Compounds and methods for producing the same, compositions, resist films, and pattern formation methods.

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

[Technical Field]

[0001] The present invention relates to compounds, methods for producing the same, compositions, resist films, pattern forming methods, and lithography underlayer films and optical articles formed by the compositions. [Background technology]

[0002] In the manufacturing of semiconductor devices, microfabrication is performed using lithography with photoresist materials. However, in recent years, with the increasing integration and speed of LSIs (large-scale integrated circuits), further miniaturization using pattern rules has become necessary.

[0003] Conventional resist materials are polymer-based resist materials capable of forming amorphous thin films. Examples include polymer-based resist materials such as polymethyl methacrylate and polyhydroxystyrene or polyalkyl methacrylate having dissociable reactive groups. Line patterns of approximately 45 to 100 nm are formed by irradiating a resist thin film, prepared by coating a solution of such polymer-based resist material onto a substrate, with ultraviolet light, far ultraviolet light, electron beams, extreme ultraviolet light (EUV), X-rays, etc. (see, for example, Non-Patent Document 1).

[0004] However, polymer-based resist materials have large molecular weights, ranging from approximately 10,000 to 100,000, and a wide molecular weight distribution. Therefore, lithography using polymer-based resist materials results in roughness on the surface of fine patterns, making it difficult to control pattern dimensions and reducing yield. Consequently, there are limitations to miniaturization using conventional polymer-based resist materials. To create finer patterns, various low-molecular-weight resist materials have been proposed.

[0005] For example, alkali-developable negative-type radiation-sensitive compositions using low molecular weight polynuclear polyphenol compounds as the main component have been proposed (see, for example, Patent Documents 1 and 2). Also, as a candidate for a low molecular weight resist material with high heat resistance, alkali-developable negative-type radiation-sensitive composition using low molecular weight cyclic polyphenol compounds as the main component has been proposed (see, for example, Patent Document 3 and Non-Patent Document 2). Furthermore, it is known that polyphenol compounds, as base compounds for resist materials, can impart high heat resistance despite their low molecular weight and are useful for improving the resolution and roughness of resist patterns (see, for example, Non-Patent Document 3). In addition, Patent Document 4 discloses a resist material in which calixarenes are intermolecularly crosslinked.

[0006] Furthermore, electron beam or extreme ultraviolet (EUV) lithography has a different reaction mechanism than conventional photolithography. Moreover, electron beam or EUV lithography aims to form fine patterns of several tens of nanometers. As the resist pattern size decreases, the resist material must be highly sensitive to the exposure light source. In particular, EUV lithography requires high sensitivity of the resist composition in terms of throughput.

[0007] As resist materials that improve these properties, inorganic resist materials containing, for example, titanium, hafnium, or zirconium have been proposed (see, for example, Patent Documents 5 and 6). [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2005-326838 [Patent Document 2] Japanese Patent Publication No. 2008-145539 [Patent Document 3] Japanese Patent Publication No. 2009-173623 [Patent Document 4] Japanese Patent Publication No. 2017-88847 [Patent Document 5] Japanese Patent Publication No. 2015-75500 [Patent Document 6] Japanese Patent Publication No. 2015-108781 [Non-patent literature]

[0009] [Non-Patent Document 1] Shinji Okazaki, et al., "40 Years of Lithography Technology," S&T Publishing. [Non-Patent Document 2] T.Nakayama,M.Nomura,K.Haga,M.Ueda:Bull.Chem.Soc.Jpn.,71,2979(1998) [Non-Patent Document 3] Shinji Okazaki, et al., "New Developments in Photoresist Material Development," CMC Publishing Co., Ltd., September 2009, pp. 211-259. [Overview of the project] [Problems that the invention aims to solve]

[0010] However, inorganic resist materials have low sensitivity, and there is a need for further improvements in resolution. Furthermore, in optical articles, compositions with high sensitivity and high resolution are desired. In view of these circumstances, the object of the present invention is to provide compounds and compositions that provide resist materials with high sensitivity and high resolution. [Means for solving the problem]

[0011] As a result of diligent research to solve the aforementioned problems, the inventors have found that a specific compound can solve the aforementioned 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 dissociable bond that dissociates under acidic or alkaline conditions. [2] The compound according to [1], wherein the polyphenol is calixarene. [3] The compound described in [1] or [2], which is a compound represented by the formula (P-0C) or (P-1C) described later. [4] The compounds described in [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 dissociable bond is an ester bond. [6] The compound described in any of [1] to [5], wherein the intramolecular crosslinking group is represented by formula (C-0) described later. [7] A compound according to any of [1] to [6], wherein the intramolecular crosslinking group in the above formula (P-0C) is represented by the formula (C-0A) described later. [8] A compound represented by formula (M-0) described later, as one of the compounds listed in [1] to [7]. [9] The compound described in [8], represented by formula (M-0A) described later.

[10] A compound according to any of [1] to [6], wherein the intramolecular crosslinking group in the above formula (P-1C) is represented by the formula (C-1A) described later.

[11] A compound represented by formula (M-1) described later, as described in any of [1] to [6] or

[10] .

[12] The compound described in

[11] , represented by formula (M-1A) described later.

[13] A method for producing a compound according to any one of [1] to

[12] , comprising the step of reacting a polyphenol with a crosslinking agent containing a dissociable bond that dissociates under acidic or alkaline conditions to intramolecularly crosslink two or more hydroxyl groups of the polyphenol with the compound.

[14] The method for manufacturing described in

[13] , wherein the crosslinking agent is represented by the formula (C-hal) described later.

[15] The method for producing the crosslinking agent described later by formula (C-0hal) or (C-1hal), as described in

[14] .

[16] A resist film-forming composition containing any of the compounds described in [1] to

[12] or a derivative thereof.

[17] The resist film forming composition according to

[16] , further comprising a component selected from the group consisting of a solvent, an acid generator, an acid crosslinking agent, and combinations thereof.

[18] A resist film formed from the composition described in

[16] or

[17] .

[19] A film formation step of forming a film on a substrate using the resist film formation composition described in

[16] or

[17] , An exposure step of exposing the aforementioned film, A developing step is performed to develop the film exposed in the exposure step to form a pattern, A pattern formation method including the following.

[20] A curable composition containing any of the compounds described in [1] to

[12] or a derivative thereof. [twenty one] The curable composition according to

[20] , further containing a silicon-containing compound. [twenty two] The curable composition according to

[21] , wherein the silicon-containing compound is a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzed condensate thereof. [twenty three] A curable composition according to any one of

[20] to

[22] , further comprising a component selected from the group consisting of a solvent, an acid generator, an acid crosslinking agent, and combinations thereof. [twenty four] A lower layer film formed from any of the curable compositions described in

[20] to

[23] . [twenty five] A step of forming a resist underlayer film using a curable composition described in any of

[20] to

[23] , The steps include forming at least one photoresist layer on the resist underlayer film, A step of irradiating a predetermined region of the photoresist layer with radiation and performing development, A pattern forming method comprising the following:

[26] An optical article formed from any of the curable compositions described in

[20] to

[23] .

[27] A step of dissolving a compound or derivative thereof described in any of [1] to

[12] in a solvent containing an organic solvent that is not arbitrarily miscible with water to obtain a solution (B), A first extraction step involves contacting the obtained solution (B) with an acidic aqueous solution to extract impurities from the compound or its derivative, A purification method that includes [details omitted].

[28] The purification method according to

[27] , wherein the acidic aqueous solution is an aqueous solution of one or more mineral acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; or an aqueous solution of one or more organic acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.

[29] The purification method according to

[27] or

[28] , wherein the organic solvent that is arbitrarily immiscible 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.

[30] A purification method according to any one of

[27] to

[29] , further comprising a second extraction step of bringing the solution phase containing the compound or derivative into contact with water after the first extraction step to extract impurities from the compound or derivative. [Effects of the Invention]

[0012] The present invention provides compounds and compositions that give resist materials having high sensitivity and high resolution. [Brief explanation of the drawing]

[0013] [Figure 1] 1H-NMR spectrum of BAB-DMHDO [Figure 2] IR spectrum of BAB-DMHDO [Figure 3] 1H-NMR spectrum of BCA[4]-co-BAB-DMHDO [Figure 4] IR spectrum of BCA[4]-co-BAB-DMHDO [Modes for carrying out the invention]

[0014] The following describes embodiments of the present invention (which may be referred to as "this embodiment"). This embodiment is an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0015] [Compound] In this embodiment, the hydroxyl groups of the polyphenol are intramolecularly crosslinked with groups containing dissociable bonds that dissociate under acidic or alkaline conditions. Specifically, in one embodiment, the compound comprises a group having the structure -OAO- which crosslinks two hydroxyl groups together. In this case, A is a divalent organic group that dissociates under acidic or alkaline conditions. In another embodiment, the compound has three or more hydroxyl groups intramolecularly crosslinked.

[0016] Dissociable bonds that dissociate under acidic or alkaline conditions are not limited to any bonds that dissociate under those conditions, but examples include ester bonds and amide bonds.

[0017] A polyphenol is a compound having two or more phenolic hydroxyl groups, preferably a calixarene. In this embodiment, calixarene refers to a cyclic compound obtained by a condensation reaction between a phenolic compound and an aldehyde.

[0018] The compound according to this embodiment is preferably represented by the following formula (P-0C).

[0019] [ka]

[0020] 1) L1 ~L 4 Regarding L 1 ~L 4 is, independently, a single bond, a linear alkylene group having 1 to 20 carbon atoms which may have a substituent, a branched alkylene group having 3 to 20 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent, an arylene group having 6 to 24 carbon atoms which may have a substituent, -O-, -OC(=O)-, -OC(=O)O-, -O-R 2 -C(=O)O-, -N(R 20 )-C(=O)-, -N(R 20 )-C(=O)O-, -S-, -SO-, -SO2- and a divalent organic group selected from the group consisting of any combination thereof.

[0021] As the linear alkylene group, preferably an alkylene group having 1 to 4 carbon atoms is mentioned. As the branched alkylene group, preferably an alkylene group having 3 to 6 carbon atoms is mentioned. As the cycloalkylene group, preferably a cycloalkylene group having 5 to 7 carbon atoms is mentioned. As the arylene group, preferably a phenylene group, a naphthylene group are mentioned. 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 a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, preferably a hydrogen atom or a methyl group.

[0022] In one aspect, two or more L 1 ~L 4 is -O-R 2 -C(=O)O group and can participate in intramolecular crosslinking. When two or more L 1 ~L 4 participate in intramolecular crosslinking, some R 16 ~R 19 preferably participate in intramolecular crosslinking as a divalent group. Also, R 2 is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group.

[0023] 2) R 16 ~R 19 About R 16 ~R 19 If it does not participate in intramolecular crosslinking, it is a group independently selected from the following: Linear alkyl groups having 1 to 20 carbon atoms, which may have substituents; Cycloalkyl groups having 3 to 20 carbon atoms, which may have substituents; A C6-C20 aryl group which may have substituents; A C1-C20 alkoxyl group which may have substituents; Cyano group; Nitro group; Hydroxyl group; Heterocyclic group; halogen atom; Carboxyl group; Alkylsilyl groups having 1 to 20 carbon atoms; A group selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group, which have the property of dissociating in the presence of acid; Hydrogen atom. R 16 ~R 19 If the group is involved in intramolecular crosslinking, it may be a divalent group derived independently from a group selected from the above.

[0024] The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a t-butyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms. The aryl group is preferably a phenyl group or a naphthyl group. The alkoxyl group is preferably an alkoxyl group having 1 to 4 carbon atoms.

[0025] Examples of the heterocyclic group include heterocyclic groups having 4 to 20 carbon atoms and containing O, S, or N as heteroatoms, preferably furanyl groups, thiophenyl groups, imidazolyl groups, pyrrolyl groups, pyridyl groups, etc. Examples of the alkylsilyl group include alkylsilyl groups having 1 to 20 carbon atoms.

[0026] Examples of halogen atoms include F, Cl, Br, and I, but F or Cl is preferred.

[0027] As substituted methyl groups having 2 to 20 carbon atoms that dissociate in the presence of acid, substituted methyl groups having 4 to 18 carbon atoms are preferred, and substituted methyl groups having 6 to 16 carbon atoms are more preferred. Specific examples of substituted methyl groups, though not limited to the following, include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, 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-methoxyphenacyl group, piperonyl group, and the substituent group represented by the following formula (1). In the following formula (1), R 2A R is an alkyl group having 1 to 4 carbon atoms. 2A Specific examples include, but are not limited to, methyl groups, ethyl groups, isopropyl groups, n-propyl groups, t-butyl groups, and n-butyl groups.

[0028] [ka]

[0029] As a 1-substituted ethyl group having 3 to 20 carbon atoms that dissociates in the presence of acid, a 1-substituted ethyl group having 5 to 18 carbon atoms is preferred, and a substituted ethyl group having 7 to 16 carbon atoms is more preferred. Specific examples of 1-substituted ethyl groups, though not limited to the following, include 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 the substituent group represented by the following formula (2). In the following formula (2), R 2A This is defined by equation (1) above.

[0030] [ka]

[0031] As a 1-substituted n-propyl group having 4 to 20 carbon atoms that dissociates in the presence of acid, a 1-substituted n-propyl group having 6 to 18 carbon atoms is preferred, and a 1-substituted n-propyl group having 8 to 16 carbon atoms is more preferred. Specific examples of 1-substituted n-propyl groups, though not limited to those listed below, include 1-methoxy-n-propyl and 1-ethoxy-n-propyl groups.

[0032] As a 1-branched alkyl group having 3 to 20 carbon atoms that dissociates in the presence of acid, a 1-branched alkyl group having 5 to 18 carbon atoms is preferred, and a branched alkyl group having 7 to 16 carbon atoms is more preferred. Specific examples of 1-branched alkyl groups, though not limited to the following, include isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, 2-methyladamantyl group, and 2-ethyladamantyl group.

[0033] As a silyl group having 1 to 20 carbon atoms that dissociates in the presence of acid, a silyl group having 3 to 18 carbon atoms is preferred, and a silyl group having 5 to 16 carbon atoms is more preferred. Specific examples of silyl groups, though not limited to the following, include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, t-butyldimethylsilyl, t-butyldiethylsilyl, t-butyldiphenylsilyl, tri-t-butylsilyl, and triphenylsilyl.

[0034] As acyl groups having 2 to 20 carbon atoms that dissociate with acid, acyl groups having 4 to 18 carbon atoms are preferred, and acyl groups having 6 to 16 carbon atoms are more preferred. Specific examples of acyl groups, though not limited to the following, include acetyl groups, phenoxyacetyl groups, propionyl groups, butyryl groups, heptanolyl groups, hexanoyl groups, valeryl groups, pivaloyl groups, isovaleryl groups, lauryl groups, adamantylcarbonyl groups, benzoyl groups, and naphthoyl groups.

[0035] As a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms that dissociates in the presence of acid, a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms is preferred, a 1-substituted alkoxymethyl group having 4 to 18 carbon atoms is more preferred, and a 1-substituted alkoxymethyl group having 6 to 16 carbon atoms is even more preferred. Specific examples of 1-substituted alkoxymethyl groups, though not limited to the following, include 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group, and 1-adamantylmethoxymethyl group.

[0036] As a cyclic ether group having 2 to 20 carbon atoms that dissociates in the presence of acid, a cyclic ether group having 4 to 18 carbon atoms is preferred, and a cyclic ether group having 6 to 16 carbon atoms is more preferred. Specific examples of cyclic ether groups, though not limited to the following, include tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 4-methoxytetrahydropyranyl group, and 4-methoxytetrahydrothiopyranyl group.

[0037] As for alkoxycarbonyl groups having 2 to 20 carbon atoms that have the property of dissociating with acid, alkoxycarbonyl groups having 4 to 18 carbon atoms are preferred, and alkoxycarbonyl groups having 6 to 16 carbon atoms are more preferred. Specific examples of alkoxycarbonyl groups, though not limited to the following, include methoxycarbonyl groups, ethoxycarbonyl groups, n-propoxycarbonyl groups, isopropoxycarbonyl groups, n-butoxycarbonyl groups, t-butoxycarbonyl groups, and groups represented by n=0 in the following formula (3).

[0038] As alkoxycarbonylalkyl groups that have the property of dissociating in the presence of acid, alkoxycarbonylalkyl groups having 3 to 20 carbon atoms are preferred, alkoxycarbonylalkyl groups having 4 to 18 carbon atoms are more preferred, and alkoxycarbonylalkyl groups having 6 to 16 carbon atoms are even more preferred. Specific examples of alkoxycarbonylalkyl groups, though not limited to those listed below, include methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, and groups represented by n=1 to 4 in the following formula (3).

[0039] [ka]

[0040] In the above equation (3), R 3A n is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer from 0 to 4.

[0041] 3) L 1 R 16 ~L 4 R 19 About the basis m 7~10 These represent the number of these bases and are independent integers from 1 to 4. 7~10 If the value is large, the compound may become unstable, so m 7~10 Preferably, it is 1 to 2, more preferably 1.

[0042] L 1 R 16 ~L 4 R 19 At least two of the groups are ether-bonded to the benzene ring and form intramolecular crosslinking groups. In one embodiment, L 1 R 16 ~L 4 R 19 Two of the groups form an intramolecular crosslinking group represented by formula (C-0).

[0043] [ka]

[0044] In the above formula, A is R 16 ~R 19 It is a divalent group derived from the aforementioned alkyl groups; cycloalkyl groups; aryl groups; alkoxyl groups; heterocyclic groups; carboxyl groups; alkylsilyl groups having 1 to 20 carbon atoms; and divalent groups derived from groups that dissociate with acid. Considering the ease of compound production, A is preferably an alkylene group having 4 to 10 carbon atoms. Therefore, L 1 R 16 ~L 4 R 19 Two of the groups more preferably form an intramolecular bridging group represented by formula (C-0A).

[0045] [ka]

[0046] 4) R 12 ~R 15 About R 12 ~R 15 R is independently a hydrogen atom, a C1-C20 alkyl group, or a C6-C24 aryl group represented by the following formula (P-0C-1), or a group derived therefrom. The C1-C20 alkyl group is R 16 ~R 19 The things explained in R can be listed. 12 ~R 15 Preferably, it is a hydrogen atom.

[0047] [ka]

[0048] In equation (P-0C-1), R 21 The following can be selected. A C1-C20 alkyl group which may have substituents; Cycloalkyl groups having 3 to 20 carbon atoms, which may have substituents; A C6-C20 aryl group which may have substituents; A C1-C20 alkoxy group which may have substituents, Cyano group; Nitro group; Heterocyclic group; halogen atom; Carboxyl group; Alkylsilyl groups having 1 to 20 carbon atoms; A group selected from the group consisting of a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, a 1-branched alkyl group having 3 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group, which has the property of dissociating in the presence of acid.

[0049] Specific examples of these elements are R16 ~R 19 As explained above, p 7 is R 21 This represents the number of integers, which are independently integers from 0 to 5. 7 It is preferably 0 to 1, more preferably 0.

[0050] The compound of this embodiment is preferably represented by formula (P-0A). In the formula, R A R is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, preferably a t-butyl group. In the compound, R is in formula (P-0C). 12 ~R 15 is a hydrogen atom, m 7~10 The value is 2. And there are two L in one benzene ring. 1 R 16 Of these, one is R A (For example L 1 R is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. 16 (This is a hydrogen atom), and the other is D. Other L atoms present in the benzene ring. 2 R 17 ~L 4 R 19 The same applies to D. 1 ~D 4 Two or more of these groups are intramolecular crosslinking groups that are ether-bonded to a benzene ring, D 1 ~D 4 Of these, the group that does not participate in the crosslinking is the OH group. In particular, D 1 and D 4 And, or D 2 and D 3 It is preferable that these two components form an intramolecular crosslinking group. This intramolecular crosslinking group is represented, for example, by the formula (C-0) or formula (C-0A) described above.

[0051] [ka]

[0052] The compound of this embodiment is more preferably represented by formula (P-0B).

[0053] [ka]

[0054] The compound of this embodiment is particularly preferably represented by formula (M-0). 0 is a base represented by equation (X-0). A is defined as described above.

[0055] [ka]

[0056] The compound of this embodiment is particularly preferably represented by formula (M-0A). 0 This is a base represented by the formula (X-0A).

[0057] [ka]

[0058] In the present invention, unless otherwise defined, "substitution" means that one or more hydrogen atoms in a functional group are replaced by a substituent. Substituents are not particularly limited, but examples include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, amino groups having 0 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, acyl groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, alkyloyloxy groups having 1 to 20 carbon atoms, aryloyloxy groups having 7 to 30 carbon atoms, or alkylsilyl groups having 1 to 20 carbon atoms.

[0059] The compound according to this embodiment is preferably represented by the following formula (P-1C).

[0060] [Chemical Formula]

[0061] 1) L 5 ~L 12 Regarding L 5 ~L 12 is independently a single bond, a linear alkylene group having 1 to 20 carbon atoms which may have a substituent, a branched alkylene group having 3 to 20 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 20 carbon atoms which may have a substituent, an arylene group having 6 to 24 carbon atoms which may have a substituent, -O-, -OC(=O)-, -OC(=O)O-, -O-R 2 -C(=O)O-, -N(R 20 )-C(=O)-, -N(R 20 )-C(=O)O-, -S-, -SO-, -SO2- and a divalent organic group selected from the group consisting of any combination thereof.

[0062] Examples of the linear alkylene group, the branched alkylene group, the cycloalkylene group, and the arylene group include those described by formula (P-0C). R 2 And R 20 is as described by formula (P-0C).

[0063] In one embodiment, two or more L 5 ~L 12 are -O-R 2 -C(=O)O groups and can participate in intramolecular crosslinking. When two or more L 5 ~L 12 participate in intramolecular crosslinking, some R 30 ~R 37 preferably participate in intramolecular crosslinking as a divalent group. R 2 is as described by formula (P-0C).

[0064] 2) R 30 ~R 37 Regarding R 30 ~R 37If it does not participate in intramolecular crosslinking, it is a group independently selected from the following: Linear alkyl groups having 1 to 20 carbon atoms, which may have substituents; Cycloalkyl groups having 3 to 20 carbon atoms, which may have substituents; A C6-C20 aryl group which may have substituents; A C1-C20 alkoxyl group which may have substituents; Cyano group; Nitro group; Hydroxyl group; Heterocyclic group; halogen atom; Carboxyl group; Alkylsilyl groups having 1 to 20 carbon atoms; These groups have the property of dissociating in the presence of acid, including substituted methyl groups with 2 to 20 carbon atoms, 1-substituted ethyl groups with 3 to 20 carbon atoms, 1-substituted n-propyl groups with 4 to 20 carbon atoms, 1-branched alkyl groups with 3 to 20 carbon atoms, silyl groups with 1 to 20 carbon atoms, acyl groups with 2 to 20 carbon atoms, and other groups with 2 to 20 carbon atoms. A group selected from the group consisting of 1-substituted alkoxyalkyl groups, cyclic ether groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, and alkoxycarbonylalkyl groups; Hydrogen atom. R 30 ~R 37 If the group is involved in intramolecular crosslinking, it may be a divalent group derived independently from a group selected from the above.

[0065] Examples of the alkyl group, cycloalkyl group, aryl group, and alkoxyl group are those described by formula (P-0C). Examples of the heterocyclic group, alkylsilyl group, halogen atom, and acid-dissociative group are those described by formula (P-0C).

[0066] 3) L 5 R 30 ~L 12 R 37 About m 11~18These represent the number of these bases and are independent integers from 1 to 4. 11~18 If the value is large, the compound may become unstable, so m 11~18 Preferably, it is 1 to 2, more preferably 1.

[0067] L 5 R 30 ~L 12 R 37 At least two of the groups are ether-bonded to the benzene ring and form intramolecular crosslinking groups. In one embodiment, L 5 R 30 ~L 12 R 37 Two of the groups form an intramolecular crosslinking group represented by formula (C-0). However, in this case, A in formula (C-0) is R 30 ~R 37 It is a divalent group derived from [the above]. The specific A is as described above. R 30 ~R 37 Two of the groups preferably form an intramolecular crosslinking group represented by formula (C-1A).

[0068] [ka]

[0069] 4) R 22 ~R 29 About R 22 ~R 29 R is independently a hydrogen atom, a C1-C20 alkyl group, or a C6-C24 aryl group represented by the formula (P-0C-1) or a group derived therefrom. As the C1-C20 alkyl group, 16 ~R 19 The things explained in R can be listed. 22 ~R 29 Preferably, it is a hydrogen atom.

[0070] The compound of this embodiment is preferably represented by formula (P-1A). In the formula, R BR is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, preferably a t-butyl group. In the compound, R is in formula (P-1C). 22 ~R 29 is a hydrogen atom, m 11~18 The value is 2. And there are two L in one benzene ring. 5 R 30 Of these, one is R B (For example L 5 R is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms. 30 (This is a hydrogen atom), and the other is D. Other L atoms present in the benzene ring. 6 R 31 ~L 12 R 37 The same applies to D. 5 ~D 12 Two or more of these groups are intramolecular crosslinking groups that are ether-bonded to a benzene ring, D 5 ~D 12 Of these, the group that does not participate in the crosslinking is the OH group. In particular, D 5 and D 11 And, or D 9 and D 13 It is preferable that these two components form an intramolecular crosslinking group. Such intramolecular crosslinking groups are, for example, as described above.

[0071] [ka]

[0072] The compound of this embodiment is more preferably represented by formula (P-1B).

[0073] [ka]

[0074] The compound of this embodiment is particularly preferably represented by formula (M-1). 0 is a base represented by equation (X-1). A is R 30 ~R 37It is a divalent group derived from [the original source].

[0075] [ka]

[0076] The compound of this embodiment is particularly preferably represented by formula (M-1A). 1 This is a group represented by the formula (X-1A).

[0077] [ka]

[0078] [Method for producing compounds] The method for producing the compound according to this embodiment comprises a step of reacting a polyphenol with a crosslinking agent containing a dissociable bond that dissociates under acidic or alkaline conditions to intramolecularly crosslink two or more hydroxyl groups of the polyphenol with the compound.

[0079] The polyphenols mentioned above can be used. Examples of crosslinking agents include compounds having ester bonds or amide bonds. The crosslinking agent is preferably represented by formula (C-hal), more preferably by formula (C-0hal) or formula (C-1hal). In the formula, A is defined as described above. X is a halogen atom, preferably F, Cl, or Br, more preferably Br.

[0080] The reaction temperature and time are determined appropriately from the viewpoint of reaction rate and reduction of by-products, but for example, it can be carried out at around -10 to 30°C. The solvent is also not limited, but halogenated hydrocarbons can be used. Furthermore, a basic compound may be used in combination to trap the generated hydrogen halides. Examples of such compounds include amines such as pyridine.

[0081] [ka]

[0082] [Composition] The compound according to this embodiment is suitable as a lithography material. A 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 this embodiment, and can be used for resist applications (i.e., resist compositions), etc. The compound according to this embodiment is a curable composition. The curable composition can be, for example, a composition for forming a lithography underlayer film, a composition for forming an optical article, etc., but is not limited to these. The curable composition may be radiation-curable or thermosetting, but radiation-curable is more preferable. The composition according to this embodiment is manufactured by the process of preparing the compound according to this embodiment as described above. For example, it can be manufactured by mixing the compound according to this embodiment with other components such as a solvent in a known way.

[0083] 1) Lithography material composition The lithography material composition according to this embodiment comprises the lithography material according to this embodiment and a solvent. Since the lithography material composition has high sensitivity and high resolution, it can form a good resist pattern. Furthermore, because the molecules of the compound according to this embodiment have a moderate diffusion rate, it exhibits high resolution while maintaining high sensitivity. In addition, because the compound has a moderate molecular weight, it is not easily volatile, and film loss during curing is relatively small, allowing the composition to form a highly flat film.

[0084] <Properties of compositions for forming resist films> As described above, the lithography material of this embodiment can be used for resist applications, and amorphous films can be formed by known methods such as spin coating. Furthermore, depending on the type of developer used, either a positive-type resist pattern or a negative-type resist pattern can be produced. The resist film formation composition will be described below.

[0085] In this embodiment, when the resist film forming composition is a positive-type resist pattern, the dissolution rate of the amorphous film formed by spin-coating the composition in the developer at 23°C is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and even more preferably 0.0005 to 5 Å / sec. A dissolution rate of 5 Å / sec or less allows for a resist that is insoluble in the developer. Furthermore, a dissolution rate of 0.0005 Å / sec or higher may improve resolution. This is presumed to be because the change in solubility of the compound according to this embodiment before and after exposure increases the contrast at the interface between the exposed portion that dissolves in the developer and the unexposed portion that does not dissolve in the developer. It also has the effect of reducing line edge roughness and defects.

[0086] In this embodiment, when the resist film forming composition is a negative-type resist pattern, the dissolution rate of the amorphous film formed by spin-coating the composition in the developer at 23°C is preferably 10 Å / sec or higher. A dissolution rate of 10 Å / sec or higher makes the film easily soluble in the developer and more suitable for resist formation. Furthermore, a dissolution rate of 10 Å / sec or higher may also improve resolution. This is presumed to be because the microscopic surface areas of the compound according to this embodiment dissolve, reducing line edge roughness. It also has the effect of reducing defects. The dissolution rate can be determined by immersing the amorphous film in the developer for a predetermined time at 23°C and measuring the film thickness before and after immersion by visual inspection, ellipsometer, or known method such as the QCM method.

[0087] When the resist film forming composition of this embodiment is a positive-type resist pattern, the dissolution rate in the developer at 23°C of the portion of the amorphous film formed by spin-coating the composition with radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray is preferably 10 Å / sec or higher. A dissolution rate of 10 Å / sec or higher makes the material easily soluble in the developer and more suitable for resist formation. Furthermore, a dissolution rate of 10 Å / sec or higher may also improve resolution. This is presumed to be because the microscopic surface portion of the compound according to this embodiment dissolves, reducing line edge roughness. It also has the effect of reducing defects.

[0088] When the resist film forming composition of this embodiment is a negative-type resist pattern, the dissolution rate in the developer at 23°C of the portion of the amorphous film formed by spin-coating the composition with radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and even more preferably 0.0005 to 5 Å / sec. If the dissolution rate is 5 Å / sec or less, the resist can be made insoluble in the developer. Furthermore, if the dissolution rate is 0.0005 Å / sec or higher, the resolution may be improved. This is presumed to be because the change in solubility of the compound according to this embodiment before and after exposure increases the contrast at the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer. In addition, there is an effect of reducing line edge roughness and defects.

[0089] <Other components of the resist film forming composition> The resist film-forming composition of this embodiment contains the compound according to this embodiment as a solid component. In addition to the compound according to this embodiment, the resist film-forming composition of this embodiment further contains a solvent.

[0090] The solvent used in the resist film-forming composition of this embodiment is not particularly limited, but examples include: ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (PGMEA), 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; methyl lactate, ethyl lactate, n-propyl lactate, n-propyl lactate. Lactic acid esters such as methyl acetate, n-amyl lactate; aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methyl Other esters such as butyl propionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-lactones. These solvents can be used individually or in combination of two or more.

[0091] The solvent used in the resist film forming composition of this embodiment is preferably a safe solvent, more preferably at least one selected from esters such as PGMEA, butyl acetate, ethyl propionate, and ethyl lactate; polyhydric alcohol ethers such as PGME; and aprotic polar solvents such as CHN, CPN, 2-heptanone, and anisole, and even more preferably at least one selected from PGMEA, PGME, and CHN.

[0092] In the resist film forming composition of this embodiment, the relationship between the amount of solid component and the amount of solvent is not particularly limited, but it is preferably 1 to 80% by mass of solid component and 20 to 99% by mass of solvent, more preferably 1 to 50% by mass of solid component and 50 to 99% by mass of solvent, even more preferably 2 to 40% by mass of solid component and 60 to 98% by mass of solvent, and particularly preferably 2 to 10% by mass of solid component and 90 to 98% by mass of solvent.

[0093] The resist film forming composition of this embodiment may also contain, as other solid components, at least one selected from the group consisting of an acid generator (C), an acid crosslinking agent (G), an acid diffusion control agent (E), and other components (F).

[0094] In the resist film forming composition of this embodiment, the content of the compound according to this embodiment is not particularly limited, but is preferably 50 to 99.4% by mass of the total mass of the solid components (the sum of the solid components used optionally, such as the compound according to this embodiment, the acid generator (C), the acid crosslinking agent (G), the acid diffusion control agent (E), and other components (F), hereinafter the same), more preferably 55 to 90% by mass, even more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. With the above content, the resolution is further improved and the line edge roughness (LER) is further reduced.

[0095] <Acid Generator (C)> The resist film forming composition of this embodiment preferably contains one or more acid generators (C) that directly or indirectly generate acid upon irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam.

[0096] In this case, in the resist film forming composition of this embodiment, the content of the acid generator (C) is preferably 0.001 to 49% by mass of the total mass of the solid components, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass. By using the acid generator (C) within the above content range, a pattern profile with even higher sensitivity and even lower edge roughness can be obtained.

[0097] In the resist film forming composition of this embodiment, the method of acid generation is not limited as long as acid is generated in the system. If an excimer laser is used instead of ultraviolet rays such as g-rays and i-rays, finer processing is possible, and if an electron beam, extreme ultraviolet rays, X-rays, or ion beam is used as a high-energy beam, even finer processing is possible.

[0098] The acid generator (C) is not particularly limited, and examples include compounds disclosed in International Publication No. 2017 / 033943. Acid generators having an aromatic ring are preferred as acid generators (C), acid generators having an aryl group-containing sulfonate ion are more preferred, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferred. Using such an acid generator can reduce line edge roughness.

[0099] Furthermore, the resist film forming composition of this embodiment preferably further contains a diazonaphthoquinone photoactive compound as an acid generator. The diazonaphthoquinone photoactive compound is a diazonaphthoquinone substance, including polymeric and nonpolymeric diazonaphthoquinone photoactive compounds, and is not particularly limited as long as it is generally used as a photosensitive component in positive-type resist compositions. One or more types can be arbitrarily selected and used. Among these, nonpolymeric diazonaphthoquinone photoactive compounds are preferred from the viewpoint of low roughness and solubility, more preferably low molecular weight compounds with a molecular weight of 1500 or less, even more preferably with a molecular weight of 1200 or less, and particularly preferably with a molecular weight of 1000 or less. A preferred specific example of such a nonpolymeric diazonaphthoquinone photoactive compound is the nonpolymeric diazonaphthoquinone photoactive compound disclosed in International Publication No. 2016 / 158881. The acid generator (C) can be used alone or in combination of two or more types.

[0100] <Acid crosslinking agent (G)> The resist film-forming composition of this embodiment preferably contains one or more acid crosslinking agents (G) when used as a negative-type resist material or as an additive to increase the pattern strength in a positive-type resist material. An acid crosslinking agent (G) is a compound that can crosslink the compound according to this embodiment intramolecularly or intermolecularly in the presence of an acid generated from an acid generator (C). Such an acid crosslinking agent (G) is not particularly limited, but examples include compounds having one or more crosslinkable groups that can crosslink the compound according to this embodiment.

[0101] Specific examples of such crosslinkable groups are not limited to, but include, for example, (i) hydroxyalkyl groups such as -R-OH (where R is an alkylene group having 1 to 6 carbon atoms), -RO-R' (where R is an alkylene group having 1 to 6 carbon atoms, and 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) or groups derived therefrom; (ii) carbonyl groups such as formyl group, -R-COOH (where R is an alkylene group having 1 to 6 carbon atoms) or groups derived therefrom; (iii) dimethylaminomethyl group, diethylaminomethyl group Examples of nitrogen-containing groups include (iv) nitrogen-containing groups such as methyl nomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, and morpholinomethyl group; (v) groups derived from aromatic groups such as allyloxy (alkyl groups having 1 to 6 carbon atoms) and aralkyloxy (alkyl groups having 1 to 6 carbon atoms) such as benzyloxymethyl group and benzoyloxymethyl group; and (vi) polymerizable multiple bond-containing groups such as vinyl group and isopropenyl group. The crosslinkable group of the acid crosslinking agent (G) is preferably a hydroxyalkyl group and an alkoxyalkyl group, with alkoxymethyl group being particularly preferred.

[0102] The acid crosslinking agent (G) having the crosslinkable group is not particularly limited, but examples include (i) methylol group-containing compounds such as methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing glycoluryl compounds, and methylol group-containing phenol compounds; (ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluryl compounds, and alkoxyalkyl group-containing phenol compounds; (iii) carboxymethyl group-containing compounds such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycoluryl compounds, and carboxymethyl group-containing phenol compounds; and (iv) epoxy compounds such as bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, and poly(hydroxystyrene)-based epoxy compounds.

[0103] As the acid crosslinking agent (G), compounds having phenolic hydroxyl groups, and compounds and resins in which the crosslinking group is introduced into the acidic functional groups in an alkali-soluble resin to impart crosslinking properties can be used. In this case, the introduction rate of the crosslinking group is not particularly limited, and is adjusted to, for example, 5 to 100 mol%, preferably 10 to 60 mol%, and more preferably 15 to 40 mol%, relative to the total acidic functional groups in the compound having phenolic hydroxyl groups and the alkali-soluble resin. This range is preferable because it allows for sufficient crosslinking reaction, avoiding a decrease in residual film percentage, swelling of the pattern, meandering, etc.

[0104] In the resist film-forming composition of this embodiment, the acid crosslinking agent (G) is preferably an alkoxyalkylated urea compound or its resin, or an alkoxyalkylated glycoluryl compound or its resin (acid crosslinking agent (G1)), a phenol derivative having 1 to 6 benzene rings in the molecule and 2 or more hydroxyalkyl groups or alkoxyalkyl groups throughout the molecule, wherein the hydroxyalkyl group or alkoxyalkyl group is bonded to any of the aforementioned benzene rings (acid crosslinking agent (G2)), or a compound having at least one α-hydroxyisopropyl group (acid crosslinking agent (G3)). For example, the compounds disclosed in International Publication No. 2017 / 033943 are examples.

[0105] In the resist film forming composition of this embodiment, the content of the acid crosslinking agent (G) is preferably 0.5 to 49% by mass of the total mass of the solid components, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass. A content of 0.5% by mass or more of the acid crosslinking agent (G) is preferable because it improves the effect of suppressing the solubility of the resist film in alkaline developer, thereby suppressing a decrease in the residual film rate and preventing swelling or meandering of the pattern. On the other hand, a content of 49% by mass or less is preferable because it suppresses a decrease in the heat resistance of the resist.

[0106] Furthermore, the content of at least one compound selected from the acid crosslinking agents (G1), (G2), and (G3) in the acid crosslinking agent (G) is not particularly limited and can be in various ranges depending on the type of substrate used when forming the resist pattern.

[0107] <Acid diffusion control agent (E)> The resist film forming composition of this embodiment may contain an acid diffusion control agent (E) that controls the diffusion of acid generated from the acid generator in the resist film upon irradiation, thereby preventing undesirable chemical reactions in unexposed areas. By using such an acid diffusion control agent (E), the storage stability of the resist film forming composition is improved. Furthermore, the resolution is further improved, and changes in the line width of the resist pattern due to variations in the pre-irradiation and post-irradiation rest time can be suppressed, resulting in extremely excellent process stability.

[0108] Such acid diffusion control agents (E) are not particularly limited and include, for example, radiodegradable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds. Examples of acid diffusion control agents (E) include the compounds disclosed in International Publication No. 2017 / 033943. Acid diffusion control agents (E) can be used alone or in combination of two or more.

[0109] The content of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass of the total mass of the solid components, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass. When the content of the acid diffusion control agent (E) is within the above range, deterioration of resolution, pattern shape, dimensional fidelity, etc., can be further suppressed. Furthermore, even if the settling time from electron beam irradiation to heating after radiation irradiation is long, the shape of the upper layer of the pattern will not deteriorate. In addition, when the content of the acid diffusion control agent (E) is 10% by mass or less, deterioration of sensitivity, developability of unexposed areas, etc., can be prevented. Furthermore, by using such an acid diffusion control agent, the storage stability of the resist film forming composition is improved, the resolution is improved, and changes in the line width of the resist pattern due to variations in the settling time before and after radiation irradiation can be suppressed, resulting in extremely excellent process stability.

[0110] <Other ingredients (F)> The resist film-forming composition of this embodiment may optionally contain one or more additives as other components (F), such as dissolution accelerators, dissolution controllers, sensitizers, surfactants, and organic carboxylic acids or phosphorus oxoacids or derivatives thereof, to the extent that they do not hinder the objective of this embodiment. Examples of other components (F) include compounds disclosed in International Publication No. 2017 / 033943.

[0111] The total content of other components (F) is preferably 0 to 49% by mass of the total mass of the solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0112] In the resist film forming composition of this embodiment, the content of the compound, acid generator (C), acid diffusion control agent (E), and other components (F) according to this embodiment (compound / acid generator (C) / acid diffusion control agent (E) / other components (F)) is preferably 50-99.4 / 0.001-49 / 0.001-49 / 0-49, more preferably 55-90 / 1-40 / 0.01-10 / 0-5, even more preferably 60-80 / 3-30 / 0.01-5 / 0-1, and particularly preferably 60-70 / 10-25 / 0.01-3 / 0, based on solid mass %.

[0113] The content ratio of each component is selected from various ranges such that its total mass equals 100%. This content ratio results in superior performance in areas such as sensitivity, resolution, and developability.

[0114] The method for preparing the resist film-forming composition of this embodiment is not particularly limited. For example, one method may involve dissolving each component in a solvent to form a homogeneous solution, and then filtering it as needed using, for example, a filter with a pore size of about 0.2 μm.

[0115] The resist film-forming composition of this embodiment may contain a resin to the extent that it does not hinder the objective of the present invention. The resin is not particularly limited and examples include novolac resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers or derivatives thereof containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. The content of the resin is not particularly limited and is appropriately adjusted depending on the type of compound used in this embodiment, but is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass per 100 parts by mass of the compound.

[0116] <Pattern Formation Method> When forming a pattern on a substrate using a lithography material, for example, a pattern formation method can be used that includes a film formation step of forming a film on a substrate using the lithography material or a composition containing the same according to this embodiment (hereinafter, these may be collectively referred to as "lithography material, etc."), an exposure step of exposing the film, and a development step of developing the film exposed in the exposure step to form a pattern.

[0117] For example, when forming a resist pattern using the lithography material of this embodiment, the method for forming the pattern (resist pattern) is not particularly limited. A preferred method includes a film formation step of applying a resist film forming composition containing the lithography material described above onto a substrate to form a film (resist film), an exposure step of exposing the formed film (resist film), and a development step of developing the film (resist film) exposed in the exposure step to form a pattern (resist pattern). The resist pattern of this embodiment can also be formed as an upper resist in a multilayer process.

[0118] The method for forming a specific resist pattern is not particularly limited, but examples include the following: First, a resist film is formed by applying the composition onto a conventionally known substrate using coating means such as rotary coating, casting, or roll coating. Conventionally known substrates are not particularly limited, and examples include substrates for electronic components or those on which a predetermined wiring pattern is formed. More specifically, although not particularly limited, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. The material for the wiring pattern is not particularly limited, but examples include copper, aluminum, nickel, and gold. In addition, an inorganic film or an organic film may be provided on the aforementioned substrate as needed. The inorganic film is not particularly limited, but examples include inorganic anti-reflective films (inorganic BARC). The organic film is not particularly limited, but examples include organic anti-reflective films (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

[0119] Next, the coated substrate is heated as needed. The heating conditions vary depending on the composition of the resist, but are preferably 20 to 250°C, and more preferably 20 to 150°C. Heating may improve the adhesion of the resist to the substrate, which is preferable. Then, the resist film is exposed to radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam to form a desired pattern. The exposure conditions are appropriately selected according to the composition of the resist composition.

[0120] In the resist pattern formation method of this embodiment, heating after radiation irradiation is preferable in order to stably form high-precision fine patterns during exposure. The heating conditions vary depending on the formulation of the composition, but are preferably 20 to 250°C, and more preferably 20 to 150°C.

[0121] Next, the exposed resist film is developed with a developer to form a predetermined resist pattern. It is preferable to select a solvent with a solubility parameter (SP value) close to that of the compound used in this embodiment as the developer. Polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, or alkaline aqueous solutions can be used. Depending on the type of developer, a positive resist pattern or a negative resist pattern can be produced. Generally, a negative resist pattern is obtained with polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, or hydrocarbon solvents, while a positive resist pattern is obtained with an alkaline aqueous solution. Examples of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and alkaline aqueous solutions include those disclosed in International Publication No. 2017 / 033943.

[0122] The aforementioned solvents may be mixed in multiple quantities, or mixed with other solvents or water within a range that provides satisfactory performance. However, in order to fully realize the effects of the present invention, the water content of the entire developer solution is preferably less than 70% by mass, more preferably less than 50% by mass, more preferably less than 30% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. That is, the content of the organic solvent in the developer solution is not particularly limited, but is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, even more 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, relative to the total amount of the developer solution.

[0123] In particular, a developer containing at least one solvent selected from ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is preferred in order to improve the resist performance such as the resolution and roughness of the resist pattern.

[0124] The vapor pressure of the developer is not particularly limited, but is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20°C. By setting 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, improving temperature uniformity across the wafer surface, and consequently improving dimensional uniformity across the wafer surface. An example of a developer having such a vapor pressure is the developer disclosed in International Publication No. 2017 / 033943.

[0125] A suitable amount of surfactant may be added to the developing solution as needed. While the surfactant is not particularly limited, examples include ionic or nonionic fluorine-based or silicon-based surfactants. Examples of these fluorine or silicone-based surfactants include those described in Japanese Patent Publication No. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, U.S. Patent No. 5405720, 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, and 5824451, and are preferably nonionic surfactants. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicone-based surfactant.

[0126] The amount of surfactant used is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the developing solution.

[0127] For example, development methods such as immersing the substrate in a tank filled with developer for a certain period of time (dip method), developing by piling the developer onto the substrate surface using surface tension and letting it remain still for a certain period of time (paddle method), spraying the developer onto the substrate surface (spray method), and continuously dispensing the developer onto a substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispensing method) can be applied. There are no particular restrictions on the time for developing the pattern, but it is preferably 10 to 90 seconds.

[0128] Alternatively, after the development process, a step may be performed to stop the development process while replacing the solvent with another solvent.

[0129] It is preferable that the development process includes a step of washing with a rinsing solution containing an organic solvent.

[0130] The rinsing solution used in the rinsing step after development is not particularly limited as long as it does not dissolve the resist pattern hardened by crosslinking, and a solution containing a general organic solvent or water can be used. Preferably, the rinsing solution contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, after development, a washing step is performed using a rinsing solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. Even more preferably, after development, a washing step is performed using a rinsing solution containing an alcohol solvent or an ester solvent. Even more preferably, after development, a washing step is performed using a rinsing solution containing a monohydric alcohol. Particularly preferably, after development, a washing step is performed using a rinsing solution containing a monohydric alcohol with 5 or more carbon atoms. There is no particular limit to the time for rinsing the pattern, but it is preferably 10 to 90 seconds.

[0131] Here, the monohydric alcohol used in the rinsing step after development is not particularly limited, but examples include linear, branched, and cyclic monohydric alcohols. Specifically, 1-butanol, 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, and 4-octanol can be used. Particularly preferred monohydric alcohols with 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol.

[0132] The aforementioned components may be mixed in multiple quantities, or they may be mixed with other organic solvents before use.

[0133] The water content in the rinse solution is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less. By reducing the water content to 10% by mass or less, better developing characteristics can be obtained.

[0134] The vapor pressure of the rinsing solution used after development is preferably 0.05 kPa or more and 5 kPa or less at 20°C, more preferably 0.1 kPa or more and 5 kPa or less, and even more preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinsing solution to 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is further improved, swelling caused by the penetration of the rinsing solution is further suppressed, and the dimensional uniformity within the wafer surface is further improved.

[0135] The rinse solution can also be used with an appropriate amount of surfactant added.

[0136] In the rinsing process, the developed wafer is cleaned using a rinsing solution containing the aforementioned organic solvent. The cleaning method is not particularly limited, but for example, a method of continuously applying the rinsing solution onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or a method of spraying the rinsing solution onto the substrate surface (spray method) can be applied. Among these, it is preferable to perform the cleaning using the rotary coating method, and after cleaning, rotate the substrate at a rotational speed of 2000 rpm to 4000 rpm to remove the rinsing solution from the substrate.

[0137] A patterned wiring substrate is obtained by etching after forming a resist pattern. The etching method can be any known method, such as dry etching using plasma gas or wet etching using an alkaline solution, cupric chloride solution, or ferric chloride solution.

[0138] Plating can also be performed after forming the resist pattern. The plating method is not particularly limited, but examples include copper plating, solder plating, nickel plating, and gold plating.

[0139] The residual resist pattern after etching can be removed with an organic solvent. The organic solvent is not particularly limited, but examples include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). The removal method is not particularly limited, but examples include immersion methods and spray methods. The wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate and may have small-diameter through-holes.

[0140] In this embodiment, the wiring substrate can also be formed by a method in which a resist pattern is formed, a metal is deposited in a vacuum, and then the resist pattern is dissolved in a solution, i.e., the lift-off method.

[0141] 2) Composition for forming a lithography underlayer film, lithography underlayer film, and pattern formation method [First Embodiment] <Composition for forming lower layer film for lithography> The lithography underlayer film forming composition according to the first embodiment of the present invention contains the compound according to this embodiment and a silicon-containing compound (for example, a hydrolyzable organosilane, its hydrolysate, or its hydrolyzed condensate). The lithography underlayer film forming composition of this embodiment can form a lithography underlayer film such as a resist underlayer film, and has high heat resistance and high solvent solubility. Therefore, it has excellent rectangularity of pattern. In addition, it enables the reduction of film defects (thin film formation), has high adhesion, good storage stability, high sensitivity and long-term lightfastness, and can impart a good resist pattern shape. Furthermore, because the molecules of the compound according to this embodiment have an appropriate diffusion rate, they exhibit high resolution while maintaining high sensitivity. Moreover, because the compound has an appropriate molecular weight, it is not easily volatile, and film loss during curing is relatively small, so the lithography underlayer film forming composition can form a lithography underlayer film with high flatness.

[0142] The lithography underlayer film formation composition of this embodiment can be suitably used in a multilayer resist method, for example, in which a resist underlayer film is further provided between an upper resist (such as a photoresist) and a hard mask or organic underlayer film. In such a multilayer resist method, for example, a resist underlayer film is formed on a substrate via an organic underlayer film or a hard mask by a coating method, and an upper resist (for example, a photoresist, electron beam resist, or EUV resist) is formed on the resist underlayer film. 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, the organic underlayer film is etched to transfer the pattern, and the substrate is processed using the organic underlayer film.

[0143] In other words, the lithography underlayer (resist underlayer) formed using the lithography underlayer formation composition of this embodiment is less prone to intermixing with the upper resist, has heat resistance, and, for example, its etching rate to halogen-based (fluorine-based) etching gases is greater than that of the patterned upper resist used as a mask, thus enabling the creation of a rectangular and well-formed pattern. Furthermore, the lithography underlayer (resist underlayer) formed using the lithography underlayer formation composition of this embodiment has high resistance to oxygen-based etching gases, so it can function as a good mask when patterning layers provided on a substrate, such as hard masks. The lithography underlayer formation composition of this embodiment can also be used in configurations where multiple resist underlayers are stacked. In this case, the position of the resist underlayer formed using the lithography underlayer formation composition of this embodiment (which layer it is stacked in) is not particularly limited; it may be directly beneath the upper resist, the layer located closest to the substrate, or sandwiched between resist underlayers.

[0144] When forming fine patterns, the resist film thickness tends to be thin to prevent pattern collapse. Due to the thinning of the resist, dry etching to transfer the pattern to the film in the underlying layer requires a higher etching rate than that of the upper layer for pattern transfer to be possible. In this embodiment, an organic underlayer film can be placed on the substrate, which is then coated with the resist underlayer film of this embodiment (containing a silicon-based compound), and then further coated with a resist film (organic resist film). The dry etching rate differs greatly between films with organic components and films with inorganic components depending on the selection of etching gas. Films with organic components have a higher dry etching rate with oxygen-based gases, while films with inorganic components have a higher dry etching rate with halogen-containing gases.

[0145] For example, a resist underlayer with a pattern transferred to it can be used to dry etch an organic underlayer with an oxygen-based gas to transfer a pattern to the organic underlayer, and then substrate processing can be performed using a halogen-containing gas on the organic underlayer with the transferred pattern. The lithography underlayer (resist underlayer) formed using the lithography underlayer formation composition of this embodiment has good adhesion, so the deformation of the transferred pattern can also be suppressed.

[0146] Furthermore, the resist underlayer film formed by the lithography underlayer film-forming composition of this embodiment contains the compound according to this embodiment, which has excellent absorption ability to active light, and a silicon-containing compound (for example, a hydrolyzable organosilane, its hydrolysate, or its hydrolyzed condensate), thereby improving the sensitivity of the upper resist, preventing intermixing with the upper resist, and resulting in a rectangular pattern shape for the resist underlayer film after exposure and development. This enables substrate processing with fine patterns.

[0147] Furthermore, the resist underlayer film formed using the lithography underlayer film formation composition of this embodiment has high heat resistance and can be used even under high-temperature baking conditions. In addition, because it has a relatively low molecular weight and low viscosity, it is easy to uniformly fill even substrates with steps (especially fine spaces and hole patterns), and as a result, planarization and filling characteristics tend to be relatively advantageously improved.

[0148] The lithography underlayer film forming composition may further contain a solvent, an acid generator, an acid crosslinking agent, or a combination thereof. Other optional components may include organic polymer compounds, surfactants, water, alcohol, and curing catalysts. From the viewpoint of coatability and quality stability, the content of the compound according to this embodiment in the lithography underlayer film forming composition is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, and particularly preferably 3.0 to 40% by mass.

[0149] <Solvent> As the solvent used in this embodiment, any known solvent can be used as appropriate, as long as it at least dissolves the compound portion according to this embodiment. For example, a solvent that may be included in a lithography underlayer film forming composition disclosed in International Publication No. 2017 / 188450 is an example. The solvent is preferably a safe solvent, more preferably at least one selected from esters such as PGMEA, butyl acetate, ethyl propionate, and ethyl lactate; polyhydric alcohol ethers such as PGME; and aprotic polar solvents such as CHN, CPN, 2-heptanone, and anisole, and even more preferably at least one selected from PGMEA, PGME, and CHN.

[0150] The solvent content is not particularly limited, but from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass, more preferably 200 to 8,000 parts by mass, and even more preferably 200 to 5,000 parts by mass, per 100 parts by mass of the total solid content of the lithography underlayer film forming composition.

[0151] <Acid crosslinking agent> The lithography underlayer film forming composition may contain one or more acid crosslinking agents when used as a negative-type resist material or as an additive to increase the pattern strength in a positive-type resist material. Examples of acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") that can form crosslinks in the presence of an acid. For example, an acid crosslinking agent that may be included in a lithography underlayer film forming composition disclosed in International Publication No. 2017 / 188450 can be cited. Also, for example, the one described in International Publication No. WO2013 / 024779 can be cited as a specific example of the acid crosslinking agent.

[0152] The content of the acid crosslinking agent is not particularly limited, but from the viewpoint of solubility and shape stability of the coating film, it is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 20 parts by mass, and even more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total solid content of the lithography underlayer film forming composition.

[0153] <Silicon-containing compounds> The silicon-containing compound may be either an organosilicon-containing compound or an inorganic silicon-containing compound, but an organosilicon-containing compound is preferred. Examples of the inorganic silicon-containing compound include polysilazane compounds made of silicon oxides, silicon nitrides, and silicon oxidnitrides that can be formed by coating at low temperatures. Examples of the organosilicon-containing compound include polysilsesquioxane-based compounds, hydrolyzable organosilanes, their hydrolysates, or their hydrolyzed condensates. The specific polysilsesquioxane-based material is not limited to the following, but for example, those described in Japanese Patent Publication No. 2007-226170 and Japanese Patent Publication No. 2007-226204 can be used. Furthermore, the hydrolyzable organosilane, its hydrolysate, or its hydrolyzed condensate may include at least one hydrolyzable organosilane selected from the group consisting of the hydrolyzable organosilane of formula (D1) and formula (D2), their hydrolysates, or their hydrolyzed condensates (hereinafter, these may simply be referred to as "at least one organosilicon compound selected from the group consisting of formulas (D1) and (D2)"). When the lithography underlayer film forming composition contains at least one organosilicon compound selected from the group consisting of formulas (D1) and (D2), the Si-O bond can be easily controlled by adjusting the curing conditions, it is also cost-effective, and it is suitable for introducing organic components. Therefore, a layer formed using the lithography underlayer film forming composition, which comprises at least one organosilicon compound selected from the group consisting of formulas (D1) and (D2), is useful as an intermediate layer of a resist layer (a layer between the upper resist layer and an organic underlayer film provided on the substrate).

[0154] Formula (D1): (R 3 ) a Si(R 4 ) 4-a (In formula (D1), R 3represents an "organic group" having an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, an epoxy group, an acryloyl 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 is bonded to a silicon atom by 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.)

[0155] Formula (D2): [(R 5 ) c Si(R 6 ) 4-c 2Y b (In 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.)

[0156] In the composition, the ratio of the compound according to this embodiment and a silicon-containing compound (for example, at least one organosilicon compound selected from the group consisting of formula (D1) and formula (D2)) can be used in a molar ratio range of 1:2 to 1:200. In order to obtain a good resist shape, for example, it can be used in a range of 1:2 to 1:100 in the above molar ratio. At least one organosilicon compound selected from the group consisting of formula (D1) and formula (D2) is preferably used as a hydrolysis condensate (a polymer of polyorganosiloxane).

[0157] R in the hydrolyzable organosilane represented by formula (D1) 3This refers to an "organic group" having an alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkenyl group, epoxy group, acryloyl group, methacryloyl group, mercapto group, alkoxyaryl group, acyloxyaryl group, isocyanurate group, hydroxyl group, cyclic amino group, or cyano group, or a combination thereof, and is bonded to a silicon atom by a Si-C bond, R 4 represents an alkoxy group, acyloxy group, or halogen group, and a represents an integer from 0 to 3.

[0158] R of hydrolyzable organosilane of formula (D2) 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.

[0159] Examples of hydrolyzable organosilanes represented by formulas (D1) and (D2) include hydrolyzable organosilanes that may be included in compositions for forming underlayer films for lithography, as disclosed in International Publication No. 2017 / 188450.

[0160] In this embodiment, the compound according to this embodiment and hydrolyzable organosilanes, etc., may be reacted to form a film as a mixture. Alternatively, the compound according to this embodiment in the lithography underlayer film-forming composition and the above-mentioned hydrolyzable organosilanes, etc., may be subjected to hydrolysis condensation using one or more compounds selected from inorganic acids, aliphatic sulfonic acids, and aromatic sulfonic acids as an acid catalyst.

[0161] Examples of acid catalysts used in this case include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, etc. The amount of catalyst used is 10 per mole of monomer (total amount of the compound according to this embodiment and hydrolyzable organosilane, etc.) -6 ~10 moles is preferred, and 10 moles is comfortable. -5~5 moles, more preferably 10 -4 It is approximately 1 mole.

[0162] The amount of water added when hydrolyzing and condensing these monomers is preferably 0.01 to 100 moles per mole of hydrolyzable substituent attached to the monomer (compounds according to this embodiment and hydrolyzable organosilanes, etc.), more preferably 0.05 to 50 moles, and even more preferably 0.1 to 30 moles. Adding 100 moles or less is economical because it does not require excessively large equipment for the reaction.

[0163] The procedure involves, for example, adding a monomer to an aqueous catalyst solution to initiate the hydrolysis condensation reaction. At this time, an organic solvent may be added to the aqueous catalyst solution, or the monomer may be diluted with an organic solvent beforehand, or both may be done. The reaction temperature is preferably 0 to 100°C, more preferably 40 to 100°C. It is preferable to maintain the temperature at 5 to 80°C when adding the monomer dropwise, and then allow it to mature at 40 to 100°C.

[0164] Examples of organic solvents that can be added to an aqueous catalyst solution or used to dilute monomers include the organic solvents disclosed in International Publication No. 2017 / 188450.

[0165] The amount of organic solvent used is preferably 0 to 1,000 ml per mole of monomer (total amount of the compound according to this embodiment and hydrolyzable organosilane, etc.), and particularly preferably 0 to 500 ml. Using 1,000 ml or less of organic solvent is economical because it does not require an excessively large reaction vessel.

[0166] Subsequently, 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 solution of the reaction mixture. At this time, the amount of alkaline substance that can be used for neutralization is preferably 0.1 to 2 equivalents relative to the acid used in the catalyst. This alkaline substance can be any substance that exhibits alkalinity in water.

[0167] Next, it is preferable to remove by-products such as alcohol produced by the hydrolysis condensation reaction from the reaction mixture. The temperature at which the reaction mixture is heated depends on the type of organic solvent added and the type of alcohol produced by the reaction, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of reduced pressure at this time varies depending on the type of organic solvent and alcohol to be removed, the exhaust system, the condensing system, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and even more preferably 50 kPa or less in absolute pressure. It is difficult to know the exact amount of alcohol removed at this time, but it is desirable that approximately 80% or more by mass of the produced alcohol is removed.

[0168] Next, the acid catalyst used in the hydrolysis condensation may be removed from the reaction mixture. An example of a method for removing the acid catalyst is to mix the reaction mixture with water and extract the product with an organic solvent. The organic solvent used in this case 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 can be cited.

[0169] Furthermore, when removing the acid catalyst used in hydrolysis condensation from the reaction mixture, it is also possible to use a mixture of a water-soluble organic solvent and a water-insoluble organic solvent. For example, the mixture disclosed in International Publication No. 2017 / 188450 is one such example.

[0170] The mixing ratio of the water-soluble organic solvent and the water-insoluble organic solvent is selected as appropriate, but preferably it is 0.1 to 1,000 parts by mass of the water-soluble organic solvent per 100 parts by mass of the water-insoluble organic solvent, more preferably 1 to 500 parts by mass, and even more preferably 2 to 100 parts by mass.

[0171] In both cases—the product with residual acid catalyst and the product from which the acid catalyst has been removed—a solution of the product can be obtained by adding the final solvent and exchanging the solvent under reduced pressure. The temperature of the solvent exchange at this time depends on the type of reaction solvent or extraction solvent to be removed, but is preferably 0 to 100°C, more preferably 10 to 90°C, and even more preferably 15 to 80°C. The degree of reduced pressure at this time varies depending on the type of extraction solvent to be removed, the exhaust system, the condenser, and the heating temperature, but is preferably below atmospheric pressure, more preferably 80 kPa or less in absolute pressure, and even more preferably 50 kPa or less in absolute pressure.

[0172] <Other optional ingredients> In addition to the components mentioned above, the composition may optionally include organic polymer compounds, crosslinking agents, and surfactants.

[0173] By using an organic polymer compound, the dry etching rate (decrease in film thickness per unit time), decay coefficient, refractive index, etc., of the resist underlayer film formed from the lithography underlayer film forming composition can be adjusted. There are no particular restrictions on the organic polymer compound, and various organic polymers can be used. Condensation polymers and addition polymers can be used, etc. For example, the organic polymer compounds disclosed in International Publication No. 2017 / 188450 can be used.

[0174] By using a crosslinking agent, it is possible to adjust the dry etching rate (the amount of film thickness reduction per unit time) of the resist underlayer film formed from the composition for forming a lower layer film for lithography. There are no particular limitations on the crosslinking agent, and various crosslinking agents can be used. Specific examples of the crosslinking agent that can be used in the present embodiment include, for example, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, compounds containing a double bond such as an alkenyl ether group, and those having at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group as a substituent (crosslinkable group), but are not particularly limited thereto. For example, the crosslinking agent disclosed in International Publication No. 2017 / 188450 can be mentioned.

[0175] In the composition for forming a lower layer film for lithography, the content of the crosslinking agent is not particularly limited, but is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the compound according to the present embodiment. By setting it within the above-mentioned preferable range, the occurrence of a 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.

[0176] The surfactant is effective in suppressing the occurrence of surface defects and the like when the composition for forming a lower layer film for lithography is applied to a substrate. Examples of the surfactant contained in the composition for forming a lower layer film for lithography include, for example, the surfactants disclosed in International Publication No. 2017 / 188450. When the surfactant is used, its ratio is, for example, 0.0001 parts by mass to 5 parts by mass, or 0.001 parts by mass to 1 part by mass, or 0.01 parts by mass to 0.5 parts by mass, based on 100 parts by mass of the compound according to the present embodiment.

[0177] <Lower Layer Film for Lithography and Pattern Forming Method> A lithography underlayer film according to the first embodiment of the present invention can be formed using the lithography underlayer film forming composition according to the first embodiment of the present invention. The lithography underlayer film of this embodiment can be suitably used as an underlayer (resist underlayer film) of a photoresist (upper layer) used in a multilayer resist method.

[0178] In this embodiment, for example, a resist underlayer film can be formed using a lithography underlayer film forming composition, at least one photoresist layer can be formed on the resist underlayer film, and then a pattern can be formed by irradiating a predetermined area of ​​the photoresist layer with radiation and performing development.

[0179] Furthermore, one embodiment of the pattern formation method according to the first embodiment of the present invention, using the lithography underlayer forming composition according to the first embodiment of the present invention prepared as described above, is a pattern formation method that involves forming an organic underlayer on a substrate using a coating-type organic underlayer material, forming a resist underlayer on the organic underlayer using the lithography underlayer forming composition according to the first embodiment of the present invention, forming an upper resist on the resist underlayer using an upper resist composition, forming an upper resist pattern on the upper resist film, transferring the pattern to the resist underlayer by etching using the upper resist pattern as a mask, transferring the pattern to the organic underlayer by etching using the resist underlayer on which the pattern has been transferred as a mask, and further transferring the pattern to the substrate (workpiece) by etching using the organic underlayer on which the pattern has been transferred as a mask.

[0180] Another embodiment of the pattern formation method according to the first embodiment of the present invention is a pattern formation method comprising: forming an organic hard mask mainly composed of carbon on a substrate by CVD; forming a resist underlayer on the organic hard mask using the lithography underlayer forming composition of the first embodiment of the present invention; forming an upper resist film on the resist underlayer using the upper resist film composition; forming an upper resist pattern on the upper resist film; transferring the pattern to the resist underlayer by etching using the upper resist pattern as a mask; transferring the pattern to the organic hard mask by etching using the resist underlayer on which the pattern has been transferred as a mask; and further transferring the pattern to the substrate (workpiece) by etching using the organic hard mask on which the pattern has been transferred as a mask.

[0181] As the substrate, for example, a semiconductor substrate can be used. As the semiconductor substrate, a silicon substrate can generally be used, but it is not particularly limited, and materials different from the workpiece layer can be used, such as Si, amorphous silicon (α-Si), p-Si, SiO2, SiN, SiON, W, TiN, Al, etc.

[0182] Furthermore, as the metal constituting the base material (workpiece; including the semiconductor substrate), any of silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, or molybdenum, or alloys thereof, can be used.

[0183] Furthermore, a semiconductor substrate can be used as the workpiece layer (workpiece portion) on which a metal film, metal carbide film, metal oxide film, metal nitride film, metal oxide carbide film, or metal oxide nitride film has been deposited. Examples of such metal-containing workpiece layers include Si, SiO2, SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, W, W-Si, Al, Cu, Al-Si, and various low-dielectric films and their etching stopper films, which can typically be formed to a thickness of 50 to 10,000 nm, particularly 100 to 5,000 nm.

[0184] In the pattern formation method of this embodiment, an organic underlayer film or an organic hard mask can be formed on a substrate. Of these, the organic underlayer film can be formed from a coating-type organic underlayer film material using a rotary coating method or the like, and the organic hard mask can be formed from an organic hard mask material mainly composed of carbon using a CVD method. The types of such organic underlayer films and organic hard masks are not particularly limited, but when the upper resist film is patterned by exposure, it is preferable that they exhibit sufficient anti-reflective film function. By forming such an organic underlayer film or organic hard mask, the pattern formed by the upper resist film can be transferred onto the substrate (workpiece) without causing size conversion differences. Note that a hard mask "mainly composed of carbon" means a hard mask in which 50% or more of the solid content is composed of a carbon-based material such as amorphous carbon hydride, also called amorphous carbon, and denoted as aC:H. aC:H films can be deposited by various techniques, but plasma chemical vapor deposition (PECVD) is widely used due to its cost-effectiveness and the ability to adjust the film quality. For example, one can refer to the hard mask described in Japanese Patent Publication No. 2013-526783.

[0185] The resist underlayer film using the resist underlayer film forming composition of this embodiment, which is used in the pattern formation method of this embodiment, can be fabricated on a workpiece that has an organic underlayer film or the like prepared by spin coating or the like from the lithography underlayer film forming composition. When forming the resist underlayer film by spin coating, it is desirable to evaporate the solvent after spin coating and bake to promote the crosslinking reaction in order to prevent 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 device being manufactured, a bake temperature of 400°C or lower is particularly preferable in order to reduce thermal damage to the device. The bake time is preferably in the range of 10 seconds to 300 seconds.

[0186] Furthermore, in the pattern formation method of this embodiment, as a method for forming a pattern on the upper resist film, one of the following methods can be suitably used: lithography using light with a wavelength of 300 nm or less or EUV light; electron beam direct lithography; and induced self-assembly. By using such a method, a fine pattern can be formed on the resist upper film.

[0187] The upper resist film composition can be appropriately selected depending on the method of forming a pattern on the upper 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. Examples of such photoresist film materials include those that form a photoresist film and, after exposure, dissolve the exposed areas with an alkaline developer to form a positive pattern, and those that form a negative pattern by dissolving the unexposed areas with a developer made of an organic solvent.

[0188] The resist underlayer film formed from the lithography underlayer film forming composition of this embodiment may absorb light depending on the wavelength of light used in the lithography process. In such cases, it can function as an anti-reflective film that prevents reflected light from the substrate.

[0189] Furthermore, in addition to its function as a hard mask, the underlayer film of the EUV resist can also be used for the following purposes. The lithography underlayer film forming composition according to this embodiment can be used as an underlayer anti-reflection film of an EUV resist that can prevent reflection of undesirable exposure light, such as the aforementioned 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. Reflection can be efficiently prevented in the underlayer of the EUV resist. In addition, since the underlayer film forming composition has excellent EUV absorption ability, it can exert a sensitizing effect on the upper resist composition, contributing to improved sensitivity. When used as an underlayer film of an EUV resist, the process can be carried out in the same way as for an underlayer film of a photoresist.

[0190] [Second Embodiment] <Composition for forming lower layer film for lithography> The lithography underlayer film forming composition according to the second embodiment of the present invention is a lithography underlayer film forming composition containing the compound according to this embodiment. The lithography underlayer film forming composition of this embodiment enables the reduction of film defects (thin film formation), has good storage stability, high sensitivity and long-term light resistance, and can impart a good resist pattern shape. The lithography underlayer film forming composition of this embodiment may not contain silicon-containing compounds.

[0191] The lithography underlayer formation composition of this embodiment is applicable to a wet process and can realize a lithography underlayer formation composition useful for forming a photoresist underlayer with excellent heat resistance, adhesion, step-filling characteristics, and especially flatness. Furthermore, because this lithography underlayer formation composition uses a compound having a specific structure that allows for a relatively high crosslinking density and high solvent solubility, film degradation during baking is suppressed, and an underlayer with excellent etching resistance to fluorine gas-based plasma etching and the like can be formed. Moreover, because it has excellent adhesion to the resist layer, an excellent resist pattern can be formed. Because the lithography underlayer formation composition of this embodiment is particularly excellent in heat resistance, step-filling characteristics, and flatness, it can be used, for example, as a resist underlayer formation composition provided as the bottom layer among multiple resist layers. However, the resist underlayer formed using the lithography underlayer formation composition of this embodiment may further include other resist underlayers between it and the substrate.

[0192] The lithography underlayer film-forming composition according to this embodiment may further contain, in addition to the compound according to this embodiment, a solvent, an acid generator, an acid crosslinking agent, and the like. Furthermore, optional components such as a basic compound, water, alcohol, and a curing catalyst may be included. From the viewpoint of coatability and quality stability, the content of the compound according to this embodiment in the lithography underlayer film-forming composition is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, and particularly preferably 3.0 to 40% by mass.

[0193] <Solvent> The solvent used in this embodiment is the same as that described in the first embodiment. The amount is also the same as described in the first embodiment.

[0194] <Acid crosslinking agent> As described above, the lithography underlayer film forming composition of this embodiment may contain an acid crosslinking agent as needed, from the viewpoint of suppressing intermixing. Examples of acid crosslinking agents that can be used in this embodiment include, but are not limited to, compounds containing double bonds such as melamine compounds, epoxy compounds, guanamine compounds, glycoluryl compounds, urea compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and alkenyl ether groups, which have at least one group selected from methylol, alkoxymethyl, and acyloxymethyl groups as a substituent (crosslinking group). These acid crosslinking agents can be used individually or in combination of two or more. They may also be used as additives. Compounds containing hydroxyl groups can also be used as crosslinking agents. Specific examples of the acid crosslinking agents include, for example, those described in International Publication No. 2013 / 024779.

[0195] In the lithography underlayer film forming composition of this embodiment, the content of the acid crosslinking agent is not particularly limited, but is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, based on 100 parts by mass of the total solid content of the lithography underlayer film forming composition. By setting the content within the above preferred range, the occurrence of mixing with the resist layer tends to be suppressed, the anti-reflective effect is enhanced, and the film formation performance after crosslinking tends to be improved.

[0196] <Acid Generator> The lithography underlayer film forming composition of this embodiment may contain an acid generator as needed, from the viewpoint of further promoting the thermal crosslinking reaction. Known acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of these can be used. As the acid generator, for example, the one described in International Publication WO2013 / 024779 can be used.

[0197] In the lithography underlayer film forming composition of this embodiment, the content of the acid generator is not particularly limited, but is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 40 parts by mass, per 100 parts by mass of the total solid content of the lithography underlayer film forming composition. By setting the content within the above preferred range, the amount of acid generated tends to increase, thereby enhancing the crosslinking reaction, and the occurrence of mixing with the resist layer tends to be suppressed.

[0198] <Basic compounds> Furthermore, the lithography underlayer film-forming composition of this embodiment may contain a basic compound from the viewpoint of improving storage stability, etc.

[0199] Basic compounds act as quenchers for acids, preventing trace amounts of acid generated by acid generators from advancing the crosslinking reaction. Examples of such basic compounds include, but are not limited to, primary, secondary, or tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having carboxyl groups, nitrogen-containing compounds having sulfonyl groups, nitrogen-containing compounds having hydroxyl groups, nitrogen-containing compounds having hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives. Specific examples of basic compounds can be found, for example, those described in International Publication No. 2013 / 024779.

[0200] In the lithography underlayer film-forming composition of this embodiment, the content of the basic compound is not particularly limited, but is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total solid content of the lithography underlayer film-forming composition. By keeping it within the above preferred range, storage stability tends to be improved without excessively impairing the crosslinking reaction.

[0201] Furthermore, the lithography underlayer film-forming composition of this embodiment may contain other resins or compounds for the purpose of imparting thermosetting properties or controlling absorbance. Examples of such other resins or compounds include, but are not limited to, naphthol resins, xylene resin naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth)acrylate, dimethacrylate, trimethacrylate, tetramethacrylate, vinylnaphthalene, polyacenaphthylene and other naphthalene rings, biphenyl rings such as phenanthrenequinone and fluorene, heteroatoms such as thiophene and indene, heterocycles containing heteroatoms, and resins that do not contain aromatic rings; rosin-based resins, cyclodextrins, adamantane(poly)ol, tricyclodecane(poly)ol and their derivatives and other resins or compounds containing alicyclic structures. The known additives mentioned above are not limited to, but include, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.

[0202] <Method for forming a resist underlayer and pattern for lithography> A lithography resist underlayer film according to the second embodiment of the present invention is formed using the lithography underlayer film forming composition 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.

[0203] Furthermore, the pattern formation method according to the second embodiment of the present invention comprises the steps of: forming a resist underlayer film on a substrate using the lithography underlayer film forming composition of the second embodiment of the present invention (Step A-1); forming at least one photoresist layer on the resist underlayer film (Step A-2); and, after forming at least one photoresist layer in Step A-2, irradiating a predetermined area of ​​the photoresist layer with radiation to perform development (Step A-3). Note that "photoresist layer" refers to the outermost layer of the resist layer, that is, the layer provided on the front side (opposite side from the substrate) of the resist layer.

[0204] Furthermore, another pattern formation method according to the second embodiment of the present invention includes the steps of: forming a resist underlayer film on a substrate using the lithography underlayer film forming composition of the second embodiment of the present invention (Step B-1); forming a resist intermediate layer film on the underlayer film using a resist intermediate layer film material (e.g., a silicon-containing resist layer) (Step B-2); forming at least one photoresist layer on the resist intermediate layer film (Step B-3); forming a resist pattern by irradiating a predetermined area of ​​the photoresist layer with radiation and developing it after forming at least one photoresist layer in Step B-3 (Step B-4); and forming a pattern on a substrate by etching the resist intermediate layer film using the resist pattern as a mask after the resist pattern has been formed in Step B-4, etching the underlayer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained underlayer film pattern as an etching mask (Step B-5).

[0205] The resist underlayer film for lithography according to this embodiment is formed from the lithography underlayer film forming composition of this embodiment, but the method of formation is not particularly limited, and known methods can be applied. For example, the resist underlayer film can be formed by applying the lithography underlayer film forming composition of this embodiment to a substrate by known coating or printing methods such as spin coating or screen printing, and then removing it by volatilizing the organic solvent.

[0206] When forming the resist underlayer film, it is preferable to perform a bake treatment to suppress the mixing phenomenon with the upper resist (e.g., photoresist layer or resist interlayer film) and to promote the crosslinking reaction. In this case, the bake temperature is not particularly limited, but is preferably in the range of 80 to 450°C, and more preferably 200 to 400°C. The bake time is also not particularly limited, but is preferably in the range of 10 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 around 30 to 20,000 nm, and more preferably 50 to 15,000 nm.

[0207] After fabricating a resist underlayer on a substrate, a resist intermediate layer can be provided between the photoresist layer and the resist underlayer. For example, in a two-layer process, a silicon-containing resist layer or a single-layer resist made of ordinary hydrocarbons can be provided as a resist intermediate layer on top of the resist underlayer. Also, for example, in a three-layer process, it is preferable to fabricate a silicon-containing intermediate layer between the resist intermediate layer and the photoresist layer, and then a silicon-free single-layer resist layer on top of that. Known photoresist materials can be used to form these photoresist layers, resist intermediate layers, and the resist layers provided between these layers.

[0208] For example, as a silicon-containing resist material for a two-layer process, a positive-type photoresist material is preferably used, from the viewpoint of oxygen gas etching resistance, in which a silicon atom-containing polymer such as a polysilsesquioxane derivative or vinylsilane derivative is used as the base polymer, and further containing an organic solvent and, if necessary, a basic compound. Here, as the silicon atom-containing polymer, known polymers used in this type of resist material can be used.

[0209] Furthermore, for example, a polysilsesquioxane-based intermediate layer is preferably used as a silicon-containing intermediate layer for a three-layer process. By giving the resist intermediate layer film an anti-reflective effect, reflection tends to be effectively suppressed. For example, in a 193nm exposure process, if a material containing many aromatic groups and having high substrate etching resistance is used as the resist underlayer film, the k value tends to increase and substrate reflection tends to increase. However, by suppressing reflection with the resist intermediate layer film, substrate reflection can be reduced to 0.5% or less. While not limited to the following, polysilsesquioxane that can be crosslinked with acid or heat and into which phenyl groups or light-absorbing groups having silicon-silicon bonds are introduced is preferably used for 193nm exposure.

[0210] Furthermore, a resist interlayer film formed by the Chemical Vapor Deposition (CVD) method can also be used. While not limited to the following, a highly effective anti-reflective interlayer film produced by the CVD method is known, for example, a SiON film. Generally, forming a resist interlayer film by wet processes such as spin coating or screen printing is simpler and more cost-effective than the CVD method. In a three-layer process, the upper resist can be either positive or negative, and the same type of single-layer resist commonly used can be used.

[0211] Furthermore, the resist underlayer film of this embodiment can also be used as an anti-reflective film for ordinary single-layer resists or as a base material for suppressing pattern deformation. Since the resist underlayer film of this embodiment has excellent etching resistance for base processing, it can also be expected to function as a hard mask for base processing.

[0212] When forming a resist layer using the known photoresist material described above, a wet process such as spin coating or screen printing is preferably used, similar to the method used to form the resist underlayer. After applying the resist material by spin coating or the like, pre-baking is usually performed, preferably at a bake temperature of 80 to 180°C and a bake time of 10 to 300 seconds. Subsequently, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain the resist pattern. The thickness of each resist film is not particularly limited, but is generally preferred to be 30 nm to 500 nm, and more preferably 50 nm to 400 nm.

[0213] Furthermore, the exposure light should be appropriately selected depending on the photoresist material being used. Generally, high-energy rays with wavelengths of 300 nm or less can be used, specifically excimer lasers at 248 nm, 193 nm, and 157 nm, soft X-rays, electron beams, and X-rays at 3 to 20 nm.

[0214] The resist pattern formed by the method described above has pattern deformation suppressed by the resist underlayer film of this embodiment. Therefore, by using the resist underlayer film of this embodiment, a finer pattern can be obtained, and the exposure amount required to obtain that resist pattern can be reduced.

[0215] Next, etching is performed using the obtained resist pattern as a mask. In a two-layer process, gas etching is preferably used for etching the resist underlayer. Gas etching using oxygen gas is preferred. In addition to oxygen gas, it is also possible to add inert gases such as He and Ar, or gases such as CO, CO2, NH3, SO2, N2, NO2, and H2. Furthermore, gas etching can be performed using only CO, CO2, NH3, N2, NO2, and H2 gases without using oxygen gas. The latter gases are particularly preferred for sidewall protection to prevent undercutting of the pattern sidewalls.

[0216] 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) in the three-layer process. The same gas etching methods as those described in the two-layer process above can be applied. In particular, it is preferable to process the intermediate layer in the three-layer process using a fluorocarbon-based gas to mask the resist pattern. Subsequently, as described above, the resist underlayer can be processed by performing, for example, oxygen gas etching using the intermediate layer pattern as a mask.

[0217] In this case, when forming an inorganic hard mask intermediate layer, a silicon oxide film, silicon nitride film, or silicon oxynitride film (SiON film) is formed by CVD or ALD. The method for forming the nitride film is not limited to the following, but for example, the method described in Japanese Patent Application Publication No. 2002-334869 and WO2004 / 066377 can be used. A photoresist film can be formed directly on such an intermediate layer, but an organic anti-reflective coating (BARC) may be formed on the intermediate layer by spin coating, and then a photoresist film may be formed on top of that.

[0218] A polysilsesquioxane-based intermediate layer is also preferably used as an intermediate layer. By giving the resist intermediate film an anti-reflective effect, reflection tends to be effectively suppressed. The specific material of the polysilsesquioxane-based intermediate layer is not limited to the following, but for example, those described in Japanese Patent Publication No. 2007-226170 and Japanese Patent Publication No. 2007-226204 can be used.

[0219] Furthermore, substrate etching can be performed using conventional methods. For example, if the substrate is SiO2 or SiN, etching can be performed primarily with fluorocarbon gases, while for p-Si, Al, or W, etching can be performed primarily with chlorine or bromine gases. When etching the substrate with fluorocarbon gases, the silicon-containing resist in a two-layer resist process and the silicon-containing intermediate layer in a three-layer resist process are stripped simultaneously with the substrate processing. On the other hand, when etching the substrate with chlorine or bromine gases, the silicon-containing resist layer or silicon-containing intermediate layer is stripped separately, and generally, dry etching with fluorocarbon gas is performed after the substrate processing.

[0220] The resist underlayer film of this embodiment exhibits excellent etching resistance of these substrates. While known substrates can be appropriately selected and used, they are not particularly limited and include Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc. The substrate may also be a laminate having a film to be processed (processed substrate) on a base material (support). Examples of such processed films include various low-k films and their stopper films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and are usually made of a different material than the base material (support). The thickness of the substrate or film to be processed is not particularly limited, but is usually preferably around 50 nm to 10,000 nm, and more preferably 75 nm to 5,000 nm.

[0221] The resist underlayer film of this embodiment exhibits excellent embedding flatness on substrates with steps. While known methods can be appropriately selected and used for evaluating embedding flatness, and are not particularly limited, for example, a solution of each compound adjusted to a predetermined concentration can be applied to a silicon substrate with steps by spin coating, followed by solvent removal drying at 110°C for 90 seconds to form an underlayer film of a predetermined thickness. The difference in underlayer film thickness (ΔT) between the line and space region and the open region without a pattern can then be measured using an ellipsometer after baking at a temperature of approximately 240-300°C for a predetermined time, thereby evaluating the embedding flatness on a stepped substrate.

[0222] 3) Compositions for forming optical articles and optical articles The optical component forming composition according to this embodiment is an optical component forming composition containing the compound according to this embodiment. This optical component forming composition is useful for forming optical articles. By containing the compound according to this embodiment, the optical component forming composition of this embodiment can be expected to produce optical articles with high refractive index and high transparency, as well as storage stability, structure formation ability (film formation ability), and heat resistance.

[0223] From the viewpoint of miniaturizing optical components and improving light-gathering efficiency, the refractive index of the optical article is preferably 1.65 or higher, more preferably 1.70 or higher, and even more preferably 1.75 or higher. From the viewpoint of improving light-gathering efficiency, the transparency of the optical article is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher.

[0224] The method for measuring refractive index is not particularly limited, and known methods can be used. Examples include spectroscopic ellipsometry, minimum deflection method, critical angle method (Abbe method, Pulfrich method), V-block method, prism coupler method, and immersion method (Becke line method). The method for measuring transparency is not particularly limited, and known methods can be used. Examples include spectrophotometers and spectroscopic ellipsometry.

[0225] Furthermore, the cured product obtained by curing the optical component forming composition according to this embodiment, which forms an optical article, can be a three-dimensional crosslinked product, and discoloration can be suppressed by heat treatment over a wide range from low to high temperatures, and high refractive index and high transparency can be expected.

[0226] The optical component forming composition of this embodiment may further contain a solvent in addition to the compound according to this embodiment. The solvent may be the same as the solvent used in the lithography underlayer forming composition of this embodiment described above.

[0227] In the optical component forming composition of this embodiment, the relationship between the amount of solid component and the amount of solvent is not particularly limited, but it is preferably 1 to 80% by mass of solid component and 20 to 99% by mass of solvent, more preferably 1 to 50% by mass of solid component and 50 to 99% by mass of solvent, even more preferably 2 to 40% by mass of solid component and 60 to 98% by mass of solvent, and particularly preferably 2 to 10% by mass of solid component and 90 to 98% by mass of solvent. Note that the optical component forming composition of this embodiment may also contain no solvent.

[0228] The optical component forming composition of this embodiment may also contain, as another solid component, at least one selected from the group consisting of an acid crosslinking agent (G), an acid diffusion control agent (E), and other components (F).

[0229] In the optical component forming composition of this embodiment, the content of the compound according to this embodiment is not particularly limited, but is preferably 50 to 99.4% by mass of the total mass of the solid components (the sum of the solid components used optionally, such as the compound according to this embodiment, the acid crosslinking agent (G), the acid diffusion control agent (E), and other components (F), and the same applies hereinafter), more preferably 55 to 90% by mass, even more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass.

[0230] <Acid Generator (C)> The optical component forming composition of this embodiment preferably contains one or more acid generators (C) that generate acid directly or indirectly by heat. The acid generator (C) is not particularly limited and can be the same as, for example, the acid generator (C) that can be included in the lithography underlayer forming composition of this embodiment described above.

[0231] In the optical component forming composition of this embodiment, the content of the acid generator (C) is preferably 0.001 to 49% by mass of the total mass of the solid components, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass. By using the acid generator (C) within the above content range, an even higher refractive index can be obtained.

[0232] <Acid crosslinking agent (G)> The optical component forming composition of this embodiment preferably contains one or more acid crosslinking agents (G) when used as an additive to increase the strength of the structure. The acid crosslinking agent (G) is not particularly limited and can be the same as, for example, the acid crosslinking agent (G) that can be included in the lithography underlayer forming composition of this embodiment described above.

[0233] In the optical component forming composition of this embodiment, the content of the acid crosslinking agent (G) is preferably 0.5 to 49% by mass of the total mass of the solid components, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass. A content of 0.5% by mass or more of the acid crosslinking agent (G) is preferable because it can improve the effect of suppressing the solubility of the optical component forming composition in organic solvents, while a content of 49% by mass or less is preferable because it can suppress the decrease in heat resistance of the optical component forming composition.

[0234] Furthermore, the content of at least one compound selected from the acid crosslinking agents (G1), (G2), and (G3) in the acid crosslinking agent (G) is not particularly limited and can be in various ranges depending on the type of substrate used when forming the optical component composition.

[0235] <Acid diffusion control agent (E)> The optical component forming composition of this embodiment may contain an acid diffusion control agent (E) that controls the diffusion of acid generated from the acid generator within the optical component forming composition, thereby preventing undesirable chemical reactions. By using such an acid diffusion control agent (E), the storage stability of the optical component forming composition is improved. Furthermore, resolution is further improved, and changes in the line width of the structure due to variations in the setting 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 included in the lithography underlayer forming composition of this embodiment described above.

[0236] The content of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass of the total mass of the solid components, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass. When the content of the acid diffusion control agent (E) is within the above range, deterioration of resolution, pattern shape, dimensional fidelity, etc., can be further suppressed. Furthermore, even if the settling time from electron beam irradiation to heating after radiation irradiation is long, the shape of the upper layer of the pattern will not deteriorate. In addition, when the content of the acid diffusion control agent (E) is 10% by mass or less, deterioration of sensitivity, developability of unexposed areas, etc., can be prevented. Furthermore, by using such an acid diffusion control agent, the storage stability of the optical component forming composition is improved, the resolution is improved, and changes in the line width of the optical component forming composition due to variations in the settling time before and after radiation irradiation can be suppressed, resulting in extremely excellent process stability.

[0237] <Other ingredients (F)> The optical component forming composition of this embodiment may optionally contain one or more additives as other components (F), such as dissolution accelerators, dissolution controllers, sensitizers, surfactants, and organic carboxylic acids or phosphorus oxoacids or derivatives thereof, to the extent that they do not hinder the purpose of this embodiment. Other components (F) can be, for example, the same as other components (F) that may be included in the lithography underlayer forming composition of this embodiment described above.

[0238] The total content of other components (F) is preferably 0 to 49% by mass of the total mass of the solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0239] In the optical component forming composition of this embodiment, the content of the compound, acid diffusion control agent (E), and other components (F) according to this embodiment (compound / acid diffusion control agent (E) / other components (F)) is preferably 50-99.4 / 0.001-49 / 0.001-49 / 0-49, more preferably 55-90 / 1-40 / 0.01-10 / 0-5, even more preferably 60-80 / 3-30 / 0.01-5 / 0-1, and particularly preferably 60-70 / 10-25 / 0.01-3 / 0. The content ratio of each component is selected from each range so that the sum is 100% by mass. With the above content ratio, performance such as sensitivity, resolution, and developability is further improved.

[0240] The method for preparing the optical component forming composition of this embodiment is not particularly limited. For example, one method may involve dissolving each component in a solvent to form a homogeneous solution at the time of use, and then filtering it as needed using, for example, a filter with a pore size of about 0.2 μm.

[0241] The optical component forming composition of this embodiment may contain other resins as long as they do not hinder the objectives of the present invention. These other resins are not particularly limited and include, for example, novolac resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers or derivatives thereof containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. The content of these resins is not particularly limited and can be appropriately adjusted depending on the type of compound used according to this embodiment.

[0242] Furthermore, the cured product of this embodiment is obtained by curing the optical component forming composition and can be used as various resins. These cured products can be used in a variety of applications as highly versatile materials that impart various properties such as high melting point, high refractive index, and high transparency. The cured product can be obtained by using known methods corresponding to each composition, such as light irradiation and heating.

[0243] These cured products can be used as various synthetic resins such as epoxy resins, polycarbonate resins, and acrylic resins, and furthermore, their functional properties can be utilized to create optical components such as lenses and optical sheets.

[0244] [Purification method] The method for purifying the compound of this embodiment comprises the steps of: dissolving the compound or its derivative in a solvent containing an organic solvent that is not arbitrarily miscible with water to obtain a solution (B); and a first extraction step of contacting the obtained solution (B) with an acidic aqueous solution to extract impurities from the compound or its derivative.

[0245] Specifically, the compound is dissolved in an organic solvent that is not arbitrarily miscible with water, and the solution is brought into contact with an acidic aqueous solution for extraction. This process transfers the metal components contained in the compound to the aqueous phase, after which the organic phase and aqueous phase are separated for purification. This method significantly reduces the content of various metals in the compound or its derivatives. Examples of derivatives of the compound include resins obtained by reacting the compounds with each other or with other compounds. Hereinafter, the compounds or their derivatives in this embodiment will also be collectively referred to as "compounds of this embodiment, etc."

[0246] An organic solvent that is not arbitrarily miscible with water refers to an organic solvent whose solubility in water is less than 50% by mass at any temperature between 20 and 90°C. From the viewpoint of productivity, this solubility is preferably less than 25% by mass. The organic solvent that is not arbitrarily miscible with water is not limited, but an organic solvent that can be safely applied to semiconductor manufacturing processes is preferred. The amount of organic solvent used is usually about 1 to 100 times the mass of the compound of the present invention.

[0247] Specific examples of solvents used in the purification method include those described in International Publication WO2015 / 080240. These solvents may be used individually or in combination of two or more. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate are preferred, with cyclohexanone and propylene glycol monomethyl ether acetate being particularly preferred.

[0248] As the acidic aqueous solution, it is appropriately selected from aqueous solutions of generally known organic and inorganic compounds dissolved in water. For example, those described in International Publication WO2015 / 080240 can be cited. These acidic aqueous solutions can be used individually 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 one or more organic acid aqueous solutions selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid are preferred. In this case, the water used should preferably have a low metal content, such as deionized water, in accordance with the purpose of the present invention.

[0249] The pH of the acidic aqueous solution is not limited, but an aqueous solution with excessively high acidity is undesirable as it may adversely affect the compound of the present invention. Typically, the pH range is about 0 to 5, and more preferably about 0 to 3.

[0250] The amount of acidic aqueous solution used is not limited, but if the amount is too small, it will be necessary to perform many extractions to remove the metal, and conversely, if it is too large, the overall volume of liquid will be large and workability may be reduced. The amount of aqueous solution used is usually 10 to 200% by mass, preferably 20 to 100% by mass, relative to the solution containing the compound of this embodiment and the organic solvent.

[0251] The temperature during the extraction process is typically 20 to 90°C, preferably in the range of 30 to 80°C. The extraction operation is carried out by thoroughly mixing the two components, for example by stirring, and then allowing it to stand. This causes the metal components contained in the compound of this embodiment to migrate to the aqueous phase. Furthermore, this process reduces the acidity of the solution, thereby suppressing the deterioration of the compound of the present invention.

[0252] The oil phase containing the compound of this embodiment is recovered from the mixture after the above treatment by decantation or the like. The standing time is not limited, but if the standing time of the mixture is too short, the separation of the oil phase containing the organic solvent from the aqueous phase will not be sufficient, which is undesirable. The standing time is usually 1 minute or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more. The extraction treatment may be performed once or multiple times.

[0253] The recovered oil phase is preferably subjected to a washing treatment with water, i.e., an extraction treatment using water (second extraction step). This treatment can be carried out as described above. The oil phase obtained after washing in this manner may contain water, but this 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 known treatments such as vacuum distillation or reprecipitation. [Examples]

[0254] The embodiment will be described in more detail below with reference to examples. However, the present invention is not limited to these examples.

[0255] [Example 1] 1) Synthesis of BCA[4]-co-BAB-DMHDO In a 100 ml round-bottom flask, 2,5-dimethyl-2,5-hexanediol (17 mmol, 2.49 g), pyridine (40 mmol, 3.22 ml), and CCl4 (40 ml) were added. The mixture was cooled to 0°C, and bromoacetyl bromide (40 mmol, 8.07 g) was slowly added. The mixture was stirred for 1 hour. The reaction was then carried out at room temperature with stirring for 24 hours. After the reaction was complete, the salt was removed by gravity filtration, the filtrate was diluted with diethyl ether, and washed in this order with 1 N aqueous HCl solution and saturated sodium bicarbonate solution. After drying the solution, it was concentrated to obtain a pale yellow solid. 1 The samples were analyzed by 1H-NMR and IR. These spectra are shown in Figures 1 and 2. The yield was 5.14 g, and the yield rate was 82%.

[0256] [ka]

[0257] BCA[4] (0.4 mmol, 0.26 g), K2CO3 (2 mmol, 0.276 g), TBAB (0.1 mmol, 0.032 g), and NMP (12 ml) were added to a test tube and stirred at 80°C for 2 hours to produce phenoxide. Then, the 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 the reaction was complete, the mixture was reprecipitation in a 0.5 N aqueous HCl solution and filtered using a Kiriyama funnel (registered trademark). After thoroughly washing with water, the mixture was dried under reduced pressure at 60°C for more than one day to obtain a milky brown solid. 1 The samples were analyzed using 1H-NMR, IR, and GPC. The yield was 0.344 g, and the yield rate was 60%. Thermal analysis was also performed. These spectra are shown in Figures 3 and 4, and the analytical results are shown in Table 1.

[0258] [ka]

[0259] [Table 1]

[0260] 2) Evaluation of BCA[4]-co-BAB-DMHDO A resist film-forming composition was prepared by dissolving BCA[4]-co-BAB-DMHDO and a photoacid generator (PAG) in PGMEA as the solvent. 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: approximately 60 nm) was formed using a spin coater, and a sensitivity curve was created by exposure, development, and rinsing. The film formation conditions, exposure amount, and development conditions are shown below. The sensitivity evaluation result was E0 = 0.8 mJ / cm 2 It was revealed that it possesses extremely high sensitivity characteristics.

[0261] Film deposition conditions Slope 30s, 4000 RPM Prebake at 110℃ for 1 minute Development conditions PEB 110℃ 1min Immersed in 2.38% by mass TMAH aqueous solution for 30s Immerse in pure water for 15 seconds.

[0262] [Example 2] Except for 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) and BCA[8] (0.2 mmol, 0.26 g) instead of BCA[4] (0.4 mmol, 0.26 g), 0.2 g of BCA[8]-co-BAB-DMODO was obtained in the same manner as in Example 1. The sensitivity of the obtained BCA[8]-co-BAB-DMODO was evaluated in the same manner as in Example 1, and the result was E0 = 1.0 mJ / cm². 2 It was highly sensitive.

[0263] [ka]

[0264] [ka]

[0265] [Comparative Example 1] Evaluation results of a composition using AC-1 as a resist material 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare the reaction solution. This 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 resulting resin was coagulated and purified, and the resulting white powder was filtered and dried overnight under reduced pressure at 40°C to obtain AC-1, represented by the following formula. Sensitivity evaluation was performed in the same manner as in Example 1 except that AC-1 was used, and it was found to be inferior to the compounds of this embodiment, BCA[4]-co-BAB-DMHDO and BCA[8]-co-BAB-DMODO. [ka]

Claims

1. A compound for forming a resist film, represented by the following formula (M-0A). 【Chemistry 1】 【Chemistry 2】

2. A compound for forming a resist film, represented by the following formula (M-1A). 【Transformation 3】 【Chemistry 4】

3. A method for producing a resist film-forming compound according to claim 1, comprising the step of reacting a polyphenol with a crosslinking agent represented by the following formula (C-0hal) to intramolecularly crosslink two or more hydroxyl groups of the polyphenol with the compound. 【Transformation 5】

4. A method for producing a resist film-forming compound according to Claim 2, comprising the step of reacting a polyphenol with a crosslinking agent represented by the following formula (C-1hal) to intramolecularly crosslink two or more hydroxyl groups of the polyphenol with the compound. 【Transformation 6】

5. A resist film forming composition containing the resist film forming compound according to claim 1 or 2.

6. The resist film forming composition according to claim 5, further comprising a component selected from the group consisting of a solvent, an acid generator, an acid crosslinking agent, and combinations thereof.

7. A resist film formed from the composition according to claim 5 or 6.

8. A film formation step of forming a film on a substrate using the resist film forming composition according to claim 5 or 6, An exposure step of exposing the aforementioned film, A developing step is performed to develop the film exposed in the exposure step to form a pattern, A pattern formation method including the following.

9. A curable composition for forming a resist film containing the compound described in claim 1 or 2.

10. The curable composition for forming a resist film according to claim 9, further containing a silicon-containing compound.

11. The curable composition for forming a resist film according to claim 10, wherein the silicon-containing compound is a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzed condensate thereof.

12. A curable composition for forming a resist film according to any one of claims 9 to 11, further comprising a component selected from the group consisting of a solvent, an acid generator, an acid crosslinking agent, and combinations thereof.

13. A lower layer film formed from a curable composition for forming a resist film according to any one of claims 9 to 12.

14. A step of forming a resist underlayer film using a curable composition for resist film formation according to any one of claims 9 to 12, The steps include forming at least one photoresist layer on the resist underlayer film, A step of irradiating a predetermined region of the photoresist layer with radiation and performing development, A pattern forming method comprising the following:

15. An optical article formed from a curable composition for forming a resist film according to any one of claims 9 to 12.

16. A step of obtaining a solution (B) by dissolving the resist film-forming compound according to claim 1 or 2 in a solvent containing an organic solvent that is optionally immiscible with water, The first extraction step involves contacting the obtained solution (B) with an acidic aqueous solution to extract impurities from the compound, A purification method that includes [details omitted].

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