Compound, resin, composition, method for forming resist pattern, method for forming circuit pattern and purification method

Abstract

To provide a novel compound useful as a film-forming material for lithography, a resin containing a structural unit derived from the compound, a composition, a resist pattern formation method, a circuit pattern formation method, and a purification method.SOLUTION: The present invention provides a compound represented by formula (0).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound, a resin, a composition, a method for forming a resist pattern, a method for forming a circuit pattern, and a purification method. [Background technology]

[0002] In the manufacture of semiconductor devices, microfabrication is carried out by lithography using photoresist materials, but in recent years, with the increasing integration and speed of LSI (large-scale integrated circuits), there is a demand for even finer pattern rules. In addition, the light source for lithography used in forming resist patterns has been shortened from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm), and the introduction of extreme ultraviolet light (EUV, 13.5 nm) is also expected.

[0003] However, in lithography using conventional polymer resist materials, the molecular weight is large, about 10,000 to 100,000, and the molecular weight distribution is wide, so that roughness occurs on the pattern surface, making it difficult to control the pattern dimensions, and there is a limit to miniaturization. Therefore, various low molecular weight resist materials have been proposed so far in order to provide resist patterns with higher resolution. Since low molecular weight resist materials have small molecular sizes, it is expected to provide resist patterns with high resolution and low roughness.

[0004] Currently, various low molecular weight resist materials are known. For example, an alkali-developable negative radiation-sensitive composition using a low molecular weight polynuclear polyphenol compound as a main component (see, for example, Patent Document 1 and Patent Document 2) has been proposed, and an alkali-developable negative radiation-sensitive composition using a low molecular weight cyclic polyphenol compound as a main component (see, for example, Patent Document 3 and Non-Patent Document 1) has also been proposed as a candidate for a low molecular weight resist material having high heat resistance. In addition, it is known that a polyphenol compound, as a base compound of a resist material, can impart high heat resistance despite its low molecular weight, and is useful for improving the resolution and roughness of a resist pattern (see, for example, Non-Patent Document 2).

[0005] Furthermore, Patent Document 4 proposes a resist composition that contains a compound of a specific structure and an organic solvent as a material that has excellent etching resistance and is soluble in a solvent to which a wet process can be applied.

[0006] In addition, as the resist pattern becomes finer, problems such as resolution problems or the resist pattern collapsing after development arise, so that it is desirable to make the resist thinner. However, simply making the resist thinner makes it difficult to obtain a resist pattern with a thickness sufficient for substrate processing. Therefore, a process is required in which, in addition to the resist pattern, an underlayer film is formed between the resist and the semiconductor substrate to be processed, and this underlayer film also functions as a mask during substrate processing.

[0007] Currently, various types of underlayer films for lithography are known. For example, unlike conventional underlayer films with a high etching rate, a material for forming an underlayer film for a multilayer resist process containing a resin component having at least a substituent that generates a sulfonic acid residue by detaching an end group when a certain energy is applied and a solvent has been proposed as a material for realizing a resist underlayer film having a dry etching rate selectivity close to that of a resist (see, for example, Patent Document 5). In addition, a material for forming an underlayer film for lithography having a dry etching rate selectivity smaller than that of a resist has been proposed as a material for realizing an underlayer film for lithography having a dry etching rate selectivity smaller than that of a resist (see, for example, Patent Document 6). Furthermore, a material for forming a resist underlayer film for lithography having a dry etching rate selectivity smaller than that of a semiconductor substrate has been proposed as a material for forming an underlayer film for lithography containing a polymer obtained by copolymerizing a repeating unit of an acenaphthylene derivative with a repeating unit having a substituted or unsubstituted hydroxyl group (see, for example, Patent Document 7).

[0008] On the other hand, as a material having high etching resistance for this type of resist underlayer film, amorphous carbon underlayer film formed by chemical vapor deposition (CVD) using methane gas, ethane gas, acetylene gas, etc. as raw materials is well known. However, from the viewpoint of process, there is a demand for a resist underlayer film material that can be formed by a wet process such as spin coating or screen printing.

[0009] Furthermore, Patent Document 8 describes a material for forming an underlayer film for lithography that contains a compound with a specific structure as a material that has excellent etching resistance, high heat resistance, is soluble in a solvent, and can be used in a wet process.

[0010] As for the method of forming the intermediate layer used in forming the resist underlayer film in the three-layer process, for example, a method of forming a silicon nitride film (see, for example, Patent Document 9) and a method of forming a silicon nitride film by CVD (see, for example, Patent Document 10) are known. In addition, as the intermediate layer material for the three-layer process, a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 11 and 12). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2005-326838 A [Patent Document 2] JP 2008-145539 A [Patent Document 3] JP 2009-173623 A [Patent Document 4] International Publication No. 2013 / 024778 [Patent Document 5] JP 2004-177668 A [Patent Document 6] JP 2004-271838 A [Patent Document 7] JP 2005-250434 A [Patent Document 8] International Publication No. 2013 / 024779 [Patent Document 9] JP 2002-334869 A [Patent Document 10] International Publication No. 2004 / 066377 [Patent Document 11] JP 2007-226170 A [Patent Document 12] JP 2007-226204 A [Non-patent literature]

[0012] [Non-Patent Document 1] T.Nakayama,M.Nomura,K.Haga,M.Ueda:Bull.Chem.Soc.Jpn.,71,2979(1998) [Non-Patent Document 2] Shinji Okazaki and 22 others, "New Developments in Photoresist Material Development," CMC Publishing Co., Ltd., September 2009, pp. 211-259 Summary of the Invention [Problem to be solved by the invention]

[0013] However, the materials described in Patent Documents 1 to 12 and Non-Patent Documents 1 and 2 still have room for improvement in terms of simultaneously satisfying high levels of solubility in organic solvents, etching resistance, and resist pattern formability as film-forming materials for lithography.

[0014] The present invention has been made in consideration of the problems associated with the above-mentioned conventional techniques, and has an object to provide a novel compound useful as a film-forming material for lithography, a resin containing a structural unit derived from the compound, a composition, a method for forming a resist pattern, a method for forming a circuit pattern, and a purification method. [Means for solving the problem]

[0015] As a result of intensive research aimed at solving the above problems, the inventors have discovered that a novel compound having a specific structure and a resin derived from the novel compound are useful as a film-forming material for lithography, and have thus completed the present invention.

[0016] That is, the present invention includes the following aspects. [1] A compound represented by the following formula (0): [ka] (In the formula (0), R 0are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group, a crosslinkable group, a dissociable group, a thiol group, or a hydroxyl group, wherein R 0 At least one of R 0 The alkyl group, the aryl group, the alkenyl group, the alkynyl group, and the alkoxy group in the formula (I) may contain an ether bond, a ketone bond, or an ester bond; R 2 are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group, a crosslinkable group, a dissociable group, a thiol group or a hydroxyl group, wherein R 2 The alkyl group, the aryl group, the alkenyl group, the alkynyl group, and the alkoxy group in the formula (I) may contain an ether bond, a ketone bond, or an ester bond; n 1 are each independently an integer of 1 to 2, n 0 are each independently 0 to (4+2n 1 ), where n 0 At least one of the following is 1~(4+2n 1 ) and n 4 are each independently an integer of 0 to 1, n 5 are each independently 0 to (4+2n 4 ) is an integer. [2] The compound according to [1], wherein the compound represented by formula (0) is represented by the following formula (1): [ka] (In the above formula (1), R 2 , n 1 , n 4 and n 5 is defined as the same as formula (0), R's each independently represent a hydrogen atom, a linear alkyl group having 1 to 30 carbon atoms which may have a substituent, a branched or cyclic alkyl group having 3 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, a crosslinkable group or a dissociable group, wherein at least one of R's is a hydrogen atom, a crosslinkable group or a dissociable group, R 1 each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group or a thiol group, wherein the alkyl group, the aryl group, the alkenyl group, the alkynyl group and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, n 2 are each independently 1 to (4+2n 1 ), n 3 are each independently 0 to (4+2n 1 -n 2 ) is an integer. [3] The compound according to [2], wherein the compound represented by formula (1) is represented by the following formula (2): [ka] (In the formula (2), R, R 1 , R 2 , n4 and n 5 is defined as the same as formula (1), n 2 are each independently an integer from 1 to 6, n 3 are each independently 0 to (6-n 2 ) is an integer. [4] The compound according to [2], wherein the compound represented by formula (1) is represented by the following formula (3): [ka] (In the above formula (3), R 1 , R 2 , n 4 and n 5 is defined as the same as formula (1), n 3 are each independently an integer of 0 to 5. [5] The compound according to [2], wherein the compound represented by formula (1) is represented by the following formula (4): [ka] (In the formula (4), R, R 1 , R 2 , n 1 , n 2 and n 3 is defined as the same as formula (1), n 5 are each independently an integer of 0 to 4. [6] The compound according to [2], wherein the compound represented by formula (1) is represented by the following formula (5): [ka] (In the above formula (5), R 1 and R 2 is defined as the same as formula (1), n 3 are each independently an integer of 0 to 5, n 5are each independently an integer of 0 to 4. [7] A resin having a structural unit derived from the compound according to any one of [1] to [6]. [8] The resin according to [7], having a structure represented by the following formula (6): [ka] (In the formula (6), L is a divalent group having 1 to 60 carbon atoms, and M is a unit structure derived from the compound according to any one of claims 1 to 6.) [9] A composition comprising the compound according to any one of [1] to [6] and / or the resin according to [7] or [8].

[10] The composition described in [9], further comprising a solvent.

[11] The composition according to [9] or

[10] , further comprising an acid generator.

[12] The composition according to any one of [9] to

[11] , further comprising a crosslinking agent.

[13] The composition according to any one of [9] to

[12] , which is used for forming a film for lithography.

[14] The composition according to any one of [9] to

[12] , which is used for forming a resist film.

[15] The composition according to any one of [9] to

[12] , which is used for forming a resist underlayer film.

[16] a photoresist layer forming step of forming a photoresist layer on a substrate using the composition according to

[13] or

[14] ; a developing step of irradiating a predetermined region of the photoresist layer formed in the photoresist layer forming step with radiation and developing the photoresist layer to obtain a resist pattern; A method for forming a resist pattern comprising the steps of:

[17] The method for forming a resist pattern according to

[16] , wherein the resist pattern is an insulating film pattern.

[18] a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition according to

[13] or

[15] ; a photoresist layer forming step of forming at least one photoresist layer on the resist underlayer film formed in the resist underlayer film forming step; a developing step of irradiating a predetermined region of the photoresist layer formed in the photoresist layer forming step with radiation and developing the photoresist layer to obtain a resist pattern; A method for forming a resist pattern comprising the steps of:

[19] a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition according to

[13] or

[15] ; an intermediate layer film forming step of forming an intermediate layer film on the resist underlayer film formed in the resist underlayer film forming step; a photoresist layer forming step of forming at least one photoresist layer on the intermediate layer film formed in the intermediate layer film forming step; a resist pattern forming step of irradiating a predetermined region of the photoresist layer formed in the photoresist layer forming step with radiation and developing the photoresist layer to form a resist pattern; an intermediate layer film pattern forming step of etching the intermediate layer film using the resist pattern formed in the resist pattern forming step as a mask to form an intermediate layer film pattern; a resist underlayer film pattern forming step of etching the resist underlayer film using the intermediate layer film pattern formed in the intermediate layer film pattern forming step as a mask to form a resist underlayer film pattern; a substrate pattern forming step of etching the substrate using the resist underlayer film pattern formed in the resist underlayer film pattern forming step as a mask to form a pattern on the substrate; A method for forming a circuit pattern comprising the steps of:

[20] A method for purifying the compound according to any one of [1] to [6] and / or the resin according to [7] or [8], comprising the steps of: A purification method comprising an extraction step of contacting a solution containing an organic solvent optionally immiscible with water and the compound and / or resin with an acidic aqueous solution to extract the compound and / or resin. Effect of the Invention

[0017] According to the present invention, it is possible to provide compounds, resins, and compositions that are useful as film-forming materials for lithography, as well as methods for forming resist patterns, methods for forming circuit patterns, and purification methods using them. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, an embodiment of the present invention (also referred to as "the present embodiment") will be described. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only the present embodiment.

[0019] In this specification, unless otherwise specified, the term "alkyl group" may be a linear or branched alkyl group, or a cyclic alkyl group, and is used in the sense that includes both. Similarly, unless otherwise specified, the term "alkoxy group" may be a linear or branched alkoxy group, or a cyclic alkoxy group, and is used in the sense that includes both.

[0020] [Compound] The compound of this embodiment is a compound represented by the following formula (0) (hereinafter, also simply referred to as "compound (0)"). [ka] (In the formula (0), R 0are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group, a crosslinkable group, a dissociable group, a thiol group, or a hydroxyl group, wherein R 0 At least one of R 0 The alkyl group, the aryl group, the alkenyl group, the alkynyl group, and the alkoxy group in the formula (I) may contain an ether bond, a ketone bond, or an ester bond; R 2 are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group, a crosslinkable group, a dissociable group, a thiol group or a hydroxyl group, wherein R 2 The alkyl group, the aryl group, the alkenyl group, the alkynyl group, and the alkoxy group in the formula (I) may contain an ether bond, a ketone bond, or an ester bond; n 1 are each independently an integer of 1 to 2, n 0 are each independently 0 to (4+2n 1 ), where n 0 At least one of the following is 1~(4+2n 1 ) and n 4 are each independently an integer of 0 to 1, n 5 are each independently 0 to (4+2n 4 ) is an integer.

[0021] Compound (0) is preferably a compound represented by the following formula (0') (hereinafter, also simply referred to as "compound (0')"). [ka] (In the above formula (0'), R 0 , R 2 , n 1 , n 0 , n 4 and n 5 has the same meaning as in formula (0), p1, p2, p3, and p4 each represent a condensation position in each condensed ring, and n1' represents an integer of 0 to 1. In the formula (0'), the condensation positions in the condensed ring (anthracene ring) are more preferably p1, p2 and / or p3, p4 in the above formula (0'). The condensation positions referred to here are the positions of the anthracene ring (n 1' This refers to the position of the edge shared by each aromatic ring within the structure (i.e., the symmetry of the aromatic rings).

[0022] Since the compound of this embodiment has the above structure, it is useful as a film-forming material for lithography. More specifically, the compound (0) of this embodiment typically has the following characteristics (I) to (IV) (hereinafter, also simply referred to as "predetermined characteristics").

[0023] (I) Compound (0) of the present embodiment has excellent solubility in organic solvents (especially safe solvents). Therefore, for example, when compound (0) of the present embodiment is used as a film-forming material for lithography, a film for lithography can be formed by a wet process such as spin coating or screen printing.

[0024] (II) The compound (0) of this embodiment has a relatively high carbon concentration and a relatively low oxygen concentration. In addition, when the compound (0) of this embodiment has a phenolic hydroxyl group in the molecule, it is particularly useful for forming a cured product by reaction with a curing agent, but the compound (0) of this embodiment alone can also form a cured product by crosslinking the phenolic hydroxyl group during high-temperature baking. Due to these factors, when the compound (0) of this embodiment has a phenolic hydroxyl group, it can exhibit particularly high heat resistance, and when the compound (0) of this embodiment is used as a film-forming material for lithography, the deterioration of the film during high-temperature baking is suppressed, and a lithography film having excellent etching resistance against oxygen plasma etching and the like can be formed.

[0025] (III) As described above, the compound (0) of this embodiment can exhibit high heat resistance and etching resistance, and has excellent adhesion to resist films and resist intermediate layer film materials. Therefore, when the compound (0) of this embodiment is used as a film-forming material for lithography, a film for lithography having excellent resist pattern formability can be formed. Here, the term "resist pattern formability" refers to a property in which no major defects are observed in the resist pattern shape and both resolution and sensitivity are excellent.

[0026] (IV) The compound (0) of the present embodiment has a high refractive index due to its high aromatic ring density, and is suppressed from becoming discolored even when subjected to heat treatment, and has excellent transparency.

[0027] The functional groups constituting the compound of this embodiment will be described below.

[0028] The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, a 2,2,4-trimethylpentyl group, an n-octyl group, an isooctyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hex ... Examples of the alkyl group include linear or branched alkyl groups having 1 to 30 carbon atoms, such as decyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-heneicosyl group, n-tricosyl group, n-pentacosyl group, n-heptacosyl group, and n-nonacosyl group. From the viewpoint of making the specific characteristics of the present embodiment more effective, linear or branched alkyl groups having 1 to 20 carbon atoms are preferred, and linear or branched alkyl groups having 1 to 10 carbon atoms are more preferred. Examples of the cyclic alkyl group include monocyclic groups (monocyclic cycloalkyl groups) and polycyclic groups (polycyclic cycloalkyl groups). Examples of the monocyclic group include, but are not limited to, monocyclic groups having 3 to 30 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and cycloicosyl group. The polycyclic group is not particularly limited, but examples thereof include polycyclic groups having 7 to 30 carbon atoms, such as a dicyclopentyl group, a dicyclohexyl group, a norbornyl group, an adamantyl group, a tricyclodecyl group, and a tetracyclododecyl group.

[0029] The alkyl group may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), a nitro group, an amino group that may have a substituent, a carboxyl group, a thiol group, and a hydroxyl group. The number of the substituent is not particularly limited, and may be one or more.

[0030] The aryl group is not particularly limited, and examples thereof include aryl groups having 6 to 30 carbon atoms, such as a phenyl group, a naphthyl group (e.g., a 1-naphthyl group and a 2-naphthyl group), an anthryl group (e.g., a 1-anthryl group), and a phenanthryl group (e.g., a 1-phenanthryl group). From the viewpoint of making the predetermined characteristics of the present embodiment more effective, an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, is preferable, and a phenyl group is more preferable.

[0031] The aryl group may have a substituent. The substituent is not particularly limited, but may be, for example, the substituent exemplified as the substituent of the alkyl group in formula (0) and the alkyl group exemplified as the alkyl group in formula (0). The number of the substituent is not particularly limited, and may be one or more.

[0032] The alkenyl group is not particularly limited, and examples thereof include alkenyl groups having 2 to 30 carbon atoms, such as ethenyl, propenyl, butenyl, pentenyl, and hexenyl. The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified as the substituents of the alkyl group in formula (0) and the alkyl groups exemplified as the alkyl group in formula (0). The number of the substituents is not particularly limited, and may be one or more.

[0033] The alkynyl group is not particularly limited, and examples thereof include alkynyl groups having 2 to 30 carbon atoms, such as ethynyl and propargyl groups. The alkynyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified as the substituents of the alkyl group in formula (0) and the alkyl groups exemplified as the alkyl group in formula (0). The number of the substituents is not particularly limited, and may be one or more.

[0034] The alkoxy group is not particularly limited, but examples thereof include -OR a (wherein Ra represents an alkyl group exemplified as the alkyl group in formula (0). ) and other alkoxy groups having 1 to 30 carbon atoms are included. Among these, from the viewpoint of making the predetermined characteristics of the present embodiment more effective, it is preferable to use a linear or branched alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxo group, or a tert-butoxy group, more preferably a linear or branched alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy group or an ethoxy group. The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituents exemplified as the substituents of the alkyl group in formula (0) and the alkyl group exemplified as the alkyl group in formula (0). The number of substituents is not particularly limited, and may be one or more.

[0035] The halogen atom is not particularly limited, but examples thereof include a chlorine atom, a bromine atom, and an iodine atom.

[0036] In formula (0), R 0 At least one of R 0 By having this, the material has a predetermined characteristic. In addition, when the compound (0) of the present embodiment is a compound represented by formula (0'), the density tends to be high, so the number of atoms contained per unit thickness increases, and the etching resistance tends to be particularly high. From the same viewpoint, when the condensation positions in the condensed ring (anthracene ring) in formula (0') are p1, p2, p3, and p4 in formula (0'), the etching resistance tends to be further increased.

[0037] In the present embodiment, the term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, but examples thereof include alkoxy groups having 1 to 20 carbon atoms, groups having an allyl group, groups having a (meth)acryloyl group, groups having an epoxy (meth)acryloyl group, groups having a hydroxyl group, groups having a urethane (meth)acryloyl group, groups having a glycidyl group, groups having a vinyl-containing phenylmethyl group, groups having various alkynyl groups, groups having a carbon-carbon double bond, groups having a carbon-carbon triple bond, and groups containing these groups, and the like, and the like, and the like, can be mentioned as groups that crosslink in the presence or absence of a catalyst. The above-mentioned "groups containing these groups" are preferably alkoxy groups represented by -ORx (Rx is a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy (meth)acryloyl group, a group having a hydroxyl group, a group having a urethane (meth)acryloyl group, a group having a glycidyl group, a group having a vinyl-containing phenylmethyl group, a group having various alkynyl groups, a group having a carbon-carbon double bond, a group having a carbon-carbon triple bond, and groups containing these groups.). In this specification, when the functional groups (excluding the crosslinkable group) described above as constituting the compound of this embodiment overlap with the crosslinkable group, those without crosslinkability are treated as corresponding to each functional group, and those with crosslinkability are treated as corresponding to the crosslinkable group, based on the presence or absence of crosslinkability.

[0038] The group having an allyl group is not particularly limited, but examples thereof include groups represented by the following formula (X-1).

[0039] [ka] (In formula (X-1), n X1 is an integer from 1 to 5.

[0040] The group having a (meth)acryloyl group is not particularly limited, but examples thereof include groups represented by the following formula (X-2).

[0041] [ka] (In formula (X-2), n X2 is an integer from 1 to 5, and R X is a hydrogen atom or a methyl group.

[0042] The group having an epoxy(meth)acryloyl group is not particularly limited, but examples thereof include a group represented by the following formula (X-3): Here, the epoxy(meth)acryloyl group refers to a group generated by reaction of an epoxy(meth)acrylate with a hydroxyl group.

[0043] [ka] (In formula (X-3), n x3 is an integer from 0 to 5, preferably 0; R X is a hydrogen atom or a methyl group, and a methyl group is preferable.

[0044] The group having a urethane (meth)acryloyl group is not particularly limited, but examples thereof include groups represented by the following formula (X-4).

[0045] [ka] (In the general formula (X-4), n x4 is an integer of 0 to 5, preferably 0; s is an integer of 0 to 3, preferably 0; R X is a hydrogen atom or a methyl group, and a methyl group is preferable.

[0046] The group having a hydroxyl group is not particularly limited, but examples thereof include groups represented by the following formula (X-5).

[0047] [ka] (In the general formula (X-5), n x5is an integer of 1 to 5, preferably 1.

[0048] The group having a glycidyl group is not particularly limited, but examples thereof include groups represented by the following formula (X-6).

[0049] [ka] (In formula (X-6), n x6 is an integer from 1 to 5.

[0050] The group having a vinyl-containing phenylmethyl group is not particularly limited, but examples thereof include groups represented by the following formula (X-7).

[0051] [ka] (In formula (X-7), n x7 is an integer of 1 to 5, preferably 1.

[0052] The groups having various alkynyl groups are not particularly limited, but examples thereof include groups represented by the following formula (X-8).

[0053] [ka] (In formula (X-8), n x8 is an integer from 1 to 5.

[0054] Examples of the carbon-carbon double bond-containing group include a (meth)acryloyl group, a substituted or unsubstituted vinylphenyl group, a group represented by the following formula (X-9-1), etc. Examples of the carbon-carbon triple bond-containing group include a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propargyl group, and groups represented by the following formulas (X-9-2) and (X-9-3), etc.

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] In the above formula (X-9-1), R X9A , R X9B and R X9C are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X9D , R X9E and R X9F are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0059] In the present embodiment, the term "dissociable group" refers to a group that dissociates in the presence or absence of a catalyst. Among dissociable groups, an acid-dissociable group refers to a group that is cleaved in the presence of an acid and changes into an alkali-soluble group or the like. The alkali-soluble group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group, and the like. Among these, from the viewpoint of easy availability of an introduction reagent, a phenolic hydroxyl group and a carboxyl group are preferred, and a phenolic hydroxyl group is more preferred. The acid-dissociable group preferably has the property of undergoing a chain cleavage reaction in the presence of an acid, in order to enable pattern formation with high sensitivity and high resolution. The acid-dissociable group is not particularly limited, but can be appropriately selected from those proposed for example in hydroxystyrene resins, (meth)acrylic acid resins, and the like used in chemically amplified resist compositions for KrF or ArF. Specific examples of the acid-dissociable group include those described in International Publication No. 2016 / 158168. Examples of the acid-dissociable group include 1-substituted ethyl groups, 1-substituted n-propyl groups, 1-branched alkyl groups, silyl groups, acyl groups, 1-substituted alkoxymethyl groups, cyclic ether groups, alkoxycarbonyl groups (e.g., -C(O)OC(CH3)3, etc.), and alkoxycarbonylalkyl groups (e.g., -(CH2) n C(O)OC(CH3)3, where n = 1 to 4. In this specification, when the functional groups (excluding dissociable groups) described above as constituting the compound of this embodiment overlap with dissociable groups, those that are not dissociable are treated as corresponding to the functional groups, and those that are dissociable are treated as corresponding to the dissociable groups, based on the presence or absence of dissociability.

[0060] The substituent on the dissociative group is not particularly limited, but examples thereof include a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an alkyloyloxy group, an aryloyloxy group, a cyano group, a nitro group, and a heteroatom. The halogen atom is not particularly limited, but examples thereof include a chlorine atom, a bromine atom, and an iodine atom. The alkyl group may be linear, branched or cyclic. The alkyl group is not particularly limited, but examples thereof include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, a tert-butyl group, a cyclohexyl group, and an adamantyl group. The aryl group is not particularly limited, but examples thereof include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group. The aryl group may further have a substituent such as a halogen atom or an alkyl group having 1 to 5 carbon atoms. The aralkyl group is not particularly limited, but examples thereof include a benzyl group, a phenethyl group, etc. The aralkyl group may further have a substituent such as a halogen atom or an alkyl group having 1 to 5 carbon atoms. The alkynyl group is not particularly limited, but examples thereof include an ethynyl group and a propargyl group. The acyl group is not particularly limited, but examples thereof include aliphatic acyl groups having 1 to 6 carbon atoms, such as a formyl group or an acetyl group, and aromatic acyl groups, such as a benzoyl group. The alkoxycarbonyl group is not particularly limited, but examples thereof include alkoxycarbonyl groups having 2 to 5 carbon atoms, such as a methoxycarbonyl group. The alkyloyloxy group is not particularly limited, but may be, for example, an acetoxy group. The aryloyloxy group is not particularly limited, but examples thereof include a benzoyloxy group.

[0061] The heteroatom is not particularly limited, but examples thereof include an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, and a phosphorus atom. Heteroatoms may replace carbon atoms in each group. In addition, the number of carbon atoms of each group described in this specification, when the group contains the above-mentioned substituents, is the total number of carbon atoms including the substituents.

[0062] n in compound (0) of this embodiment 1 are each independently an integer of 1 to 2, preferably 1. 0 are each independently an integer from 0 to (4+2n1), where n 0 At least one of the following is 1~(4+2n 1 ), preferably 1 to 2. 4 is an integer of 0 to 1, preferably 0. 5 is 0~(4+2n 4 ) and is preferably an integer of 0 to 2. In this embodiment, from the viewpoint of making a predetermined characteristic more effective, n 1 = 1 and n 4 It is preferred that =0.

[0063] In this embodiment, from the viewpoint of making the predetermined properties more effective, compound (0) in this embodiment preferably has a cardo structure.

[0064] Although the compound (0) of this embodiment has a relatively low molecular weight, it has high heat resistance due to the rigidity of its structure, and can therefore be used even under high temperature baking conditions.

[0065] The compound (0) of this embodiment has high solubility in organic solvents (especially safe solvents) and has excellent heat resistance and etching resistance. Therefore, a film-forming material for lithography containing the compound (0) has excellent resist pattern forming properties. Examples of the organic solvent include the organic solvents listed in the [Solvent] section of the [Composition] section described later.

[0066] The compound (0) of this embodiment has a relatively low molecular weight and low viscosity, so that even if the substrate has a step (particularly, a fine space or hole pattern, etc.), it is easy to uniformly fill every corner of the step and improve the flatness of the film. As a result, the film-forming composition for lithography containing the compound (0) has excellent filling properties and flattening properties. In addition, since the compound (0) is a compound having a relatively high carbon concentration, it can also exhibit high etching resistance.

[0067] From the viewpoints of ease of crosslinking and solubility in organic solvents, compound (0) is preferably a compound represented by the following formula (1) (hereinafter also simply referred to as "compound (1)").

[0068] [ka] (In the above formula (1), R 2 , n 1 , n 4 and n 5 is defined as the same as formula (0), R's each independently represent a hydrogen atom, a linear alkyl group having 1 to 30 carbon atoms which may have a substituent, a branched or cyclic alkyl group having 3 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an alkynyl group having 2 to 20 carbon atoms which may have a substituent, a crosslinkable group or a dissociable group, wherein at least one of R's is a hydrogen atom, a crosslinkable group or a dissociable group, R 1 each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group or a thiol group, wherein the alkyl group, the aryl group, the alkenyl group, the alkynyl group and the alkoxy group may contain an ether bond, a ketone bond or an ester bond, n 2 are each independently 1 to (4+2n 1 ), n 3 are each independently 0 to (4+2n 1 -n 2 ) is an integer.

[0069] In formula (1), the alkyl group, the aryl group, the alkenyl group, the alkoxy group, the halogen atom, the crosslinkable group, the dissociable group, and the substituent substituting each group are not particularly limited, and examples thereof include each group exemplified in the explanation of formula (0).

[0070] n 2 are each independently 1 to (4+2n 1 ), preferably 1 to 2. 3 are each independently 0 to (4+2n 1 -n 2 ) and is preferably an integer of 0 to 2.

[0071] From the viewpoint of supplyability of the raw material, compound (1) is preferably a compound represented by the following formula (2) (hereinafter, also simply referred to as "compound (2)").

[0072] [ka] (In the formula (2), R, R 1 , R 2 , n 4 and n 5 is defined as the same as formula (1), n 2 are each independently an integer from 1 to 6, n 3 are each independently 0 to (6-n 2 ) is an integer.

[0073] From the viewpoint of etching resistance, compound (2) is preferably a compound represented by the following formula (3) (hereinafter also simply referred to as "compound (3)").

[0074] [ka] (In the above formula (3), R 1 , R 2 , n 4 and n 5 is defined as the same as formula (1), n 3 are each independently an integer of 0 to 5.

[0075] From the viewpoint of raw material supply, compound (1) is preferably a compound represented by the following formula (4) (hereinafter, also simply referred to as "compound (4)").

[0076] [ka] (In the formula (4), R, R 1 , R 2 , n 1 , n 2 and n 3 is defined as the same as formula (1), n5 are each independently an integer of 0 to 4.

[0077] From the viewpoint of raw material supply, compound (1) is preferably a compound represented by the following formula (5) (hereinafter, also simply referred to as "compound (5)").

[0078] [ka] (In the above formula (5), R 1 and R 2 is defined as the same as formula (1), n 3 are each independently an integer of 0 to 5, n 5 are each independently an integer of 0 to 4.

[0079] Specific examples of the compound represented by the above formula (0) include compounds represented by the following formulas: However, the compound represented by the above formula (0) is not limited to the compounds represented by the following formulas.

[0080] [ka] [ka] [ka] [ka] [ka]

[0081] [Method for producing compound (0)] The method for producing the compound (0) of the present embodiment is not particularly limited, but may be, for example, the following method. That is, under normal pressure, a compound represented by the following formula (0-x) (hereinafter, compound (0-x)), a compound represented by the following formula (0-y) (hereinafter, compound (0-y)), and a compound represented by the following formula (0-z) (hereinafter, compound (0-z)) are subjected to a polycondensation reaction under an acid catalyst or a base catalyst to obtain the compound (0). In the above polycondensation reaction, precursors of the compound (0-x), the compound (0-y), and the compound (0-y) may also be used. The above reaction may be carried out under pressure as necessary.

[0082] [ka]

[0083] In formula (0-x), R 0 , n 0 , n 1 and n 5 are as defined in formula (0). In formula (0-x), R 0 , n 0 , n 1 and n 5 are as defined in formula (0). In formula (0-z), R 2 , n 4 and n 5 are as defined in formula (0). The compound (0-x) and the compound (0-y) may be the same.

[0084] A specific example of the polycondensation reaction is not particularly limited, but for example, compound (0) can be obtained by polycondensation reaction of compound (0-x) and compound (0-y) with compound (0-z) or a precursor thereof in the presence of an acid catalyst or a base catalyst.

[0085] Compound (0-x) and compound (0-y) are not particularly limited, but examples thereof include 2,7-dihydroxynaphthalene, 2,7-dihydroxy-3-bromonaphthalene, 2-naphthol, and 2,6-dihydroxyanthracene. These compounds are used alone or in combination of two or more. Among these compounds, 2,7-dihydroxynaphthalene is preferred.

[0086] Compound (0-z) is not particularly limited, but for example, 9-fluorenone, 11H-benzo[b]fluoren-11-one, 11H-benzo[a]fluoren-11-one, 3,6-dibromo-9H-fluoren-9-one, 2-bromo-9-fluorenone, 2,7-dihydroxy-9H-fluoren-9-one, 2-hydroxy-9-fluorenone, etc. are mentioned. These compounds are used alone or in combination of two or more. Among these compounds, 9-fluorenone is preferred.

[0087] The acid catalyst used in the above reaction is not particularly limited, but examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid, organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. These acid catalysts are used alone or in combination of two or more. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and from the viewpoint of production, such as ease of availability and ease of handling, it is preferred to use hydrochloric acid or sulfuric acid. The amount of the acid catalyst used can be appropriately set depending on the raw materials and catalyst used, as well as the reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass per 100 parts by mass of the reaction raw materials.

[0088] The base catalyst used in the above reaction is not particularly limited, and examples thereof include metal alkoxides (alkali metal or alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, etc.), metal hydroxides (alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, etc.), alkali metal or alkaline earth hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, etc., amines (for example, tertiary amines (trialkylamines such as triethylamine, aromatic tertiary amines such as N,N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, etc.), and the like. Examples of the base catalyst include organic bases such as carboxylic acid metal salts (alkali metal acetate or alkaline earth metal salts such as sodium acetate and calcium acetate). These base catalysts are used alone or in combination of two or more. Among these, metal alkoxides, metal hydroxides and amines are preferred from the viewpoint of production, and sodium hydroxide is preferred from the viewpoint of production such as ease of availability and ease of handling. The amount of the base catalyst used can be appropriately set depending on the raw materials and catalysts used, as well as the reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw materials.

[0089] In the above reaction, a reaction solvent may be used. The reaction solvent is not particularly limited, but examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, 1-methoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc. These solvents may be used alone or in combination of two or more.

[0090] The amount of the solvent used can be appropriately set depending on the raw materials and catalyst used, as well as the reaction conditions, and is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. Furthermore, the reaction temperature in the above reaction can be appropriately selected depending on the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C.

[0091] In order to obtain the compound (0) of this embodiment, the reaction temperature is preferably high, specifically, in the range of 60 to 200°C. The reaction method is not particularly limited, but for example, the raw materials (reactants) and the catalyst are charged at once, or the raw materials (reactants) are successively dropped in the presence of a catalyst. After the polycondensation reaction is completed, the isolation of the obtained compound can be carried out according to a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts present in the system, the temperature of the reaction vessel is increased to 130 to 230°C, and the volatile matter is removed at about 1 to 50 mmHg, and the target compound can be obtained by adopting a general method.

[0092] Preferable reaction conditions include using 1.0 mole to excess of the compound represented by the above formula (0-x) and the compound represented by the above formula (0-y) per mole of the ketone represented by the above formula (0-z), and further using 0.001 to 1 mole of an acid catalyst, and reacting at normal pressure at 50 to 150° C. for about 20 minutes to 100 hours.

[0093] After the reaction is completed, the target product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, and the reaction product is cooled to room temperature, filtered to separate the product, and the solid obtained is filtered and dried, and then separated and purified from the by-products by column chromatography, and the target compound (0) can be obtained by distilling off the solvent, filtering, and drying the product.

[0094] [resin] The resin of this embodiment contains a structural unit derived from the compound represented by the above formula (0). That is, the resin of this embodiment contains the compound represented by the above formula (0) as a monomer component. As the resin of this embodiment, a resin having a structure represented by formula (6) (hereinafter, also simply referred to as "resin (6)") is preferable.

[0095] [ka] (In formula (6), L is a divalent group having 1 to 60 carbon atoms, and M is a unit structure derived from a compound represented by any one of formulas (0) to (5).)

[0096] Examples of the linking group include residues derived from crosslinkable compounds described below. L is preferably a divalent hydrocarbon group having 1 to 30 carbon atoms. The divalent hydrocarbon group is not particularly limited, but examples thereof include linear or branched hydrocarbon groups such as alkylene groups, and cyclic hydrocarbon groups.

[0097] The resin (6) of this embodiment can be obtained by reacting the above compound (0) with a compound having crosslinking reactivity.

[0098] The crosslinkable compound may be any compound capable of oligomerizing or polymerizing the compound (0), and examples thereof include aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanate compounds, and unsaturated hydrocarbon group-containing compounds.

[0099] The resin (6) in the present embodiment is not particularly limited, but examples thereof include novolak resins obtained by a condensation reaction between the compound (0) and an aldehyde or a ketone, which is a crosslinkable compound.

[0100] Here, the aldehyde used in converting the compound (0) into a novolak is not particularly limited, but examples thereof include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropionaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, pentamethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentylbenzaldehyde, butylmethyl ... Examples of the aldehydes include aldehydes, hydroxybenzaldehyde, dihydroxybenzaldehyde, fluoromethylbenzaldehyde, cyclopropanecarbaldehyde, cyclobutanecarbaldehyde, cyclohexanecarbaldehyde, cyclodecanecarbaldehyde, cycloundecanecarbaldehyde, cyclopropylbenzaldehyde, cyclobutylbenzaldehyde, cyclohexylbenzaldehyde, cyclodecylbenzaldehyde, cycloundecylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural. These aldehydes may be used alone or in combination of two or more. In addition to these aldehydes, one or more ketones may also be used in combination.Among these, from the viewpoint of exhibiting high heat resistance, at least one selected from the group consisting of benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural is preferably used. is preferred, and from the viewpoint of improving the etching resistance, it is preferred to use one or more selected from the group consisting of benzaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural, and it is more preferred to use formaldehyde. The amount of aldehyde used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, per 1 mol of the above compound (0).

[0101] The ketones used in converting the compound (0) into a novolak are not particularly limited, and examples thereof include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, cyclohexanedione, cyclohexanetrione, cyclodecane trione, adamantanone, fluorenone, benzofluorenone, dibenzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, acetylmethylbenzene, acetyldimethylbenzene, acetyltrimethylbenzene, acetylethylbenzene, acetylpropylbenzene, acetylbutylbenzene, acetylpentabenzene, acetylbutylmethylbenzene, acetylhydroxybenzene, acetyldihydroxybenzene, acetylfluoromethylbenzene, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl. These ketones may be used alone or in combination of two or more.Among these, from the viewpoint of exhibiting high heat resistance, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonyl It is preferable to use one or more selected from the group consisting of acetophenone, diacetylbenzene, triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, and diphenylcarbonylbiphenyl. The amount of ketones used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 to 2 moles, per mole of the compound (0).

[0102] In the condensation reaction of the compound (0) with aldehydes or ketones, a catalyst can also be used. The acid catalyst or base catalyst used here can be appropriately selected from known ones and is not particularly limited. Such acid catalysts and base catalysts are the same as the examples given in the production method of the compound (0). These catalysts are used alone or in combination of two or more. Among them, from the viewpoint of production, organic acids and solid acids are preferred, and from the viewpoint of production, such as ease of availability and ease of handling, hydrochloric acid or sulfuric acid is preferred. The amount of the acid catalyst used can be appropriately set depending on the raw materials used and the types of catalysts used, and further reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw materials.

[0103] However, in the case of a copolymerization reaction with a compound having a non-conjugated double bond, such as indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, or limonene, aldehydes or ketones are not necessarily required.

[0104] In the condensation reaction of the compound (0) with aldehydes or ketones, a reaction solvent can also be used. The reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited, but examples thereof include water, methanol, ethanol, propanol, butanol, 1-methoxy-2-propanol, tetrahydrofuran, dioxane, or a mixture thereof. These solvents can be used alone or in combination of two or more.

[0105] The amount of the solvent used can be appropriately set depending on the raw materials used, the type of catalyst used, and further the reaction conditions, and is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. Furthermore, the reaction temperature can be appropriately selected depending on the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10 to 200°C. The reaction method may include a method in which the compound (0), aldehydes and / or ketones, and catalyst are charged all at once, or a method in which the compound (0), aldehydes and / or ketones are successively added dropwise in the presence of a catalyst.

[0106] After the polycondensation reaction is completed, the obtained resin can be isolated by a conventional method, and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts present in the system, the temperature of the reaction vessel is raised to 130 to 230°C, and volatile matters are removed at about 1 to 50 mmHg, and a general method is adopted to obtain the target product (for example, a novolak resin).

[0107] The resin (6) in this embodiment may be one obtained during the synthesis reaction of the compound (0). That is, the resin (6) may be a polymer of the compound (0) and an aldehyde or ketone derived from the raw material used in the synthesis of the compound (0).

[0108] Here, the resin (6) of the present embodiment may be a homopolymer of the compound (0) or a copolymer with other phenols, etc. The copolymerizable phenols are not particularly limited, but examples thereof include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, propylphenol, pyrogallol, and thymol.

[0109] In addition, the resin (6) of this embodiment may be copolymerized with a polymerizable monomer other than the above-mentioned other phenols. The copolymerization monomer is not particularly limited, but examples thereof include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, vinylnorbornaene, pinene, and limonene. The resin of this embodiment may be a two-component or more (e.g., two- to four-component) copolymer of the above-mentioned compound (0) and the above-mentioned phenols, a two-component or more (e.g., two- to four-component) copolymer of the above-mentioned compound (0) and the above-mentioned copolymerization monomers, or a three-component or more (e.g., three- to four-component) copolymer of the above-mentioned compound (1), the above-mentioned phenols, and the above-mentioned copolymerization monomers.

[0110] The weight average molecular weight (Mw) of the resin (6) of this embodiment is not particularly limited, but is preferably 300 to 100,000, more preferably 500 to 30,000, and even more preferably 750 to 20,000, calculated as polystyrene by GPC measurement. From the viewpoints of increasing crosslinking efficiency and suppressing volatile components during baking, the resin of this embodiment preferably has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) in the range of 1 to 7.

[0111] The above-mentioned compound (0) and / or resin (6) are preferably highly soluble in a solvent, from the viewpoint of making it easier to apply a wet process. More specifically, when propylene glycol monomethyl ether (hereinafter also referred to as "PGME") and / or propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA") is used as a solvent, the solubility of the compound (0) and / or resin (6) in the solvent is preferably 10% by mass or more. Here, the solubility in PGME and / or PGMEA is defined as "mass of compound (0) and / or resin (6) ÷ (mass of compound (0) and / or resin (6) + mass of solvent) × 100 (mass%)". For example, 10 g of the above compound (0) and / or resin (6) is evaluated as having high solubility in 90 g of PGMEA when the solubility of the compound (0) and / or resin (6) in PGMEA is "10% by mass or more," and is evaluated as not having high solubility when the solubility is "less than 10% by mass."

[0112] [Composition] The composition of the present embodiment contains a compound (0) and / or a resin (6). The composition of the present embodiment contains the compound (0) and / or resin (6) of the present embodiment, so that wet processes can be applied, and the composition has excellent heat resistance and planarization properties. In addition, the composition of the present embodiment contains the compound (0) and / or resin (6), so that film deterioration during high-temperature baking is suppressed, and a film for lithography having excellent etching resistance against oxygen plasma etching and the like can be formed. Furthermore, the composition of the present embodiment has excellent adhesion to the resist film, so that an excellent resist pattern can be formed. For this reason, the composition of the present embodiment is preferably used for forming a film for lithography. Hereinafter, the composition of the present embodiment when used for forming a film for lithography is also referred to as a film-forming composition for lithography.

[0113] In this embodiment, the film for lithography is a general term for a film used in a lithography process, and examples thereof include an upper layer film, a resist film, an intermediate film, a resist underlayer film, an anti-reflective film, and a resist permanent film. The upper layer film is disposed on the upper part of the resist film, and has water repellency, for example, and the intermediate film can also be one that has various physical properties depending on the relative positional relationship with the resist film and the resist underlayer film. In addition to the above, examples of the film for lithography include a film for filling in the step of the processed layer to flatten it, and the like. The composition of this embodiment can be used to preferably form a resist film or a resist underlayer film as a film for lithography. That is, the resist film of this embodiment and the resist underlayer film of this embodiment are formed from the composition of this embodiment.

[0114] [Components that may be included in the composition] The composition of the present embodiment may contain, in addition to the compound (0) and / or resin (6) of the present embodiment, a solvent, a crosslinking agent, a crosslinking accelerator, an acid generator, a basic compound, and other components, as necessary. In particular, when the composition of the present embodiment is used for forming a film for lithography, it is preferable to use these components in combination. Hereinafter, the solvent, crosslinking agent, crosslinking accelerator, acid generator, basic compound, and other components that may be contained in the composition of the present embodiment when it is used for forming a film for lithography will be described.

[0115] [solvent] The composition of the present embodiment may contain a solvent. The solvent is not particularly limited as long as it can dissolve the compound (0) and / or resin (6) of the present embodiment. Here, as described above, the compound (0) and / or resin (6) of the present embodiment has excellent solubility in organic solvents, so that various organic solvents are suitably used.

[0116] The solvent is not particularly limited, but examples thereof include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., cellosolve-based solvents such as PGME, PGMEA, etc., ester-based solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc., alcohol-based solvents such as methanol, ethanol, isopropanol, 1-ethoxy-2-propanol, etc., aromatic hydrocarbons such as toluene, xylene, anisole, etc. These solvents may be used alone or in combination of two or more.

[0117] Among the above-mentioned solvents, from the viewpoint of safety, it is preferable to use one or more selected from the group consisting of cyclohexanone, PGME, PGMEA, ethyl lactate, methyl hydroxyisobutyrate, and anisole. In the composition of the present embodiment, the amount of solid components is not particularly limited, but is preferably 1 to 80 mass%, more preferably 1 to 50 mass%, even more preferably 2 to 40 mass%, and even more preferably 2 to 10 mass% and 90 to 98 mass% of the solvent, relative to 100 mass% combined mass of the solid components and the solvent. In the composition of the present embodiment, the amount of the solvent is not particularly limited, but is preferably 20 to 99% by mass, more preferably 50 to 99% by mass, even more preferably 60 to 98% by mass, and even more preferably 90 to 98% by mass, relative to 100% by mass of the total mass of the solid components and the solvent. In this specification, the term "solid components" refers to components other than the solvent.

[0118] The content of the solvent is not particularly limited, but from the viewpoints of solubility and film formation, it is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, and even more preferably 200 to 1,000 parts by mass, relative to 100 parts by mass of the compound (0) and / or resin (6) of the present embodiment.

[0119] [Crosslinking agent] The composition of the present embodiment may contain a crosslinking agent from the viewpoint of suppressing intermixing, etc. The crosslinking agent is not particularly limited, but for example, those described in WO 2013 / 024779 and WO 2018 / 016614 can be used.

[0120] The crosslinking agent is not particularly limited, but examples thereof include phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds. These crosslinking agents are used alone or in combination of two or more. Among these, it is preferable to use one or more selected from the group consisting of benzoxazine compounds, epoxy compounds, and cyanate compounds, and from the viewpoint of improving etching resistance, benzoxazine compounds are more preferable.

[0121] In this embodiment, the content of the crosslinking agent is not particularly limited, but is preferably 0.1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the compound (1) and / or resin (6) of this embodiment. By having the content of the crosslinking agent within the above range, the occurrence of a mixing phenomenon with the resist film tends to be suppressed, and the antireflection effect tends to be enhanced, and the film formability after crosslinking tends to be improved.

[0122] [Crosslinking accelerator] The composition of the present embodiment may contain a crosslinking accelerator to accelerate the crosslinking reaction (curing reaction) as necessary. Examples of the crosslinking accelerator include a radical polymerization initiator.

[0123] The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or a thermal polymerization initiator that initiates radical polymerization by heat. The radical polymerization initiator is not particularly limited, but examples thereof include ketone-based photopolymerization initiators, organic peroxide-based polymerization initiators, and azo-based polymerization initiators.

[0124] Such a radical polymerization initiator is not particularly limited, but for example, those described in WO 2018 / 016614 can be used.

[0125] These radical polymerization initiators may be used alone or in combination of two or more.

[0126] The content of the radical polymerization initiator in this embodiment is not particularly limited, but is preferably 0.05 to 25 parts by mass, and more preferably 0.1 to 10 parts by mass, when the compound or resin in this embodiment is 100 parts by mass. When the content of the radical polymerization initiator is 0.05 parts by mass or more, it tends to be possible to prevent insufficient curing, while when the content of the radical polymerization initiator is 25 parts by mass or less, it tends to be possible to prevent the long-term storage stability at room temperature from being impaired.

[0127] [Acid generator] The composition of the present embodiment may contain an acid generator from the viewpoint of further promoting the crosslinking reaction by heat. As the acid generator, there are known ones that generate an acid by thermal decomposition, ones that generate an acid by light irradiation, and the like, and any of them can be used. As the acid generator, there is no particular limitation, but for example, those described in International Publication No. 2013 / 024779 can be used.

[0128] The content of the acid generator in the composition of the present embodiment is not particularly limited, but is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 40 parts by mass, relative to 100 parts by mass of the compound (0) and / or resin (9) of the present embodiment. When the content of the acid generator is within the above range, the crosslinking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist film tends to be suppressed.

[0129] [Basic compounds] The composition of the present embodiment may contain a basic compound from the viewpoint of improving storage stability, etc. The basic compound plays a role of preventing a small amount of acid generated from the acid generator from proceeding with the crosslinking reaction, that is, plays a role of a quencher for the acid. Examples of such basic compounds include, but are not limited to, those described in WO 2013 / 024779.

[0130] The content of the basic compound in the composition of the present embodiment is not particularly limited, but is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the compound (0) and / or the resin (9) of the present embodiment. By having the content of the basic compound within the above range, the storage stability tends to be improved without excessively impairing the crosslinking reaction.

[0131] [Other additives] The composition of the present embodiment may contain other resins and / or compounds for the purpose of imparting curability by heat or light or controlling absorbance. Examples of such other resins and / or compounds include, but are not limited to, naphthol resins, xylene resins, naphthol-modified resins, and phenol-modified resins of naphthalene resins; polyhydroxystyrene, dicyclopentadiene resins, (meth)acrylates, dimethacrylates, trimethacrylates, tetramethacrylates, vinylnaphthalene, polyacenaphthylene, and other naphthalene rings, phenanthrenequinone, fluorene, and other biphenyl rings, thiophene, indene, and other heterocyclic rings having heteroatoms or resins not containing aromatic rings; rosin-based resins, cyclodextrins, adamantane (poly)ols, tricyclodecane (poly)ols, and derivatives thereof, and other resins or compounds containing alicyclic structures. The composition of the present embodiment may contain known additives. Examples of known additives include, but are not limited to, heat and / or light curing catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, light curing resins, dyes, pigments, thickeners, lubricants, defoamers, leveling agents, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.

[0132] [Resist film forming composition] As described above, the composition of the present embodiment is preferably used for forming a resist film. That is, the resist film of the present embodiment contains the composition of the present embodiment. The film formed by applying the composition of the present embodiment can also be used by forming a resist pattern as necessary.

[0133] The composition of the present embodiment can be used as a film-forming composition for lithography for chemically amplified resist applications (hereinafter, also referred to as a "resist film-forming composition"). Hereinafter, components that may be contained in the resist film-forming composition will be described in particular.

[0134] The resist film forming composition of the present embodiment preferably contains a solvent. The solvent is not particularly limited, but examples thereof 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 PGMEA, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as PGME and propylene glycol monoethyl ether; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amyl lactate; methyl acetate, ethyl acetate, and n-propyl acetate. aliphatic carboxylic acid esters such as ethyl ester, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, and 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, butyl 3-methoxy-3-methylpropionate, and 3-methoxy-3-methylbutyric acid Examples of the solvent include other esters such as butyl, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (hereinafter also referred to as "CPN"), and cyclohexanone (hereinafter also referred to as "CHN"); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactones such as γ-lactone, etc. These solvents may be used alone or in combination of two or more.

[0135] The solvent used in the present embodiment is preferably a safe solvent, more preferably one or more selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and even more preferably one or more selected from PGMEA, PGME, and CHN.

[0136] In the composition for forming a resist film of the present embodiment, the amount of the solid components is not particularly limited, but is preferably 1 to 80 mass%, more preferably 1 to 50 mass%, even more preferably 2 to 40 mass%, and even more preferably 2 to 10 mass% and the solvent 90 to 98 mass%, relative to 100 mass% combined mass of the solid components and the solvent. In the composition for forming a resist film of the present embodiment, the amount of the solvent is not particularly limited, but is preferably 20 to 99 mass%, more preferably 50 to 99 mass%, even more preferably 60 to 98 mass%, and even more preferably 90 to 98 mass%, relative to 100 mass% of the total mass of the solid components and the solvent.

[0137] The composition for forming a resist film of the present embodiment may contain, as a solid component other than the compound (1) and / or the resin (6) of the present embodiment, one or more selected from the group consisting of an acid generator, an acid crosslinking agent, an acid diffusion controller, and other components.

[0138] Here, the acid generator, acid crosslinker, acid diffusion controller and other components can be any known components and are not particularly limited. For example, those described in WO 2013 / 024778 are preferred.

[0139] In the resist film-forming composition of the present embodiment, the content of the compound (0) and / or resin (9) of the present embodiment used as a resist base material is not particularly limited, but is preferably 1 to 100% by mass, more preferably 50 to 99.4% by mass, even more preferably 55 to 90% by mass, even more preferably 60 to 80% by mass, and even more preferably 60 to 70% by mass, based on the total mass of the solid components. When the content of the compound (0) and / or resin (9) is within the above range, the resolution is further improved and the line edge roughness (hereinafter also referred to as "LER") tends to be further reduced. When both the compound (0) and the resin (9) are contained, the above content is the total amount of both components.

[0140] The resist film-forming composition of the present embodiment may contain, as necessary, a dissolution promoter, a dissolution controller, a sensitizer, a surfactant, an organic carboxylic acid or a phosphorus oxoacid or a derivative thereof, a heat curing catalyst, a photocuring catalyst, a polymerization inhibitor, a flame retardant, a filler, a coupling agent, a thermosetting resin, a photocurable resin, a dye, a pigment, a thickener, a lubricant, an antifoaming agent, a leveling agent, an ultraviolet absorbing agent, a surfactant such as a nonionic surfactant, a colorant, and various additives, provided that the purpose of the present embodiment is not impaired. These additives may be used alone or in combination of two or more.

[0141] In the composition for forming a resist film of the present embodiment, the content of the compound (0) and / or resin (6) of the present embodiment, the acid generator, the acid crosslinking agent, the acid diffusion controller, and other components (compound (0) and resin (6) / acid generator / acid crosslinking agent / acid diffusion controller / other components) is, in mass % based on the solid matter, Preferably 1-100 / 0-49 / 0-49 / 0-49 / 0-99, More preferably, 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49 / 0 to 49. More preferably, it is 55-90 / 1-40 / 0.5-40 / 0.01-10 / 0-5. More preferably, the ratio is 60-80 / 3-30 / 1-30 / 0.01-5 / 0-1. Even more preferably, it is 60-70 / 10-25 / 2-20 / 0.01-3 / 0. The blending ratio of each component is selected from the respective ranges so that the sum of the components is 100% by mass. When the blending ratio of each component is within the above range, the performance such as sensitivity, resolution, and developability tends to be excellent.

[0142] The resist film-forming composition of the present embodiment is usually prepared at the time of use by dissolving each component in a solvent to obtain a homogeneous solution, and then filtering the solution, if necessary, through a filter having a pore size of about 0.2 μm, for example.

[0143] The resist film-forming composition of the present embodiment may contain other resins in addition to the resin of the present embodiment, provided that the purpose of the present embodiment is not impaired. Examples of other resins include, but are not limited to, novolac resins, polyvinylphenols, polyacrylic acid, epoxy resins, polyvinyl alcohol, styrene-maleic anhydride resins, and addition polymerization resins. The addition polymerization resin is not particularly limited, but examples thereof include polymers containing acrylic acid, vinyl alcohol, vinylphenol, or a maleimide compound as a monomer unit, and derivatives thereof. The content of the other resin is not particularly limited and may be appropriately adjusted depending on the type of compound (0) and / or resin (6) of the present embodiment used; however, the content 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 even more preferably 0 parts by mass, relative to 100 parts by mass of compound (0) and / or resin (6) of the present embodiment.

[0144] The composition for forming a resist film of this embodiment can be used to form an amorphous film by spin coating. The composition for forming a resist film of this embodiment can also be applied to general semiconductor manufacturing processes. Depending on the type of compound (0) and / or resin (6) of this embodiment and the type of developer used, either a positive resist pattern or a negative resist pattern can be produced.

[0145] In the case of a positive resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist film-forming composition of this embodiment in a 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. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in the developer and to be easily made into a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is presumably because 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 increases due to the change in solubility of the compound (0) and / or resin (6) of this embodiment before and after exposure. In addition, the effect of reducing LER and defects is also observed.

[0146] In the case of a negative resist pattern, the dissolution rate of the amorphous film formed by spin-coating the composition for forming a resist film of this embodiment in a developer at 23° C. is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, the film is easily soluble in a developer and is suitable for a resist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the micro surface portion of the compound (0) and / or the resin (6) of this embodiment dissolves, reducing LER. In addition, a defect reduction effect is also observed.

[0147] The dissolution rate can be determined by immersing an amorphous film in a developer at 23° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.

[0148] In the case of a positive resist pattern, the dissolution rate in a developer at 23°C of the portion of the amorphous film formed by spin-coating the resist film-forming composition of this embodiment, which is exposed to radiation such as KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, is preferably 10 Å / sec or more. When the dissolution rate is 10 Å / sec or more, the film is easily soluble in a developer and is suitable for a resist. When the dissolution rate is 10 Å / sec or more, the resolution may be improved. This is presumably because the micro surface portion of the compound (0) and / or the resin (6) of this embodiment dissolves, reducing LER. In addition, a defect reduction effect is also observed.

[0149] In the case of a negative resist pattern, the dissolution rate in a developer at 23°C of the portion of the amorphous film formed by spin-coating the resist film-forming composition of this embodiment, which is exposed to radiation such as KrF excimer laser, extreme ultraviolet ray, 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. When the dissolution rate is 5 Å / sec or less, it tends to be insoluble in the developer and to be easily made into a resist. When the dissolution rate is 0.0005 Å / sec or more, the resolution may be improved. This is presumably because 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 increases due to the change in solubility of the compound (0) and / or resin (6) of this embodiment before and after exposure. In addition, the effect of reducing LER and defects is also observed.

[0150] Compound 0) and / or resin (6) contained in the composition for forming a resist film of the present embodiment is soluble in a solvent selected from the group consisting of PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and exhibits the highest dissolving ability for compound 0) and / or resin (6), at 23° C., in a concentration of preferably 1 mass % or more, more preferably 5 mass % or more, and even more preferably 10 mass % or more. The compound (0) and / or resin (6) contained in the composition for forming a resist film of the present embodiment is selected from the group consisting of PGMEA, PGME, and CHN, and is soluble in a solvent exhibiting the highest solubility for component (A) at 23° C., preferably at 20% by mass or more, and more preferably at 20% by mass or more in PGMEA at 23° C. By satisfying the above conditions, the composition can be easily used in the semiconductor manufacturing process in actual production.

[0151] The resist film forming composition of this embodiment may contain other resins than those of this embodiment, as long as the object of this embodiment is not hindered. Examples of such other resins include novolac resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units, or derivatives thereof. The amount of these resins is appropriately adjusted depending on the type of compound 0) and / or resin (6) of this embodiment to be used, 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, relative to 100 parts by mass of compound 0) and / or resin (6) of this embodiment.

[0152] Furthermore, the composition for forming a resist film of the present embodiment may contain a crosslinking agent, a crosslinking accelerator, a radical polymerization initiator, an acid generator, and a basic compound exemplified in the above-mentioned "composition" (composition used for forming a film for lithography) within a range that does not impair the object of the present embodiment.

[0153] [Permanent resist film] The composition of this embodiment is more preferably used to form a resist pattern as necessary and to form a resist permanent film remaining in the final product. That is, the resist permanent film of this embodiment includes the composition of this embodiment. The film formed by applying the composition of this embodiment is suitable as a resist permanent film remaining in the final product after forming a resist pattern as necessary. Specific examples of permanent films include solder resist, packaging material, underfill material, package adhesive layer of circuit elements, etc., and adhesive layer between integrated circuit elements and circuit boards in the semiconductor device field, and thin film transistor protective film, liquid crystal color filter protective film, black matrix, spacer, etc. in the thin display field. In particular, the resist permanent film containing the composition of this embodiment has the excellent advantages of being excellent in heat resistance and moisture resistance, and being less susceptible to contamination by sublimation components. In particular, in display materials, it is a material that combines high sensitivity, high heat resistance, and moisture absorption reliability with little image quality deterioration due to important contamination.

[0154] When the composition of the present embodiment is used for a permanent resist film, in addition to a curing agent, various additives such as other resins, surfactants, dyes, fillers, crosslinking agents, and dissolution promoters can be added as necessary, and the composition can be dissolved in an organic solvent to form a composition for a permanent resist film.

[0155] [Method of forming resist pattern] The method for forming a resist pattern of the present embodiment preferably includes a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition of the present embodiment, a photoresist film forming step of forming at least one layer of photoresist film on the resist underlayer film formed in the resist underlayer film forming step, and a development step of irradiating a predetermined region of the photoresist film formed in the photoresist film forming step with radiation and developing the photoresist film to obtain a resist pattern. Such a resist pattern forming method can be used to form various patterns, and is preferably a method for forming an insulating film pattern. The method for forming a resist pattern of the present embodiment preferably includes a photoresist layer forming step of forming a photoresist layer on a substrate using the composition of the present embodiment, and a development step of irradiating a predetermined region of the photoresist layer formed in the photoresist layer forming step with radiation and developing the photoresist layer to obtain a resist pattern. Such a resist pattern forming method can also be used to form various patterns, and is preferably a method for forming an insulating film pattern.

[0156] [Circuit pattern formation method] The circuit pattern forming method of the present embodiment includes a resist underlayer film forming step of forming a resist underlayer film on a substrate using the composition of the present embodiment, an intermediate layer film forming step of forming an intermediate layer film on the resist underlayer film formed in the resist underlayer film forming step, a photoresist film forming step of forming at least one layer of photoresist film on the intermediate layer film formed in the intermediate layer film forming step, a resist pattern forming step of irradiating a predetermined region of the photoresist film formed in the photoresist film forming step with radiation and developing it to form a resist pattern, an intermediate layer film pattern forming step of etching the intermediate layer film using the resist pattern formed in the resist pattern forming step as a mask to form an intermediate layer film pattern, a resist underlayer film pattern forming step of etching the resist underlayer film using the intermediate layer film pattern formed in the intermediate layer film pattern forming step as a mask to form a resist underlayer film pattern, and a substrate pattern forming step of etching the substrate using the resist underlayer film pattern formed in the resist underlayer film pattern forming step as a mask to form a pattern on the substrate.

[0157] The resist underlayer film of the present embodiment is formed from the film-forming composition for lithography of the present embodiment. The method of forming the resist underlayer film is not particularly limited, and known methods can be applied. For example, the film-forming composition for lithography of the present embodiment is applied to a substrate by known coating methods such as spin coating or screen printing, printing methods, etc., and then the organic solvent is removed by volatilization, etc., to form a resist underlayer film.

[0158] When forming the resist underlayer film, it is preferable to bake the resist underlayer film in order to suppress the occurrence of mixing with the resist upper layer film and promote the crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450°C, more preferably 200 to 400°C. In addition, the baking 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 depending on the required performance, and is not particularly limited, but is preferably 30 to 20,000 nm, more preferably 50 to 15,000 nm.

[0159] After preparing the resist underlayer film, in the case of a two-layer process, it is preferable to prepare a silicon-containing resist film or a monolayer resist made of hydrocarbon on the resist underlayer film, and in the case of a three-layer process, it is preferable to prepare a silicon-containing intermediate layer on the resist underlayer film, and further prepare a silicon-free monolayer resist film on the silicon-containing intermediate layer.In this case, the photoresist material for forming this resist film can be a known one.

[0160] As a silicon-containing resist material for a two-layer process, from the viewpoint of etching resistance, a positive photoresist material is preferably used which uses a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative as a base polymer, and further contains an organic solvent, an acid generator, and if necessary, a basic compound, etc. Here, as the silicon atom-containing polymer, a known polymer used in this type of resist material can be used.

[0161] As the silicon-containing intermediate layer for the three-layer process, a polysilsesquioxane-based intermediate layer is preferably used. By giving the intermediate layer an effect as an anti-reflection film, reflection tends to be effectively suppressed. For example, in a 193 nm 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 be high and the substrate reflection tends to be high, but by suppressing reflection with the intermediate layer, the substrate reflection can be reduced to 0.5% or less. As the intermediate layer having such an anti-reflection effect, it is not limited to the following, but for 193 nm exposure, a polysilsesquioxane that is crosslinked by acid or heat and has a light-absorbing group having a phenyl group or a silicon-silicon bond introduced therein is preferably used.

[0162] An intermediate layer formed by a Chemical Vapour Deposition (CVD) method can also be used. As an intermediate layer produced by a CVD method and having a high effect as an anti-reflection film, for example, a SiON film is known, but is not limited to the following. In general, it is easier and more cost-effective to form an intermediate layer by a wet process such as a spin coating method or screen printing than by a CVD method. The upper layer resist in the three-layer process may be either a positive type or a negative type, and the same resist as a commonly used single layer resist can be used.

[0163] Furthermore, the resist underlayer film in this embodiment can be used as an anti-reflection film for a normal single-layer resist or as an underlayer material for suppressing pattern collapse. Since the resist underlayer film has excellent etching resistance for underlayer processing, it can also be expected to function as a hard mask for underlayer processing.

[0164] When forming a resist film using the photoresist material, a wet process such as spin coating or screen printing is preferably used, as in the case of forming the resist underlayer film. After applying the resist material by spin coating or the like, pre-baking is usually performed, and this pre-baking is preferably performed at 80 to 180° C. for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain a resist pattern. The thickness of the resist film is not particularly limited, but is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.

[0165] The exposure light may be appropriately selected depending on the photoresist material used. In general, high energy rays having a wavelength of 300 nm or less, specifically, excimer lasers having wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays having wavelengths of 3 to 20 nm, electron beams, X-rays, and the like can be used.

[0166] The resist pattern formed by the above-mentioned method is one in which pattern collapse is suppressed by the resist underlayer film. Therefore, by using the resist underlayer film of the present embodiment, a finer pattern can be obtained, and the exposure dose required to obtain the resist pattern can be reduced.

[0167] Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used for etching the resist underlayer film in the two-layer process. Etching using oxygen gas is suitable for gas etching. In addition to oxygen gas, it is also possible to add inert gases such as He and Ar, or CO, CO2, NH3, SO2, N2, NO2, and H2 gases. Gas etching can also be performed using only CO, CO2, NH3, N2, NO2, and H2 gases without using oxygen gas. In particular, the latter gas is preferably used for sidewall protection to prevent undercutting of the pattern sidewall.

[0168] On the other hand, gas etching is also preferably used for etching the middle layer in the three-layer process. The gas etching can be the same as that described in the two-layer process. In particular, the processing of the middle layer in the three-layer process is preferably performed using a fluorocarbon-based gas and a resist pattern as a mask. Then, as described above, the processing of the resist underlayer film can be performed by, for example, performing oxygen gas etching using the middle layer pattern as a mask.

[0169] Here, when forming an inorganic hard mask intermediate layer film as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxide nitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not particularly limited, but for example, the methods described in JP-A-2002-334869 (Patent Document 9) and WO2004 / 066377 (Patent Document 10) can be used. A photoresist film can be formed directly on such an intermediate layer film, but an organic anti-reflective coating (BARC) may be formed on the intermediate layer film by spin coating, and a photoresist film may be formed on the organic anti-reflective coating (BARC).

[0170] As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. By giving the resist intermediate layer film the effect of an anti-reflection film, 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 JP-A-2007-226170 (Patent Document 11) and JP-A-2007-226204 (Patent Document 12) can be used.

[0171] The next etching of the substrate can also be performed by a conventional method, for example, if the substrate is SiO2 or SiN, etching can be performed mainly with fluorocarbon-based gas, and if it is p-Si, Al, or W, etching can be performed mainly with chlorine-based or bromine-based gas. When etching the substrate with fluorocarbon-based gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are stripped at the same time as the substrate is processed. On the other hand, when the substrate is etched with chlorine-based or bromine-based gas, the silicon-containing resist film or the silicon-containing intermediate layer is stripped separately, and generally, dry etching stripping with fluorocarbon-based gas is performed after the substrate is processed.

[0172] The resist underlayer film of this embodiment has a feature of excellent resistance to etching of the substrate. The substrate can be appropriately selected from known ones, and includes, but is not limited to, Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc. The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Such a film to be processed includes, but is not limited to, various low-k films and stopper films thereof, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and is usually made of a material different from that of the base material (support). The thickness of the substrate or film to be processed is not particularly limited, but is usually preferably about 50 to 1,000,000 nm, more preferably 75 to 50,000 nm.

[0173] The composition of the present embodiment can be prepared by blending the above-mentioned components and mixing them using a stirrer, etc. Furthermore, when the composition of the present embodiment contains a filler or a pigment, it can be prepared by dispersing or mixing them using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill.

[0174] [Method for purifying compound (0) and / or resin (6)] The purification method of the compound (0) and / or resin (6) of this embodiment includes an extraction step of contacting a solution containing an organic solvent that is arbitrarily immiscible with water and the compound (0) and / or resin (6) of this embodiment (hereinafter also simply referred to as "solution (A)") with an acidic aqueous solution to perform extraction. More specifically, the purification method of this embodiment involves dissolving the compound (0) and / or resin (6) of this embodiment in an organic solvent that is arbitrarily immiscible with water, contacting the solution with an acidic aqueous solution to perform extraction treatment, thereby transferring metals contained in the solution (A) to the aqueous phase, and then separating the organic phase from the aqueous phase for purification. The purification method of this embodiment can significantly reduce the content of various metals in the compound or resin of this embodiment.

[0175] In this embodiment, the term "organic solvent that is not arbitrarily miscible with water" refers to a solvent that has a solubility in water of less than 50% by mass at 20°C, and preferably less than 25% by mass from the viewpoint of productivity. The organic solvent that is not arbitrarily miscible with water is not particularly limited, but is preferably an organic solvent that can be safely applied to the semiconductor manufacturing process. The amount of the organic solvent used is usually about 1 to 100 times by mass relative to the compound (0) and / or resin (6) of this embodiment.

[0176] Specific examples of the organic solvent include, but are not limited to, those described in International Publication WO2015 / 080240. These solvents are used alone or in combination of two or more. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, PGMEA, ethyl acetate, etc. are preferred, and cyclohexanone and PGMEA are more preferred.

[0177] The acidic aqueous solution used is appropriately selected from among aqueous solutions in which a generally known organic compound or an inorganic compound is dissolved in water. For example, those described in International Publication WO2015 / 080240 can be mentioned. These acidic aqueous solutions are used alone or in combination of two or more. Among these, aqueous solutions of sulfuric acid, nitric acid, and carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and citric acid are preferred, aqueous solutions of sulfuric acid, oxalic acid, tartaric acid, and citric acid are more preferred, and aqueous solutions of oxalic acid are even more preferred. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid are coordinated to metal ions, and a chelating effect is generated, so that it is considered that metals can be removed more easily. In addition, the water used here is preferably one with a low metal content, such as ion-exchanged water, in line with the purpose of this embodiment.

[0178] The pH of the acidic aqueous solution used in this embodiment is not particularly limited, but in general, the pH range is preferably about 0 to 5, and more preferably about 0 to 3.

[0179] The amount of the acidic aqueous solution used in this embodiment is not particularly limited, but if the amount is too small, extraction must be performed many times to remove the metal, and conversely, if the amount of the aqueous solution is too large, the total amount of liquid becomes large, which may cause operational problems. The amount of the acidic aqueous solution used is usually preferably 10 to 200% by mass, and more preferably 20 to 100% by mass, relative to the solution (A).

[0180] In the purification method of the present embodiment, for example, the above-mentioned acidic aqueous solution is brought into contact with solution (A) to extract metal components.

[0181] The temperature during the extraction treatment is usually preferably 20 to 90° C., more preferably 30 to 80° C. The extraction operation is carried out, for example, by thoroughly mixing the solution by stirring or the like, and then allowing it to stand. This causes the metal content contained in the solution (A) to migrate to the aqueous phase. This operation also reduces the acidity of the solution, making it possible to suppress deterioration of the compound (0) and / or resin (6) of this embodiment.

[0182] The resulting mixture is separated into an organic phase containing the compound (0) and / or resin (6) of this embodiment and an organic solvent, and an aqueous phase, and the organic phase containing the compound (0) and / or resin (6) of this embodiment and an organic solvent is recovered by decantation or the like. The time for leaving the mixture standing is not particularly limited, but is preferably, for example, 1 minute or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more. The extraction process may be performed only once, but it is also effective to repeat the operations of mixing, leaving the mixture standing, and separating the mixture several times.

[0183] When such an extraction treatment is performed using an acidic aqueous solution, it is preferable that the organic phase containing the compound (0) and / or resin (6) of this embodiment and the organic solvent, which is extracted and recovered from the acidic aqueous solution after the treatment, is further subjected to an extraction treatment with water. The extraction treatment is performed by thoroughly mixing the organic phase with water by stirring or the like, and then leaving it to stand. The resulting solution is separated into a solution phase containing the compound (0) and / or resin (6) of this embodiment and the organic solvent and an aqueous phase, and the solution phase containing the compound (0) and / or resin (6) of this embodiment and the organic solvent is recovered by decantation or the like. In addition, the water used here is preferably one with a low metal content, such as ion-exchanged water, in line with the object of this embodiment. The extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, leaving to stand, and separating several times. In addition, the ratio of both used in the extraction treatment, and the conditions such as temperature and time are not particularly limited, but may be the same as in the case of the contact treatment with the acidic aqueous solution described above.

[0184] Water contained in the thus obtained solution containing the compound (0) and / or resin (6) of this embodiment and an organic solvent can be easily removed by performing an operation such as distillation under reduced pressure, etc. Furthermore, the concentration of the compound (0) and / or resin (6) of this embodiment can be adjusted to any desired concentration by adding an organic solvent, if necessary.

[0185] The method for obtaining only the compound (0) and / or resin (6) of the present embodiment from the obtained solution containing the compound (0) and / or resin (6) of the present embodiment and an organic solvent can be performed by a known method such as removal under reduced pressure, separation by reprecipitation, a combination thereof, etc. If necessary, known treatments such as a concentration operation, a filtration operation, a centrifugation operation, a drying operation, etc. can be performed.

[0186] The method for evaluating the amount of impurities in compound (0) and / or resin (6) after the purification method of the present embodiment, i.e., after purification, is not particularly limited, and can be evaluated based on the amount of various metals measured by ICP-MS as described in the Examples below. EXAMPLES

[0187] The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to these examples in any way.

[0188] (LC-MS analysis: molecular weight measurement) The molecular weight of the compound or resin was measured by liquid chromatography mass spectrometry (hereinafter, simply referred to as "LC-MS analysis") using an analytical device "Acquity UPLC / MALDI-Synapt HDMS" (product name, product of Waters Corporation).

[0189] (Mn, Mw and Mw / Mn) Mn, Mw and Mw / Mn were determined in terms of polystyrene by gel permeation chromatography (GPC) analysis under the following measurement conditions. Equipment: "Shodex GPC-101" (product name, manufactured by Showa Denko K.K.) Column: "KF-80M" x 3 (product name, manufactured by Showa Denko K.K.) Eluent: Tetrahydrofuran (hereinafter referred to as "THF") Flow rate: 1mL / min Temperature: 40℃

[0190] (ICP-MS) The measurements were carried out using an inductively coupled plasma mass spectrometer (hereinafter also referred to as "ICP-MS") "ELAN DRCII" (product name, manufactured by PerkinElmer).

[0191] [Synthesis of compounds and resins] (Synthesis Example 1) Synthesis of compound (XBisN-F1) In a 1000 mL container equipped with a stirrer, a cooling tube, and a buret, 89.2 g (0.56 mol) of 2,7-dihydroxynaphthalene, 44.6 g (0.25 mol) of fluorenone, 4.86 g (0.05 mol) of sulfuric acid, and 500 mL of γ-butyrolactone were added, and the contents were stirred at 150 ° C. for 7 hours to carry out the reaction, thereby obtaining a reaction solution. The reaction solution was cooled, extracted twice with 1 L of ethyl acetate, concentrated, separated by column chromatography, and then recrystallized three times with isopropyl alcohol to obtain 1.3 g of the target compound (XBisN-F1) represented by the following formula (XBisN-F1). The molecular weight of the resulting compound (XBisN-F1) was measured by the above-mentioned "LC-MS analysis" method, and was found to be 464. Regarding the obtained compound (XBisN-F1), 1 When H-NMR (500 MHz, DMSO-d6) measurement was performed, the following peaks were found, and it was confirmed that compound (XBisN-F1) has the chemical structure of the following formula (XBisN-F1). δ (ppm) 6.7-8.1 (18H, Ph-H, naphthyl-H), 9.76 (2H, -OH). [ka]

[0192] (Synthesis Example 2) Synthesis of compound (XBisN-F1-MeBOC) In a 200mL container equipped with a stirrer, a cooling tube, and a buret, 5.5g (11.8mmol) of the compound (XBisN-F1) obtained above, 5.4g (27mmol) of t-butyl bromoacetate (manufactured by Aldrich Co.), and 100mL of acetone were charged, 3.8g (27mmol) of potassium carbonate (manufactured by Aldrich Co.) and 0.8g of 18-crown-6 were added, and the contents were stirred under reflux for 3 hours to carry out the reaction. Next, the reaction solution after the reaction was concentrated, 100g of pure water was added to the concentrated solution to precipitate the reaction product, and the solution was cooled to room temperature, and then filtered to separate the solid matter. The obtained solid was dried and then separated and purified by column chromatography to obtain 1.0 g of the compound represented by the following formula (XBisN-F1-MeBOC). When the obtained compound (XBisN-F1-MeBOC) was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure of the following formula, XBisN-F1-MeBOC). 1H-NMR (d6-DMSO): δ (ppm) 1.4 (18H, OC-CH3), 4.9 (4H, O-CH2-C), 6.7~8.1 (18H, Ph-H, naphthyl-H). [ka]

[0193] (Synthesis Example 3) Synthesis of resin (R1-XBisN-F1) A four-neck flask with a capacity of 1 L and equipped with a Dimroth condenser, a thermometer and a stirring blade, which can be opened from the bottom, was prepared. In this four-neck flask, 28 g (60 mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1, 21.0 g of a 40 mass% formalin aqueous solution (280 mmol as formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 0.97 mL of 98 mass% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged in a nitrogen gas flow, and the mixture was reacted for 7 hours under reflux at 100 ° C. under normal pressure. Then, 180.0 g of ortho-xylene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added as a dilution solvent to the reaction solution, and after standing, the aqueous phase of the lower phase was removed. Furthermore, neutralization and washing with water were performed, and ortho-xylene was distilled off under reduced pressure to obtain 23 g of a brown solid resin (R1-XBisN-F1).

[0194] The resulting resin (R1-XBisN-1) had Mn: 3650, Mw: 6950, and Mw / Mn: 1.90.

[0195] (Synthesis Example 4) Synthesis of compound (XBisN-F1-BOC) In a 200 mL container equipped with a stirrer, a cooling tube, and a buret, 5.5 g (11.8 mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1 and 5.2 g (23.8 mmol) of di-t-butyl dicarbonate (manufactured by Aldrich) were charged in 100 mL of acetone, 3.29 g (23.8 mmol) of potassium carbonate (manufactured by Aldrich) were added, and the contents were stirred at 20 ° C. for 6 hours to carry out the reaction to obtain a reaction solution. Next, the reaction solution was concentrated, and 100 g of pure water was added to the concentrated solution to precipitate the reaction product, and the solution was cooled to room temperature, and then filtered to separate the solid matter. The obtained solid matter was filtered, dried, and then separated and purified by column chromatography to obtain 0.9 g of the target compound (XBisN-F1-BOC) represented by the following formula. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the following formula (XBisN-F1-BOC). 1H-NMR (d6-DMSO): δ (ppm) 1.4 (27H, OC-CH3), 5.3 (1H, CH), 6.9~7.9 (12H, Ph-H)

[0196] 1H-NMR (d6-DMSO): δ (ppm) 1.4 (18H, OC-CH3), 6.7-8.1 (18H, Ph-H, naphthyl-H). [ka]

[0197] (Synthesis Example 5) Synthesis of compound (XBisN-F1-AL) In a 500mL container equipped with a stirrer, a cooling tube and a buret, 5.5g (11.8mmol) of the compound (XBisN-F1) obtained by the method of Synthesis Example 1, 54g (39mmol) of potassium carbonate and 200mL of dimethylformamide were charged, 77.6g (0.64mol) of allyl bromide was added, and the reaction solution was stirred at 110°C for 24 hours to carry out the reaction. Next, the reaction solution was concentrated, 500g of pure water was added to precipitate the reaction product, and after cooling to room temperature, it was separated by filtration. The obtained solid was filtered and dried, and then separated and purified by column chromatography to obtain 2.7g of the target compound (XBisN-F1AL) represented by the following formula. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure of the following formula (XBisN-F1-AL). 1H-NMR (d6-DMSO): δ(ppm) 4.8 (4H, O-CH2-C), 5.3~5.4 (4H,-C=CH2), 6.1 (2H,-CH=C), 6.7~8.1 (18H, Ph-H, naphthyl-H). [ka]

[0198] (Synthesis Example 6) Synthesis of compound (XBisN-F1-Ac) The procedure was the same as in Synthesis Example 5, except that 46.1 g (0.64 mol) of acrylic acid was used instead of 77.6 g (0.64 mol) of the above-mentioned allyl bromide, and 3.5 g of the target compound (XBisN-F1-Ac) represented by the following formula was obtained. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the following formula (XBisN-F1-Ac). 1H-NMR (d6-DMSO): δ (ppm) 5.8~6.4 (4H,-C=CH2), 6.1 (2H,-CH=C), 6.7~8.1 (18H, Ph-H, naphthyl-H). [ka]

[0199] (Synthesis Example 7) Synthesis of compound (XBisN-F1-Ea) In a 100 ml vessel equipped with a stirrer, a condenser, and a buret, 7.0 g (15.1 mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1, 5.5 g of glycidyl methacrylate, 0.45 g of triethylamine, and 0.08 g of p-methoxyphenol were placed in 70 ml of methyl isobutyl ketone, and the mixture was heated to 80° C. and stirred for 24 hours to carry out the reaction. The reaction solution was cooled to 50°C, dropped into pure water, and the precipitated solid was filtered and dried. The solid was then separated and purified by column chromatography to obtain 1.4 g of the target compound (XBisN-F1-Ea) represented by the following formula. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by the following formula (XBisN-F1-Ea). 1H-NMR (d6-DMSO): δ(ppm) 2.0 (6H, -CH3), 3.4~4.4 (9H, -CH2-, -CH-), 5.8 (2H, -OH), 6.4~6.5 (4H, -C=CH2), 6.1 (2H, -CH=C), 6.7~8.1 (18H, Ph-H, naphthyl-H). [ka]

[0200] (Synthesis Example 8) Synthesis of compound (XBisN-F1-Ua) In a 100 mL container equipped with a stirrer, a cooling tube and a buret, 7.0 g (15.1 mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1, 5.5 g of 2-isocyanatoethyl methacrylate, 0.45 g of triethylamine, and 0.08 g of p-methoxyphenol were charged in 70 mL of methyl isobutyl ketone, and the mixture was heated to 80 ° C. and stirred for 24 hours to carry out the reaction. The mixture was cooled to 50 ° C., the reaction liquid was dropped into pure water, and the precipitated solid was filtered and dried, and then separation and purification were carried out by column chromatography to obtain 1.5 g of the target compound (XBisN-F1-Ua) represented by the following formula. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the following formula (XBisN-F1-Ua). 1H-NMR (d6-DMSO): δ(ppm) 2.0 (6H, -CH3), 3.1 (4H, -CH2-), 4.6 (4H, -CH2-), 6.4~6.5 (4H, -C=CH2), 6.7~8.1 (20H, Ph-H, naphthyl-H, -NH-). [ka]

[0201] (Synthesis Example 9) Synthesis of compound (XBisN-F1-E) In a 200mL vessel equipped with a stirrer, a cooling tube and a buret, 7.0g (15.1mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1 and 10g (72mmol) of potassium carbonate were charged in 60mL of dimethylformamide, 5.0g (40.6mmol) of 2-chloroethyl acetate was added, and the reaction solution was stirred at 90°C for 12 hours to carry out the reaction. Next, the reaction solution was cooled in an ice bath to precipitate crystals, which were then separated by filtration. Next, 30g of the above-mentioned crystals, 30g of methanol, 100g of THF and a 24% aqueous sodium hydroxide solution were charged in a 500mL vessel equipped with a stirrer, a cooling tube and a buret, and the reaction solution was stirred under reflux for 4 hours to carry out the reaction. After that, the reaction solution was cooled in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried, and then separation and purification was carried out by column chromatography to obtain 3.0g of the target compound (XBisN-F1-E) represented by the following formula. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the following formula (XBisN-F1-Ua). 1H-NMR (d6-DMSO): δ (ppm) 3.7 (4H,-CH2-), 4.3 (4H,-CH2-), 5.4 (2H,-OH), 6.7~8.1 (18H, Ph-H, naphthyl-H). [ka]

[0202] (Synthesis Example 10) Synthesis of compound (XBisN-F1-PX) In a 1000mL container equipped with a stirrer, a cooling tube and a buret, 30g (65mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1-1, 47.2g of iodoanisole, 87.5g of cesium carbonate, 1.4g of dimethylglycim hydrochloride, and 0.5g of copper iodide were charged in 400mL of 1,4-dioxane, heated to 95°C and stirred for 22 hours to carry out the reaction. Next, the insoluble matter was filtered off, the filtrate was concentrated and dropped into pure water, the precipitated solid was filtered, dried, and then separated and purified by column chromatography to obtain 16g of the intermediate compound (XBisN-F1-M) represented by the following formula. [ka]

[0203] Next, 15 g of the compound represented by the above formula (XBisN-F1-M) and 80 g of pyridine hydrochloride were charged into a 1000 mL container equipped with a stirrer, a cooling tube, and a burette, and the reaction was carried out by stirring at 190 ° C for 2 hours. Next, 160 mL of hot water was added and stirred to precipitate a solid. Then, 250 mL of ethyl acetate and 100 mL of water were added, stirred, and allowed to stand. The organic layer separated was concentrated and dried, and then separated and purified by column chromatography to obtain 7 g of the target compound represented by the following formula (XBisN-F1-PX). When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by the following formula (XBisN-F1-PX). 1H-NMR (d6-DMSO): δ (ppm) 6.7-8.1 (26H, Ph-H, naphthyl-H) 9.1 (2H, OH). [ka]

[0204] (Synthesis Example 11) Synthesis of compound (XBisN-F1-PE) The reaction was carried out in the same manner as in Synthesis Example 1-10, except that the compound represented by the above formula (XBisN-F1-E) was used instead of the compound represented by the above formula (XBisN-F), to obtain 5 g of the target compound represented by the following formula (XBisN-F1-PE). When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by the following formula (XBisN-F1-PE). 1H-NMR(d6-DMSO): δ(ppm) 3.1(4H,-CH2-), 4.3(4H,-CH2-), 6.7~8.1(26H, Ph-H, naphthyl-H), 9.1(2H,OH). [ka]

[0205] (Synthesis Example 12) Synthesis of compound (XBisN-F1-G) A 100 ml container equipped with a stirrer, a cooling tube and a buret was charged with 5.5 g (11.8 mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1 and 3.7 g (27 mmol) of potassium carbonate in 100 ml of dimethylformamide, and 2.5 g (27 mmol) of epichlorohydrin was added, and the resulting reaction solution was stirred at 90 ° C. for 6.5 hours to carry out the reaction. Next, the solid content was removed from the reaction solution by filtration, cooled in an ice bath, crystals were precipitated, filtered, dried, and then separated and purified by column chromatography to obtain 1.5 g of the target compound represented by the following formula (XBisN-F1-G). When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by the following formula (XBisN-F1-G). 1H-NMR (d6-DMSO): δ (ppm) 2.3~2.7 (6H, -CH(CH2)O), 3.9~4.1 (4H, -CH2-), 6.7~8.1 (18H, Ph-H, naphthyl-H). [ka]

[0206] (Synthesis Example 13) Synthesis of compound (XBisN-F1-GE) The reaction was carried out in the same manner as in Synthesis Example 12, except that the compound represented by the formula (XBisN-F1-E) was used instead of the compound represented by the formula (XBisN-F1), to obtain 1.6 g of the target compound represented by the following formula (XBisN-F1-GE). When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by the following formula (XBisN-F1-GE). 1H-NMR(d6-DMSO): δ(ppm) 2.3~2.7(6H,-CH(CH2)O), 3.9~4.3(12H,-CH2-), 6.7~8.1(18H, Ph-H, naphthyl-H). [ka]

[0207] (Synthesis Example 14) Synthesis of compound (XBisN-F1-SX) In a 100 ml container equipped with a stirrer, a cooling tube and a buret, 5.5 g (11.8 mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1 and 3.8 g of vinylbenzyl chloride (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.) were charged in 50 ml of dimethylformamide, and in a state of being heated to 50 ° C and stirred, 5.0 g of 28 mass% sodium methoxide (methanol solution) was added from a dropping funnel over 20 minutes, and the reaction solution was stirred at 50 ° C for 1 hour to carry out the reaction. Next, 1.0 g of 28 mass% sodium methoxide (methanol solution) was added, the reaction solution was heated to 60 ° C and stirred for 3 hours, and 1.0 g of 85 mass% phosphoric acid was added, stirred for 10 minutes, cooled to 40 ° C, the reaction solution was dropped into pure water, and the precipitated solid was filtered and dried, and then separation and purification was performed by column chromatography, and 1.5 g of the target compound (XBisN-F1-SX) represented by the following formula was obtained. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the following formula (XBisN-F1-SX). 1H-NMR (d6-DMSO): δ (ppm) 5.1~5.3 (6H, -CH2-, -C=CH, CH), 5.8 (2H, -C=CH), 6.7~8.1 (28H, -CH=C, Ph-H, naphthyl-H). [ka]

[0208] (Synthesis Example 15) Synthesis of compound (XBisN-F1-SE) The reaction was carried out in the same manner as in Synthesis Example 14, except that the compound represented by the formula (XBisN-F1-E) was used instead of the compound represented by the formula (XBisN-F1), to obtain 1.6 g of the target compound represented by the following formula (XBisN-F1-SE). When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by the following formula (XBisN-F1-SE). 1H-NMR (d6-DMSO): δ(ppm) 3.8 (4H, -CH2-), 4.3 (4H, -CH2-), 4.8 (4H, -CH2-), 5.3 (2H, -C=CH), 5.8 (2H, -C=CH), 6.7~8.1 (28H, -CH=C, Ph-H, naphthyl-H). [ka]

[0209] (Synthesis Example 16) Synthesis of compound (XBisN-F1-Pr) In a 300 mL container equipped with a stirrer, a cooling tube, and a buret, 5.5 g (11.8 mmol) of the compound (XBisN-F1) obtained in Synthesis Example 1-1 and 4.8 g (40 mmol) of propargyl bromide were charged into 100 mL of dimethylformamide, and the reaction was carried out by stirring at room temperature for 3 hours to obtain a reaction solution. The reaction solution was then concentrated, and 300 g of pure water was added to the concentrated solution to precipitate the reaction product, which was then cooled to room temperature and filtered to separate the solid matter. The obtained solid matter was filtered, dried, and then separated and purified by column chromatography to obtain 2.7 g of the target compound (XBisN-F1-Pr) represented by the following formula. When the obtained compound was subjected to NMR measurement under the above-mentioned measurement conditions, the following peaks were found, and it was confirmed that the compound had a chemical structure represented by the following formula (XBisN-F1-Pr). 1H-NMR (d6-DMSO): δ (ppm) 3.5 (2H,≡CH), 4.7 (4H, -CH2-), 6.7~8.1 (18H, Ph-H, naphthyl-H). [ka]

[0210] (Synthesis Example A) A compound represented by the following formula (C-0) was synthesized in the same manner as in Synthesis Example 1, except that 2,7-dihydroxynaphthalene was changed to 2,6-dihydroxynaphthalene. [ka]

[0211] (Comparative Synthesis Example 1) Synthesis of C-1 A four-neck flask with a capacity of 10 L was prepared, which was equipped with a Dimroth condenser, a thermometer, and an agitator and could be bottomed out. In this four-neck flask, 1.09 kg (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2.1 kg of 40 mass% formalin aqueous solution (28 mol as formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and 0.97 mL of 98 mass% sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) were charged in a nitrogen stream, and the mixture was reacted for 7 hours while refluxing at 100°C under normal pressure. Then, 1.8 kg of ethylbenzene (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) was added as a dilution solvent to the reaction solution, and after standing, the aqueous phase of the lower phase was removed. Furthermore, neutralization and washing with water were performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of dimethylnaphthalene formaldehyde resin as a light brown solid. The molecular weight of the obtained dimethylnaphthalene formaldehyde resin was as follows: number average molecular weight (Mn): 562, weight average molecular weight (Mw): 1168, and dispersity (Mw / Mn): 2.08.

[0212] Next, a four-neck flask with an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer, and a stirring blade was prepared. In this four-neck flask, 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of p-toluenesulfonic acid were charged under a nitrogen gas flow, and the temperature was raised to 190 ° C. and heated for 2 hours, and then stirred. Then, 52.0 g (0.36 mol) of 1-naphthol was added, and the temperature was raised to 220 ° C. and reacted for 2 hours. After dilution with a solvent, neutralization and washing with water were performed, and the solvent was removed under reduced pressure to obtain 126.1 g of a black-brown solid resin (C-1). The obtained resin (C-1) had Mn: 885, Mw: 2220, and Mw / Mn: 2.51.

[0213] (Synthesis Example 1) Synthesis of AC-1 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 obtain a reaction solution. The reaction solution was polymerized for 22 hours under a nitrogen atmosphere while maintaining the reaction temperature at 63° C., and then the reaction solution was dropped into 400 mL of n-hexane. The resulting resin was coagulated and purified, and the resulting white powder was filtered and then dried overnight at 40° C. under reduced pressure to obtain AC-1 represented by the following formula.

[0214] [ka]

[0215] In formula AC-1, "40", "40", and "20" indicate the ratio of each constituent unit and do not indicate a block copolymer.

[0216] [Performance evaluation of compositions for forming resist films: Examples 1-1 to 21-1, A-1, and Comparative Example 1] Compositions for forming resist films having the formulations shown in Table 1 below were prepared using the compounds or resins of Synthesis Examples 1 to 21 and A and Synthesis Example 1. The acid generators, acid diffusion controllers, and organic solvents used were as follows. Acid generator: Triphenylsulfonium nonafluoromethanesulfonate (TPS-109) manufactured by Midori Chemical Co., Ltd. Acid diffusion control agent: Tri-n-octylamine (TOA) manufactured by Kanto Chemical Crosslinking agent: Sanwa Chemical's Nikalac MW-100LM Organic solvent: Kanto Chemical's propylene glycol monomethyl ether (PGME)

[0217] [Table 1]

[0218] [Evaluation method] (1) Safe solvent solubility test for compounds or resins The solubility of the compound or resin in PGME, PGMEA, and CHN was evaluated based on the amount dissolved in each solvent according to the following criteria: The amount dissolved was measured at 23°C by precisely weighing the compound or resin alone in a test tube, adding the target solvent to a specified concentration, applying ultrasonic waves in an ultrasonic cleaner for 30 minutes, and then visually observing the state of the liquid. A:5.0 mass%≦dissolution amount B:2.0 mass%≦dissolved amount<5.0 mass% C: Dissolved amount<2.0% by mass

[0219] (2) Storage stability and thin film formation of the composition for forming a resist film The storage stability of the resist film-forming composition containing the compound or resin was evaluated by preparing the resist film-forming composition, leaving it at rest for 3 days at 23°C, and visually observing whether precipitation occurred. The resist film-forming composition was spin-coated on a clean silicon wafer, and then baked before exposure (PB) on a hot plate at 110°C to form a resist film with a thickness of 50 nm. The resist film-forming composition was evaluated as × if precipitation occurred, as △ if the solution was homogeneous but the thin film had defects, and as ○ if the solution was homogeneous, the thin film had no defects, and the thin film formation was good.

[0220] (3) Resist pattern The resist film obtained in (2) above was irradiated with an electron beam in a 1:1 line and space setting with 50 nm intervals using an electron beam lithography system (ELS-7500, manufactured by Elionix Co., Ltd.). After the irradiation, the resist film was heated at 110° C. for 90 seconds and developed by immersing in an alkaline developer of 2.38% by mass of TMAH for 60 seconds. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a resist pattern. The shape of the resulting 50 nmL / S (1:1) resist pattern was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. Regarding the resist pattern shape after development, those without pattern collapse and with better rectangularity than Comparative Example 1 were rated as A, and those equivalent to or inferior to Comparative Example 1 were rated as C. Furthermore, the minimum amount of electron beam energy capable of drawing a good pattern shape was evaluated as sensitivity, i.e., a sensitivity 10% or more better than Comparative Example 1 was evaluated as S, a sensitivity less than 10% better was evaluated as A, and a sensitivity equal to or worse than Comparative Example 1 was evaluated as C.

[0221] (4) Etching resistance Etching equipment: Samco International RIE-10NR Output: 50W Pressure: 20Pa Time: 2 minutes Etching Gas Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm) The films obtained in each of the examples and comparative examples were subjected to an etching test under the above-mentioned conditions, and the etching rate was measured. The etching resistance was evaluated according to the following evaluation criteria, based on the etching rate of a resist underlayer film prepared using novolak (Gun-ei Chemical Co., Ltd.'s "PSM4357"). A: Etching rate is less than -15% compared to novolac resist underlayer film. B: Etching rate is -15% to +5% compared to novolac resist underlayer film. C: Etching rate is more than +5% compared to novolac resist underlayer film.

[0222] The compounds or resins of Synthesis Examples 1 to 21, Synthesis Example A, and Synthesis Example 1 were evaluated for solubility in a safe solvent by the above-mentioned method, and the results are shown in Table 2. Furthermore, the compositions for forming a resist film were evaluated by the above-mentioned methods, and the results are shown in Table 2.

[0223] [Table 2]

[0224] [Performance evaluation of compositions for forming resist underlayer film: Examples 1-2 to 21-2, A-2, Comparative Example 2] Each composition for forming a resist underlayer film was prepared according to the composition shown in Table 3. Next, each composition for forming a resist underlayer film was spin-coated on a silicon substrate, and then baked at 240° C. for 60 seconds and then at 400° C. for 120 seconds to prepare a resist underlayer film having a thickness of 200 nm. The acid generator, crosslinking agent, and organic solvent used were as follows. Acid generator: di-tert-butyldiphenyliodonium nonafluoromethanesulfonate (hereinafter also referred to as "DTDPI") (manufactured by Midori Chemical Co., Ltd.) Crosslinking agent: "Nicalac MX270" (hereinafter also referred to as "Nicalac") (product name, manufactured by Sanwa Chemical Co., Ltd.) Organic solvent: propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") The etching resistance was then evaluated by the above-mentioned method, and the results are shown in Table 3.

[0225] [Table 3]

[0226] (Examples 1-3 to 21-3) The resist underlayer film forming compositions prepared in each of the above Examples 1-2 to 21-2 were applied onto a SiO2 substrate having a thickness of 300 nm, and baked at 240°C for 60 seconds and then at 400°C for 120 seconds to form a resist underlayer film having a thickness of 70 nm. An ArF resist solution was applied onto the resist underlayer film, and baked at 130°C for 60 seconds to form a photoresist film having a thickness of 140 nm. The ArF resist solution was prepared by mixing 5 parts by mass of the resin (AC-1) of the synthesis example, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGMEA.

[0227] Next, the photoresist film was exposed to light using an electron beam lithography system “ELS-7500” (product name, manufactured by Elionix Co., Ltd., 50 keV), baked (PEB) at 115°C for 90 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a positive resist pattern.

[0228] The results of observing defects in the resulting resist patterns of 55 nmL / S (1:1) and 80 nmL / S (1:1) are shown in Table 4. In the table, "good" indicates that no pattern collapse was observed in the formed resist pattern, and "poor" indicates that pattern collapse was observed in the formed resist pattern.

[0229] Comparative Example 3 A photoresist film was formed directly on a SiO2 substrate in the same manner as in Example 1-3, except that no underlayer film was formed, to obtain a positive resist pattern. The results are shown in Table 4.

[0230] [Table 4]

[0231] (Examples 1-4 to 21-4) The resist underlayer film forming composition of each of Examples 1-2 to 21-2 was applied onto a SiO2 substrate having a thickness of 300 nm, and baked at 240°C for 60 seconds and then at 400°C for 120 seconds to form a resist underlayer film having a thickness of 80 nm. A silicon-containing intermediate layer material was applied onto this resist underlayer film, and baked at 200°C for 60 seconds to form an intermediate layer film having a thickness of 35 nm. Furthermore, the above-mentioned ArF resist solution was applied onto this intermediate layer film, and baked at 130°C for 60 seconds to form a photoresist film having a thickness of 150 nm. As the silicon-containing intermediate layer material, a silicon atom-containing polymer described in <Synthesis Example 1> of JP-A-2007-226170 was used. Next, the photoresist film was exposed to light using a mask with an electron beam lithography apparatus (ELIONIX; ELS-7500, 50 keV), baked (PEB) at 115°C for 90 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide (hereinafter also referred to as "TMAH") aqueous solution for 60 seconds to obtain a positive resist pattern of 55 nmL / S (1:1). Then, using a parallel plate type RIE apparatus "RIE-10NR" (trade name, Samco International), the silicon-containing intermediate layer film was dry-etched using the obtained resist pattern as a mask, followed by dry etching of the resist underlayer film using the obtained silicon-containing intermediate layer film pattern as a mask, and dry etching of the SiO2 film using the obtained resist underlayer film pattern as a mask.

[0232] The etching conditions for each are as follows. Etching conditions for resist pattern onto resist intermediate layer film Output: 50W Pressure: 20Pa Time: 1 min Etching Gas Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:8:2 (sccm) Etching conditions for resist intermediate film pattern onto resist underlayer film Output: 50W Pressure: 20Pa Time: 2 minutes Etching Gas Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm) Etching conditions for resist underlayer film pattern onto SiO2 film Output: 50W Pressure: 20Pa Time: 2 minutes Etching Gas Ar gas flow rate: C5F 12 Gas flow rate: C2F6 gas flow rate: O2 gas flow rate =50:4:3:1(sccm)

[0233] The cross-section of the pattern obtained as described above (i.e., the shape of the SiO2 film after etching) was observed using an electron microscope "S-4800" (product name, manufactured by Hitachi, Ltd.) to evaluate the resist pattern formability. The observation results are shown in Table 5. In the table, "good" indicates that no major defects were observed in the cross-section of the formed pattern, and "poor" indicates that major defects were observed in the cross-section of the formed pattern.

[0234] [Table 5]

[0235] (Example 1-5) Purification of compound (XBisN-F1) with acid In a 1000mL four-neck flask (bottom-opening type), 150g of a solution (10% by mass) in which the compound (XBisN-F1) obtained in Synthesis Example 1 was dissolved in PGMEA was charged, and heated to 80°C while stirring. Next, 37.5g of an aqueous oxalic acid solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 37.5g of ultrapure water was charged into the obtained oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes, and the aqueous phase was removed. After repeating this operation three times, the flask was heated to 80°C and the pressure inside was reduced to 200hPa or less, thereby concentrating and distilling off the residual water and PGMEA. Then, the solution was diluted with EL grade PGMEA (a reagent manufactured by Kanto Chemical Co., Ltd.) and the concentration was adjusted to 10% by mass, thereby obtaining a PGMEA solution of BiP-1 with a reduced metal content.

[0236] (Reference Example) Purification of compound (XBisN-F1) with ultrapure water The same procedure as in Example 1-5 was carried out except that ultrapure water was used instead of the aqueous oxalic acid solution, and the concentration was adjusted to 10 mass % to obtain a PGMEA solution of the compound (XBisN-F1).

[0237] The contents of various metals in the 10% by mass PGMEA solution of the compound (XBisN-F1) before the treatment, and the solutions obtained in Examples 1 to 5 and Reference Example were measured by ICP-MS. The measurement results are shown in Table 7.

[0238] [Table 6]

[0239] As is apparent from the above, the compound and resin of the present embodiment simultaneously satisfy high levels of solubility in organic solvents, etching resistance, and resist pattern formability as a film-forming material for lithography, and the compound and resin are useful as a film-forming material for lithography.

[0240] This application is based on a Japanese patent application (Patent Application No. 2019-085888) filed with the Japan Patent Office on April 26, 2019, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0241] The compound and resin of the present invention have high heat resistance and high solvent solubility, and wet processes are applicable. Therefore, the lithography film-forming material and the lithography film using the compound or resin of the present invention can be widely and effectively used in various applications requiring these performances. Therefore, the present invention can be widely and effectively used in, for example, electrical insulating materials, resist resins, semiconductor sealing resins, printed wiring board adhesives, electrical laminates mounted on electrical equipment, electronic equipment, industrial equipment, etc., matrix resins for prepregs mounted on electrical equipment, electronic equipment, industrial equipment, etc., build-up laminate materials, resins for fiber reinforced plastics, sealing resins for liquid crystal display panels, paints, various coating agents, adhesives, coating agents for semiconductors, resist resins for semiconductors, resins for forming resist underlayer films, etc. In particular, the present invention can be particularly effectively used in the field of lithography films.

Claims

[Claim 1] A compound represented by the following formula (0): 【Chemistry 1】 (In the formula (0), R 0 are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group, a crosslinkable group, a dissociable group, a thiol group, or a hydroxyl group, wherein R 0 At least one of R is a hydroxyl group, a crosslinkable group, or a dissociable group, 0 The alkyl group, the aryl group, the alkenyl group, the alkynyl group, and the alkoxy group in the formula (I) may contain an ether bond, a ketone bond, or an ester bond; R 2 are each independently an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxyl group, a crosslinkable group, a dissociable group, a thiol group or a hydroxyl group, wherein R 2 The alkyl group, the aryl group, the alkenyl group, the alkynyl group, and the alkoxy group in the formula (I) may contain an ether bond, a ketone bond, or an ester bond; n 1 are each independently an integer from 1 to 2, n 0 Each independently represents 0 to (4+2n 1 ), where n 0 At least one of the following is 1 to (4+2n 1 ) and n 4 are each independently an integer from 0 to 1, n 5 Each independently represents 0 to (4+2n 4 ) is an integer.

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