula (X-1).)

(In formula (X-1), A is a divalent group derived from R 30 to R 37.)
The compound according to claim 11, which is represented by the following formula (M-1A).

(In the formula (M-1A), X 1 is a group represented by the following formula (X-1A).)
Claims 1 to 12 include a step of reacting a polyphenol with a cross-linking agent containing a dissociative bond that dissociates under acid or alkaline conditions to intramolecularly cross-link two or more hydroxyl groups of the polyphenol with the compound. The method for producing a compound according to any one of.
The production method according to claim 13, wherein the cross-linking agent is represented by the following formula (C-hal).

(In the formula (C-hal), each X is an independently halogen atom, and
A is a divalent group derived from R 16 to R 19 , or A is a divalent group derived from R 30 to R 37. )
The production method according to claim 14, wherein the cross-linking agent is represented by the following formula (C-0hal) or (C-1hal).

(In the formula, X is an independent halogen atom.)
A composition for forming a resist film containing the compound according to any one of claims 1 to 12 or a derivative thereof.
The composition for forming a resist film according to claim 16, further containing a component selected from the group consisting of a solvent, an acid generator, an acid cross-linking agent, and a combination thereof.
A resist film formed from the composition according to claim 16 or 17.
A film forming step of forming a film on a substrate by using the resist film forming composition according to claim 16 or 17.
The exposure process for exposing the film and
A developing step of developing a film exposed in the exposure step to form a pattern, and a developing step of forming a pattern.
Pattern forming method including.
A curable composition containing the compound according to any one of claims 1 to 12 or a derivative thereof.
The curable composition according to claim 20, further containing a silicon-containing compound.
The curable composition according to claim 21, wherein the silicon-containing compound is a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzed condensate thereof.
The curable composition according to any one of claims 20 to 22, further containing a component selected from the group consisting of a solvent, an acid generator, an acid cross-linking agent, and a combination thereof.
An underlayer film formed from the curable composition according to any one of claims 20 to 23.
A step of forming a resist underlayer film using the curable composition according to any one of claims 20 to 23,
A step of forming at least one photoresist layer on the resist underlayer film and
A step of irradiating a predetermined area of the photoresist layer with radiation to develop the photoresist layer,
A pattern forming method.
An optical article formed from the curable composition according to any one of claims 20 to 23.
A step of dissolving the compound according to any one of claims 1 to 12 or a derivative thereof in a solvent containing an organic solvent that is arbitrarily immiscible with water to obtain a solution (B).
The first extraction step of bringing the obtained solution (B) into contact with an acidic aqueous solution to extract impurities in the compound or its derivative.
Purification method including.