Polymers, compositions, methods for producing polymers, compositions, film-forming compositions, resist compositions, radiation-sensitive compositions, compositions for forming underlayer films for lithography, resist pattern formation methods, methods for producing underlayer films for lithography, circuit pattern formation methods, and compositions for forming optical components.

Abstract

This polymer has a repeating unit derived from at least one type of monomer selected from the group consisting of aromatic hydroxy compounds represented by formulae (1A) and (1B). Repeating units are mutually connected by direct bonds between aromatic rings. (In formulae (1A) and (1B), R moieties are each independently an optionally substituted alkyl group having 1-40 carbon atoms, an optionally substituted aryl group having 6-40 carbon atoms, an optionally substituted alkenyl group having 2-40 carbon atoms, an alkynyl group having 2-40 carbon atoms, an optionally substituted alkoxy group having 1-40 carbon atoms, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group or a hydroxyl group, with at least one R moiety being a group containing a hydroxyl group. Each value of m is an integer between 1 and 10.)

Description

[Technical Field]

[0001] The present invention relates to polymers, compositions, methods for producing polymers, compositions, film-forming compositions, resist compositions, radiation-sensitive compositions, compositions for forming underlayer films for lithography, methods for forming resist patterns, methods for producing underlayer films for lithography, methods for forming circuit patterns, and compositions for forming optical components. [Background technology]

[0002] Polyphenol resins having repeating units derived from hydroxy-substituted aromatic compounds, etc., are known for use as encapsulants, coatings, resist materials, and semiconductor underlayer film forming materials for semiconductors. For example, the use of polyphenol compounds or resins having a specific skeleton is proposed in the following Patent Documents 1 and 2.

[0003] On the other hand, methods for producing polyphenol resins include adding and condensing phenols with formalin using acid or alkaline catalysts to produce novolac resins and resol resins. However, in recent years, since formaldehyde is used as a raw material in these phenol resin production methods, various alternative methods using substances other than formaldehyde have been studied for safety reasons. To solve this problem, a method has been proposed for producing polyphenol resins by oxidative polymerization of phenols using an enzyme with peroxidase activity, such as peroxidase, and a peroxide, such as hydrogen peroxide, in a solvent such as water or an organic solvent to produce phenol polymers. In addition, a method for producing polyphenylene oxide (PPO) by oxidative polymerization of 2,6-dimethylphenol is known (see Non-Patent Document 1 below).

[0004] In semiconductor device manufacturing, microfabrication is performed using lithography with photoresist materials. However, with the increasing integration and speed of LSIs in recent years, further miniaturization using pattern rules is required. In lithography using light exposure, which is currently used as a general-purpose technology, we are approaching the intrinsic resolution limit derived from the wavelength of the light source.

[0005] The light sources used for lithography in resist pattern formation have been shortened in wavelength from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). However, as resist patterns become finer, problems arise such as resolution issues or the resist pattern collapsing after development, making it desirable to thin the resist. To meet these demands, simply thinning the resist is insufficient to obtain a resist pattern thickness sufficient for substrate processing. Therefore, a process is needed to create a resist underlayer film between the resist and the semiconductor substrate to be processed, and to give this resist underlayer film the function of a mask during substrate processing.

[0006] Currently, various types of resist underlayers are known for such processes. For example, unlike conventional resist underlayers with high etching rates, lithography resist underlayers can be cited that have a selectivity ratio for dry etching rates close to that of the resist itself. As a material for forming such a lithography resist underlayer, a multilayer resist process underlayer forming material has been proposed that contains a resin component having at least substituents that produce sulfonic acid residues when terminal groups are removed by the application of a predetermined energy, and a solvent (see, for example, Patent Document 3 below). Furthermore, lithography resist underlayers with a selectivity ratio for dry etching rates smaller than that of the resist can also be cited. As a material for forming such a lithography resist underlayer, a resist underlayer material containing a polymer having specific repeating units has been proposed (see, for example, Patent Document 4 below). In addition, lithography resist underlayers with a selectivity ratio for dry etching rates smaller than that of semiconductor substrates can also be cited. As a material for forming such lithography resist underlayers, a resist underlayer material has been proposed that includes a polymer obtained by copolymerizing repeating units of acenaphthylenes with repeating units having substituted or unsubstituted hydroxyl groups (see, for example, Patent Document 5 below). In addition, a resist underlayer material has been proposed that includes an oxidized polymer of a specific bisnaphthol derivative (see, for example, Patent Document 6 below).

[0007] On the other hand, amorphous carbon underlayer films formed by chemical vapor deposition (CVD), using methane, ethane, or acetylene gases as raw materials, are well known as materials with high etching resistance in this type of resist underlayer film. However, from a process perspective, there is a need for resist underlayer film materials that can be formed by wet processes such as spin coating or screen printing.

[0008] Furthermore, there is a growing demand for forming lithography resist underlayers on workpieces with complex shapes, and there is a need for resist underlayer materials that can form underlayers with excellent embedding properties and surface planarization capabilities.

[0009] Regarding methods for forming the intermediate layer used in the formation of the resist underlayer in a three-layer process, for example, methods for forming silicon nitride films (see, for example, Patent Document 7 below) and CVD methods for forming silicon nitride films (see, for example, Patent Document 8 below) are known. Furthermore, as an intermediate layer material for a three-layer process, a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Document 9 below).

[0010] The present inventors have proposed compositions for forming underlayer films for lithography, comprising specific compounds or resins (see, for example, Patent Document 10 below).

[0011] Various optical component forming compositions have been proposed, such as acrylic resins (see, for example, Patent Documents 11 and 12 below) and polyphenols having a specific structure derived from allyl groups (see, for example, Patent Document 13 below). [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] International Publication No. 2013 / 024778 [Patent Document 2] International Publication No. 2013 / 024779 [Patent Document 3] Japanese Patent Publication No. 2004-177668 [Patent Document 4] Japanese Patent Publication No. 2004-271838 [Patent Document 5] Japanese Patent Publication No. 2005-250434 [Patent Document 6] Japanese Patent Publication No. 2020-027302 [Patent Document 7] Japanese Patent Publication No. 2002-334869 [Patent Document 8] International Publication No. 2004 / 066377 [Patent Document 9] Japanese Patent Publication No. 2007-226204 [Patent Document 10] International Publication No. 2013 / 024779 [Patent Document 11] Japanese Patent Publication No. 2010-138393 [Patent Document 12] Japanese Patent Publication No. 2015-174877 [Patent Document 13] International Publication No. 2014 / 123005 [Non-patent literature]

[0013] [Non-Patent Document 1] Hideyuki Higashimura, Shiro Kobayashi, Chemistry and Industry, 53, 501 (2000) [Overview of the Initiative] [Problems that the invention aims to solve]

[0014] The materials described in Patent Documents 1 and 2 still have room for improvement in performance such as heat resistance and etching resistance, and there is a need to develop new materials that are even superior in these physical properties. Furthermore, the polyphenol resin obtained based on the method described in Non-Patent Document 1 comprises both oxyphenol units and units having phenolic hydroxyl groups in their molecules. Oxyphenol units are typically obtained by bonding between a carbon atom on the aromatic ring of one phenol monomer and a phenolic hydroxyl group of the other phenol monomer. The aforementioned units having phenolic hydroxyl groups in their molecules are obtained by bonding between carbon atoms on the aromatic rings of phenol monomers. Such polyphenol resins are flexible polymers because the aromatic rings are bonded to each other via oxygen atoms, but they are undesirable from the viewpoint of crosslinkability and heat resistance because the phenolic hydroxyl groups disappear.

[0015] As mentioned above, numerous lithography film-forming materials have been proposed, but none have achieved a high level of both heat resistance and etching resistance, and the development of new materials is needed.

[0016] Furthermore, while numerous compositions for optical components have been proposed, none have achieved a high level of balance between heat resistance, transparency, and refractive index, necessitating the development of new materials.

[0017] This invention has been made in view of the above-mentioned problems, and aims to provide polymers and the like that have superior performance in terms of heat resistance, etching resistance, and other properties. [Means for solving the problem]

[0018] The inventors of the present invention conducted extensive research to solve the aforementioned problems and, as a result, discovered that the problems could be solved by using a polymer having a specific structure, thus completing the present invention.

[0019] In other words, the present invention encompasses the following embodiments. [1] A polymer having repeating units derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds represented by formulas (1A) and (1B), A polymer in which the repeating units are linked together by direct bonds between aromatic rings. [ka] (In formulas (1A) and (1B), R is independently a C1-C40 alkyl group which may be substituted, a C6-C40 aryl group which may be substituted, a C2-C40 alkenyl group which may be substituted, a C2-C40 alkynyl group which may be substituted, a C1-C40 alkoxy group which may be substituted, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group, and at least one R is a group containing a hydroxyl group, and m is independently an integer from 1 to 10.) [2] The polymer according to [1], wherein the aromatic hydroxy compounds represented by formulas (1A) and (1B) are, respectively, aromatic hydroxy compounds represented by formulas (2A) and (2B). [ka] (In equations (2A) and (2B), m 1 m is an integer between 0 and 10. 2 m is an integer between 0 and 10, and at least one m 1 or m 2 (This is an integer greater than or equal to 1.) [3] The polymer according to [1], wherein the aromatic hydroxy compounds represented by formulas (1A) and (1B) are aromatic hydroxy compounds represented by formulas (3A) and (3B), respectively. [ka] (In formulas (3A) and (3B), m 1’ (This is an integer between 1 and 10.) [4] A polymer having repeating units represented by the following formula (1A). [ka] (In formula (1A), A is an aryl group having 6 to 40 carbon atoms, which may have substituents. R 1is, independently of each other, a hydrogen atom, an alkyl group having 1 to 40 carbon atoms which may have a substituent, or an aryl group having 6 to 40 carbon atoms which may have a substituent, R 2 is, independently of each other, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group, m is, independently of each other, an integer of 0 to 4, n is, independently of each other, an integer of 1 to 3, p is an integer of 2 to 10, The symbol * represents the bonding position with an adjacent repeating unit.). [5] The polymer according to [4], wherein the repeating unit represented by the formula (1A) is the repeating unit represented by the formula (1-1-1) and / or the repeating unit represented by the formula (1-1-2).

Chemical formula

Chemical formula

Chemical formula

[10] The polymer according to [9], wherein the aromatic hydroxy compound represented by formula (1) is an aromatic hydroxy compound represented by the following formula (1-1). [ka] (In formula (1-1), R 1 And n are equivalent to those explained in equation (1) above.

[11] The aforementioned R 1 However, R A -R B The group is represented by the R A is a methine group, and the R B The polymer according to any one of [8] to

[10] , wherein is an aryl group having 6 to 40 carbon atoms, which may have substituents.

[12] A polymer having repeating units derived from heteroatom-containing aromatic monomers, A polymer in which the repeating units are linked together by direct bonding between the aromatic rings of the heteroatom-containing aromatic monomers.

[13] The polymer according to

[12] , wherein the heteroatom-containing aromatic monomer comprises a heterocyclic aromatic compound.

[14] The polymer according to

[12] or

[13] , wherein the heteroatom in the heteroatom-containing aromatic monomer comprises at least one selected from the group consisting of nitrogen atoms, phosphorus atoms, and sulfur atoms.

[15] The polymer according to any one of

[12] to

[14] , wherein the heteroatom-containing aromatic monomer comprises a monomer represented by the following formula (1-1), whether substituted or unsubstituted, or a monomer represented by the following formula (1-2), whether substituted or unsubstituted. [ka] (In the above equation (1-1), X is independently of NR 0 A group represented by a sulfur atom, an oxygen atom, or PR 0 It is a group represented by R 0 and R 1 Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. [ka] (In the above formula (1-2), Q 1 and Q 2Q is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylylene group having 2 to 20 carbon atoms, a carbonyl group, a group represented by NRa, an oxygen atom, a sulfur atom, or a group represented by PRa, where Ra is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a halogen atom, where Q is the monomer. 1 and Q 2 If both are present, at least one of them contains a heteroatom, and in the monomer Q 1 If only Q exists, 1 It contains heteroatoms, Q 3 Q is a group represented by a nitrogen atom, a phosphorus atom, or CRb, where Q is the monomer. 3 It contains heteroatoms, The aforementioned Ra and Rb are, independently, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a halogen atom.

[16] In the above equation (1-1), R 1 The polymer according to

[15] , wherein is a substituted or unsubstituted phenyl group.

[17] A polymer according to any one of

[12] to

[16] , further comprising a monomer-derived structural unit represented by the following formula (2). [ka] (In formula (2), Q4 and Q5 are single-bonded, substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 20 carbon atoms, and substituted or unsubstituted alkynylene groups having 2 to 20 carbon atoms. Q6 is a group represented by CRb', where Rb is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[18] The polymer according to any one of [1] to

[17] , further comprising a modified portion derived from a crosslinking reactive compound.

[19] A polymer according to any of [1] to

[18] , having a weight-average molecular weight of 400 to 100,000.

[20] The polymer according to any one of [1] to

[19] , wherein the solubility in 1-methoxy-2-propanol and / or propylene glycol monomethyl ether acetate is 1% by mass or more. [twenty one] The polymer according to

[20] , wherein the solubility is 10% by mass or more. [twenty two] A composition comprising the polymer described in any of [1] to

[21] . [twenty three] The composition according to

[22] , further comprising a solvent. [twenty four] The composition according to

[23] , wherein the solvent comprises one or more selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, ethyl lactate, and methyl hydroxyisobutyrate. [twenty five] The composition according to any one of

[22] to

[24] , wherein the content of impurity metals is less than 500 ppb for each type of metal.

[26] The composition according to

[25] , wherein the impurity metal contains at least one selected from the group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium.

[27] The composition according to

[25] or

[26] , wherein the content of the aforementioned impurity metal is 1 ppb or less for each type of metal.

[28] A method for producing a polymer according to any one of [1] to

[21] , A method for producing a polymer, comprising the step of polymerizing one or more monomers corresponding to the repeating units in the presence of an oxidizing agent.

[29] The method for producing a polymer according to

[28] , wherein the oxidizing agent is a metal salt or metal complex containing at least one selected from the group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium.

[30] A film-forming composition comprising a polymer described in any of [1] to

[21] .

[31] A resist composition comprising the film-forming composition described in

[30] .

[32] The resist composition according to

[31] , further comprising at least one selected from the group consisting of a solvent, an acid generator, and an acid diffusion control agent.

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

[31] or

[32] , A step of exposing at least a portion of the formed resist film, A step of developing the exposed resist film to form a resist pattern, A method for forming a resist pattern, including the method described above.

[34] A radiation-sensitive composition comprising the film-forming composition described in

[30] , a diazonaphthoquinone photoactive compound, and a solvent, The content of the solvent is 20 to 99% by mass relative to 100% by mass of the total amount of the radiation-sensitive composition. A radiation-sensitive composition in which the content of solids other than the solvent is 1 to 80% by mass relative to 100% by mass of the total amount of the radiation-sensitive composition.

[35] A step of forming a resist film on a substrate using the radiation-sensitive composition described in

[34] , A step of exposing at least a portion of the formed resist film, A method for forming a resist pattern, comprising the step of developing the exposed resist film to form a resist pattern.

[36] A composition for forming a lower layer film for lithography, comprising the film-forming composition described in

[30] .

[37] A lithography underlayer film forming composition according to

[36] , further comprising at least one selected from the group consisting of a solvent, an acid generator, and a crosslinking agent.

[38] A method for producing a lithography underlayer film, comprising the step of forming an underlayer film on a substrate using the lithography underlayer film forming composition described in

[36] or

[37] .

[39] A step of forming a base layer on a substrate using the lithography base layer formation composition described in

[36] or

[37] , The steps include forming at least one photoresist layer on the aforementioned lower film, The process involves irradiating a predetermined region of the photoresist layer with radiation and developing it to form a resist pattern. A method for forming a resist pattern, comprising the characteristics of a resist pattern.

[40] A step of forming a base layer on a substrate using the lithography base layer formation composition described in

[36] or

[37] , The process of forming an intermediate layer on the aforementioned lower layer using a resist intermediate layer material containing silicon atoms, The steps include forming at least one photoresist layer on the aforementioned intermediate layer film, The process involves irradiating a predetermined region of the photoresist layer with radiation and developing it to form a resist pattern. The process involves etching the intermediate layer using the resist pattern as a mask to form an intermediate layer pattern, The process involves etching the underlying film using the aforementioned intermediate film pattern as an etching mask to form a lower film pattern, The steps include: etching the substrate using the aforementioned lower layer film pattern as an etching mask to form a pattern on the substrate; A circuit pattern formation method having the following characteristics.

[41] A composition for forming an optical component, comprising the film-forming composition described in

[30] .

[42] The optical component forming composition according to

[41] , further comprising at least one selected from the group consisting of a solvent, an acid generator, and a crosslinking agent. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide polymers and the like that have superior performance in terms of heat resistance, etching resistance, and other properties. [Modes for carrying out the invention]

[0021] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). This embodiment is illustrative for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0022] In this specification, unless otherwise defined, "substitution" means that one or more hydrogen atoms in a functional group are replaced by a substituent. Substituents are not particularly limited, but examples include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, thiol groups, heterocyclic groups, alkyl groups having 1 to 30 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 to 30 carbon atoms, acyl groups having 1 to 30 carbon atoms, and amino groups having 0 to 30 carbon atoms. Furthermore, unless otherwise defined, "alkyl group" includes linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups. With respect to the structural formulas described herein, for example, if the line indicating a bond with a certain group C is in contact with rings A and B, as in the formula below, it means that C may be bonded to either ring A or ring B. That is, each of the n groups C in the formula below may be independently bonded to either ring A or ring B. [ka]

[0023] <polymer> The polymer of this embodiment has a predetermined structure and exhibits superior performance in terms of heat resistance, etching resistance, and other properties. Among the polymers of this embodiment, those having hydroxyl groups bonded to aromatic rings may be referred to as "polycyclic polyphenol resins." As described later, examples of polymers in this embodiment include the polymer according to the first embodiment (hereinafter also referred to as the "first polymer"), the polymer according to the second embodiment (hereinafter also referred to as the "second polymer"), the polymer according to the third embodiment (hereinafter also referred to as the "third polymer"), and the polymer according to the fourth embodiment (hereinafter also referred to as the "fourth polymer"). In other words, the polymers of this embodiment encompass the first polymer, the second polymer, the third polymer, and the fourth polymer.

[0024] In this specification, the aromatic hydroxy compounds represented by formulas (1A) and (1B) described in the section [First Polymer] below and the compounds listed as suitable therefor shall be referred to as "Compound Group 1," the aromatic hydroxy compounds represented by formula (1A-1) described in the section [Second Polymer] and the compounds listed as suitable therefor shall be referred to as "Compound Group 2," the aromatic hydroxy compounds represented by formulas (1A) and (2A) described in the section [Third Polymer] and the compounds listed as suitable therefor shall be referred to as "Compound Group 3," and the heteroatom-containing aromatic monomers described in the section [Fourth Polymer] and the compounds listed as suitable therefor shall be referred to as "Compound Group 4," and the formula numbers assigned to each compound below shall be the individual formula numbers for each compound group. That is, for example, the aromatic hydroxy compound represented by formula (1A) described in the section [First Polymer] and the compounds listed as suitable therefor shall be distinguished as being different from the aromatic hydroxy compound represented by formula (1A) described in the section [Third Polymer] and the compounds listed as suitable therefor.

[0025] [First Polymer] The first polymer is a polymer having repeating units derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds represented by the following formulas (1A) and (1B), wherein the repeating units are linked to each other by direct bonds between aromatic rings. Because the first polymer is constructed in this way, it has superior performance in terms of heat resistance, etching resistance, and other properties. [ka] (In formulas (1A) and (1B), R is independently a C1-C40 alkyl group which may be substituted, a C6-C40 aryl group which may be substituted, a C2-C40 alkenyl group which may be substituted, a C2-C40 alkynyl group which may be substituted, a C1-C40 alkoxy group which may be substituted, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group, and at least one R is a group containing a hydroxyl group, and m is independently an integer from 1 to 10.)

[0026] The formulas (1A) and (1B) in the section on [First Polymer] will be explained in detail below. The first polymer, as defined above for formulas (1A) and (1B), has a repeating unit containing at least one hydroxyl group, and therefore can also be referred to as a polycyclic polyphenol resin.

[0027] In formulas (1A) and (1B), R is independently a C1-C40 alkyl group which may be substituted, a C6-C40 aryl group which may be substituted, a C2-C40 alkenyl group which may be substituted, a C2-C40 alkynyl group which may be substituted, a C1-C40 alkoxy group which may be substituted, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group. Here, the alkyl group may be linear, branched, or cyclic. Here, at least one of R is a hydroxyl group.

[0028] Examples of alkyl groups having 1 to 40 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-dodecyl, and barrel groups. Examples of aryl groups having 6 to 40 carbon atoms include, but are not limited to, phenyl, naphthalene, biphenyl, anthrasyl, pyrenyl, and perylene groups. Alkenyl groups having 2 to 40 carbon atoms are not limited to the following, but examples include ethynyl, propenyl, butynyl, and pentynyl groups. Examples of alkynyl groups having 2 to 40 carbon atoms include, but are not limited to, acetylene groups and ethynyl groups. Examples of alkoxy groups having 1 to 40 carbon atoms include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Examples of halogen atoms include, but are not limited to, fluorine, chlorine, bromine, and iodine. Examples of heterocyclic groups include, but are not limited to, pyridine, pyrrole, pyridazine, thiophene, imidazole, furan, pyrazole, oxazole, triazole, thiazole, or benzo-fused compounds thereof.

[0029] Each of the values ​​of m is an independent integer from 1 to 10. From the viewpoint of solubility, values ​​from 1 to 4 are preferred, and from the viewpoint of raw material availability, values ​​from 1 to 2 are preferred.

[0030] In this embodiment, the aromatic hydroxy compound can be represented by formula (1A) or formula (1B) above, either alone or in combination of two or more. In this embodiment, from the viewpoint of heat resistance, it is preferable to use the compound represented by formula (1A) above as the aromatic hydroxy compound. Furthermore, from the viewpoint of solubility, it is preferable to use the compound represented by formula (1B) above as the aromatic hydroxy compound.

[0031] In this embodiment, from the viewpoint of combining heat resistance and solubility, and ease of manufacture, the aromatic hydroxy compounds represented by formulas (1A) and (1B) above are preferably the compounds represented by the following formulas (2A) and (2B), respectively.

[0032] [ka] (In equations (2A) and (2B), m 1 m is an integer between 0 and 10. 2 m is an integer between 0 and 10, and at least one m 1 or m 2 (This is an integer greater than or equal to 1.)

[0033] In this embodiment, from the viewpoint of ease of manufacture, the aromatic hydroxy compounds represented by formulas (1A) and (1B) above are preferably the compounds represented by the following formulas (3A) and (3B), respectively. [ka] (In formulas (3A) and (3B), m 1’ (This is an integer between 1 and 10.)

[0034] Specific examples of aromatic hydroxy compounds represented by formulas (1A), (2A), and (3A) are shown below, but are not limited to those listed here.

[0035] [ka] [ka]

[0036] In the above formula, R 3Each of these is independently a hydrogen atom, an optionally substituted C1-C40 alkyl group, an optionally substituted C6-C40 aryl group, an optionally substituted C2-C40 alkenyl group, an optionally substituted C2-C40 alkynyl group, an optionally substituted C1-C40 alkoxy group, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group. Here, the alkyl group may be linear, branched, or cyclic.

[0037] [ka]

[0038] The bonding order of the repeating units in the first polymer is not particularly limited. For example, there may be two or more repeating units consisting of only one unit derived from the aromatic hydroxy compound represented by formula (1A) or formula (1B), or there may be one or more units each derived from the aromatic hydroxy compound represented by formula (1A) or formula (1B). The order may also be either block copolymerization or random copolymerization.

[0039] The positions where repeating units in the first polymer are directly bonded to each other are not particularly limited. When the repeating units are represented by the general formula (1A) or formula (1B), any one carbon atom that is not bonded to a phenolic hydroxyl group or other substituents is involved in the direct bonding between monomers. In the first polymer, "the repeating units are linked by direct bonding between aromatic rings" means, as an example, that in the polymer, the carbon atoms on the aromatic ring, indicated by the aryl structure in parentheses in the formula of one repeating unit (1A), and the carbon atoms on the aromatic ring, indicated by the aryl structure in parentheses in the formula of the other repeating unit (1A), are directly bonded by single bonds, that is, without the involvement of other atoms such as carbon atoms, oxygen atoms, or sulfur atoms. Furthermore, the first polymer may include the following embodiments. (1) In one repeating unit (1A), when R is an aryl group (including when R is a 2n-valent group having an aryl group), the atom on the aromatic ring of the aryl group and the atom on the aromatic ring of the other repeating unit (1A), which is indicated by the aryl structure in parentheses in the formula, are directly bonded by a single bond. (2) In one repeating unit (1A) and the other, when R is an aryl group (including when R is a 2n-valent group having an aryl group), the atoms on the aromatic ring of the aryl group represented by R are directly bonded to each other by a single bond between one repeating unit (1A) and the other. In the first polymer, in either embodiment (1) or (2) above, from the viewpoint of heat resistance, it is preferable that one carbon atom of any of the aromatic rings having a phenolic hydroxyl group is involved in the direct bonding between the aromatic rings.

[0040] In the first polymer, the number and ratio of each repeating unit are not particularly limited, but it is preferable to adjust them as appropriate considering the application and the molecular weight values ​​described below. Furthermore, the first polymer may consist only of repeating units (1A) and / or (1B), but may also include other repeating units as long as the performance according to the application is not impaired. Other repeating units include, for example, repeating units having ether bonds formed by the condensation of phenolic hydroxyl groups, and repeating units having ketone structures. These other repeating units may also be directly bonded to repeating units (1A) and / or (1B) via aromatic rings. For example, the molar ratio [Y / X] of the total amount (Y) of repeating units (1A) and / or (1B) to the total amount (X) of the first polymer can be 0.05 to 1.00, preferably 0.45 to 1.00. The weight-average molecular weight of the first polymer is not particularly limited, but is preferably in the range of 400 to 100,000, more preferably 500 to 15,000, and even more preferably 1,000 to 12,000. The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn) in the first polymer is not particularly limited in range, as the required ratio varies depending on the application. However, as polymers having a more homogeneous molecular weight, for example, those in the range of 3.0 or less are preferred, those in the range of 1.05 to 3.0 are more preferred, those in the range of 1.05 to less than 2.0 are particularly preferred, and those in the range of 1.05 to less than 1.5 are even more preferred from the viewpoint of heat resistance.

[0041] The first polymer is preferably highly soluble in the solvent, from the viewpoint of facilitating the application of wet processes. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) is used as the solvent, the first polymer is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 20% by mass or more, and most preferably 30% by mass or more at a temperature of 23°C. Here, the solubility in PGME and / or PGMEA is defined as "mass of the first polymer ÷ (mass of the first polymer + mass of the solvent) × 100 (mass%)". For example, 10 g of the first polymer is evaluated as dissolving in 90 g of PGMEA when the solubility of the first polymer in PGMEA is "10% by mass or more", and it is evaluated as not dissolving when the solubility is "less than 10% by mass".

[0042] Assuming application to at least one application selected from the group consisting of compositions, polymer manufacturing methods, film-forming compositions, resist compositions, resist pattern formation methods, radiation-sensitive compositions, lithography underlayer film formation compositions, lithography underlayer film manufacturing methods, circuit pattern formation methods, and optical component formation compositions, and from the viewpoint of further improving heat resistance and etching resistance, it is particularly preferable that the first polymer be at least one selected from the group consisting of ANT-1, ANT-2, ANT-3, ANT-4, and PYL-5 described in the examples below.

[0043] [Second Polymer] The second polymer has repeating units represented by the following formula (1A). Because of this configuration, the second polymer exhibits superior performance in terms of heat resistance, etching resistance, and other properties. In addition to heat resistance and etching resistance, the second polymer can exhibit superior performance in other areas, such as resist pattern formation, adhesion and embedding to resist layers and resist interlayer materials, film formation, transparency, and refractory coefficient. [ka] (In formula (1A), A is an aryl group having 6 to 40 carbon atoms, which may have substituents. R 1 Each of these is independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms which may have substituents, or an aryl group having 6 to 40 carbon atoms which may have substituents. R 2 Each of these is independently an alkyl group having 1 to 40 carbon atoms which may be substituted, an aryl group having 6 to 40 carbon atoms which may be substituted, an alkenyl group having 2 to 40 carbon atoms which may be substituted, an alkynyl group having 2 to 40 carbon atoms which may be substituted, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group. m is an integer between 0 and 4, independently of each other. n is an integer between 1 and 3, independently of each other. p is an integer between 2 and 10. The symbol * indicates a connection point with an adjacent repeating unit.

[0044] The formula (1A) in the section on [Second Polymer] will be explained in detail below. As is clear from the above formula (1A), the second polymer has at least one hydroxyl group in its repeating unit, and therefore can also be called a polycyclic polyphenol resin.

[0045] In formula (1A), A is an aryl group having 6 to 40 carbon atoms, which may have substituents, and R 1 Each of these is independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms which may have substituents, or an aryl group having 6 to 40 carbon atoms which may have substituents, and R 2 Each of these is independently an alkyl group having 1 to 40 carbon atoms which may have substituents, an aryl group having 6 to 40 carbon atoms which may have substituents, an alkenyl group having 2 to 40 carbon atoms which may have substituents, an alkynyl group having 2 to 40 carbon atoms which may have substituents, an alkoxy group having 1 to 40 carbon atoms which may have substituents, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group, each independently being an integer from 0 to 4, each independently being an integer from 1 to 3, and p being an integer from 2 to 10, and the symbol * represents a bond site with an adjacent repeating unit.

[0046] The second polymer has a structure in which repeating units represented by formula (1A) are bonded to each other. That is, the second polymer has a structure in which aromatic rings represented by the aryl structure in A of the polymer are directly bonded to each other. The second polymer may be a homopolymer in which one type of repeating unit represented by formula (1A) is continuously bonded, or it may be a copolymer having two or more types of repeating units represented by formula (1A) and repeating units derived from other copolymer components. Furthermore, if it is such a copolymer, it may be a block copolymer or a random copolymer. The second polymer is more preferably a homopolymer in which one type of repeating unit represented by formula (1A) is continuously bonded, as this provides better heat resistance, better solubility in solvents, and better moldability. In the second polymer, "direct bonding of aromatic rings" means, as an example, that in the polymer, the carbon atoms on the aromatic ring represented by the aryl structure in A of one repeating unit (1A) and the carbon atoms on the aromatic ring represented by the aryl structure in A of the other repeating unit (1A) are directly bonded by a single bond, that is, without the involvement of other atoms such as carbon atoms, oxygen atoms, or sulfur atoms. Furthermore, the second polymer may include the following embodiments. (1) In one repeating unit (1A), R 1 and R 2 If either of them is an aryl group (R 1 A configuration in which an atom on the aromatic ring of the aryl group and an atom on the aromatic ring of the other repeating unit (1A), represented by the aryl structure in A of the formula, are directly bonded by a single bond (including the case where is a 2n+1 valent group having an aryl group). (2) In the repeating units (1A) of one and the other, R 1 and R 2 If either of them is an aryl group (R 1 (Including the case where is a 2n+1 valent group having an aryl group), between one repeating unit (1A) and the other, R 1 and R 2 A configuration in which atoms on the aromatic ring of the aryl group shown are directly bonded to each other by single bonds. Furthermore, in the second polymer, unless otherwise specified, the compound that forms the basis of the polymer structure is called an aromatic hydroxy compound. The second polymer is obtained by using the aromatic hydroxy compound that forms the basis of its structure as a monomer, and has a structure in which aromatic rings represented by the aryl structure in A in the polymer are directly bonded to each other. For example, a polymer having a repeating unit represented by formula (1A) is obtained by using the aromatic hydroxy compound represented by the following formula (1A-1) as a monomer, and by the direct bonding of aromatic rings represented by the aryl structure in A in formula (1A-1). [ka] (In formula (1A-1), A, R1 , R 2 m, n, and p are equivalent to those in equation (1A).

[0047] In formula (1A), A is an aryl group having 6 to 40 carbon atoms, which may have substituents. Examples of aryl groups having 6 to 40 carbon atoms include phenyl, naphthalene, biphenyl, anthrasyl, pyrenyl, and perylene groups. Among these, phenyl and naphthalene groups are preferred because they offer excellent solubility and superior performance in terms of heat resistance, etching resistance, storage stability, resist pattern formation, adhesion and embedding to resist layers and resist intermediate film materials, film formation, transparency, and refractory properties.

[0048] R 1 Each of these is independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms which may have substituents, or an aryl group having 6 to 40 carbon atoms which may have substituents. 1 From the viewpoint of combining high heat resistance and excellent solubility, it is preferable that the aryl group has 6 to 40 carbon atoms, which may have substituents. R 1 From the viewpoint of having a combination of solubility, heat resistance, and etching resistance, carboxyl groups, cyano groups, nitro groups, thiol groups, and heterocyclic groups are preferred as substituents, carboxyl groups, cyano groups, nitro groups, and thiol groups are more preferred, carboxyl groups and cyano groups are even more preferred, and cyano groups are even more preferred.

[0049] Examples of alkyl groups having 1 to 40 carbon atoms that may have substituents include methyl group, hydroxymethyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, cyanobutyl group, nitrobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-dodecyl group, and barrel group. Examples of C6-C40 aryl groups that may have substituents include phenyl, cyclohexylphenyl, phenol, cyanophenyl, nitrophenyl, naphthalene, biphenyl, anthracene, naphthacene, anthrasyl, pyrenyl, perylene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, ovalene, fluorene, benzofluorene, and dibenzofluorene. R 1 As for the choice of group, hydrogen atoms, phenyl groups, phenol groups, cyanophenyl groups, cyclohexylphenyl groups, and naphthalene groups are preferred, and hydrogen atoms, phenol groups, cyanophenyl groups, and cyclohexylphenyl groups are more preferred, as they provide even better heat resistance, even better solubility in solvents, and even better moldability. Furthermore, these groups are more preferred because, in addition to their excellent heat resistance, they tend to have a high n value and a low k value at the wavelength of 193 nm used in ArF lithography, resulting in excellent pattern transferability. Also, R 1 These may be heterocycles such as pyridine, pyrrole, pyridazine, thiophene, imidazole, furan, pyrazole, oxazole, triazole, and thiazole, as well as their benzo-fused ring derivatives.

[0050] R 2 Each of these is independently an alkyl group having 1 to 40 carbon atoms, which may be substituted; an aryl group having 6 to 40 carbon atoms, which may be substituted; an alkenyl group having 2 to 40 carbon atoms, which may be substituted; an alkoxy group having 1 to 40 carbon atoms, which may be substituted; a halogen atom; a thiol group; an amino group; a nitro group; a cyano group; a nitro group; a heterocyclic group; a carboxyl group; or a hydroxyl group. Here, the alkyl group may be linear, branched, or cyclic.

[0051] Examples of alkyl groups having 1 to 40 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-dodecyl group, and barrel group. Examples of aryl groups having 6 to 40 carbon atoms include phenyl, naphthalene, biphenyl, anthrasyl, pyrenyl, and perylene groups. Examples of alkenyl groups having 2 to 40 carbon atoms include the ethynyl group, propenyl group, butynyl group, and pentynyl group. Examples of alkynyl groups having 2 to 40 carbon atoms include acetylene groups and ethynyl groups. Examples of alkoxy groups having 1 to 40 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups.

[0052] R 2 i-propyl groups, i-butyl groups, and t-butyl groups are preferred, with t-butyl groups being more preferred, because they provide excellent solubility and exhibit superior performance in terms of heat resistance, etching resistance, storage stability, resist pattern formation, adhesion and embedding to resist layers and resist intermediate film materials, film formation, transparency, and refractory properties.

[0053] Each of the values ​​of m is an integer between 0 and 4, independently of the others. From the viewpoint of solubility, integers between 0 and 2 are preferred, integers between 0 and 1 are more preferred, and from the viewpoint of raw material availability, 0 is even more preferred.

[0054] n is an integer between 1 and 3, independently of other integers. From the viewpoint of combining solubility and heat resistance, and from the viewpoint of raw material availability, an integer between 1 and 2 is preferred, and 2 is more preferred.

[0055] p is an integer between 2 and 10. From the viewpoint of combining solubility and heat resistance, an integer between 3 and 8 is preferred, an integer between 4 and 6 is more preferred, and 4 is even more preferred.

[0056] In this embodiment, the repeating unit represented by formula (1A) is preferably the repeating unit represented by formula (1-1-1) and / or the repeating unit represented by formula (1-1-2) from the viewpoint of ease of manufacture. [ka] [ka]

[0057] In equations (1-1-1) and (1-1-2), R 1 , R 2 , m, n, p, and the symbol * are equivalent to equation (1A).

[0058] In this embodiment, the repeating unit represented by formula (1A) is more preferably at least one selected from the repeating units represented by formula (1-2-1) to formula (1-2-4) from the viewpoint of ease of manufacture. [ka] [ka] [ka] [ka]

[0059] In formulas (1-2-1) to (1-2-4), R 1 , R 2 , m, p, and the symbol * are equivalent to equation (1A).

[0060] In this embodiment, the repeating unit represented by formula (1A) is more preferably at least one selected from the repeating units represented by formula (1-3-1) to formula (1-3-12) from the viewpoint of ease of manufacture. [ka] [ka] [ka]

[0061] In formulas (1-3-1) to (1-3-12), R 1 , p, and the symbol * are equivalent to equation (1A).

[0062] R 3 Each of these is independently a hydrogen atom, an optionally substituted C1-C40 alkyl group, an optionally substituted C6-C40 aryl group, an optionally substituted C2-C40 alkenyl group, an optionally substituted C2-C40 alkynyl group, an optionally substituted C1-C40 alkoxy group, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group. Here, the alkyl group may be linear, branched, or cyclic.

[0063] In this embodiment, the repeating unit represented by formula (1A) is more preferably at least one selected from the repeating units represented by formula (1-3-1), formula (1-3-2), and formula (1-3-9), as it is easier to manufacture, provides better heat resistance, has superior solubility in solvents, and has superior moldability. Furthermore, in equations (1-3-1) to (1-3-12), R is used from the viewpoint of ease of manufacture. 3 It is more preferable that each of these groups independently be a hydrogen atom, an alkyl group having 1 to 40 carbon atoms which may have substituents, and an aryl group having 6 to 40 carbon atoms which may have substituents. As for the alkyl group having 1 to 40 carbon atoms which may have substituents, it is more preferable that it be a hydrogen atom, an i-propyl group, an i-butyl group, and a t-butyl group, with a hydrogen atom and a t-butyl group being particularly preferred, because they are easy to manufacture, have excellent solubility in solvents, and have superior moldability.

[0064] In this embodiment, the repeating unit represented by formula (1A) is more preferably at least one selected from the repeating units represented by formula (1-4-1) to formula (1-4-12) from the viewpoint of ease of manufacture.

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] In formulas (1-4-1) to (1-4-12), R 1 , p, and the symbol * are equivalent to equation (1A).

[0069] In this embodiment, the repeating unit represented by formula (1A) is more preferably at least one selected from the repeating units represented by formula (1-4-2) and formula (1-4-7), as it is easier to manufacture, provides even better heat resistance, has even better solubility in solvents, and has even better moldability.

[0070] R 1 It is preferable that the group is a hydrogen atom and one of the groups of formulas (2-1-1) to (2-1-37) because it has a better balance of solubility, heat resistance, and etching resistance. If the polymer has multiple repeating units represented by formula (1A), the R in those repeating units represented by formula (1A) 1R may be a hydrogen atom or one of the groups from formulas (2-1-1) to (2-1-37), and each repeating unit may have a different group. In each group, the dashed portion indicates the main structure of the polymer and represents the bond with the carbon atom of -CH- in formula (1A). Also, in each group, 4 R 3 It is synonymous with [the above].

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] R 1 It is more preferable that the group is a hydrogen atom or one of the groups of formula (2-1-17), formula (2-1-19), or formula (2-1-29), as this provides a better balance of solubility, heat resistance, and etching resistance.

[0079] The weight-average molecular weight (Mw) of the second polymer is preferably in the range of 400 to 100,000, more preferably 500 to 15,000, and even more preferably 3,200 to 12,000. The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn) in the second polymer varies depending on its application. However, a more homogeneous molecular weight is preferable to obtain excellent heat resistance, so it is preferably 3.0 or less, more preferably 1.05 to 3.0, even more preferably 1.05 to 2.0, and even more preferably 1.05 to 1.7 for even better heat resistance. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined by GPC measurement in terms of polystyrene equivalent.

[0080] The number of repeating units represented by formula (1A) in the second polymer is preferably 2 to 300, more preferably 2 to 100, and even more preferably 2 to 10, from the viewpoint of obtaining high heat resistance. If two or more types of repeating units represented by formula (1A) are included, the total number of these units is used, and their composition ratio can be appropriately adjusted considering the application and the weight-average molecular weight.

[0081] Furthermore, the second polymer can consist only of repeating units (1A), but may also include other repeating units as long as it does not impair the performance according to the application. Other repeating units include, for example, repeating units having ether bonds formed by the condensation of phenolic hydroxyl groups, and repeating units having ketone structures. These other repeating units may also be directly bonded to repeating unit (1A) via aromatic rings. For example, the molar ratio [Y / X] of the molar amount of repeating units (1A) to the total molar amount (X) of repeating units contained in the second polymer is 5 to 100, preferably 45 to 100.

[0082] In the second polymer, the carbon atoms in the aryl group in formula (1A) are involved in the direct bonding between monomers, for example, at the positions where the repeating units are directly bonded to each other. In the second polymer, it is preferable that carbon atoms in the aromatic ring having a phenolic hydroxyl group are involved in the direct bonding between monomers, as this provides superior heat resistance.

[0083] The second polymer may contain repeating units having ether bonds formed by the condensation of phenolic hydroxyl groups, to the extent that it does not impair performance depending on the application. It may also contain ketone structures.

[0084] The second polymer is preferably highly soluble in the solvent, from the viewpoint of facilitating the application of wet processes. For example, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) is used as the solvent, the second polymer is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more at a temperature of 23°C. Here, the solubility in PGME and / or PGMEA is defined as "total amount of the second polymer / (total amount of the second polymer + total amount of solvent) × 100 (mass%)". For example, 10g of the second polymer is evaluated as soluble in 90g of PGMEA when the solubility of the second polymer in PGMEA is "1% by mass or more", and the solubility is evaluated as not being high when the solubility is "less than 1% by mass".

[0085] Assuming application to at least one application selected from the group consisting of compositions, polymer manufacturing methods, film-forming compositions, resist compositions, resist pattern formation methods, radiation-sensitive compositions, lithography underlayer formation compositions, lithography underlayer production methods, circuit pattern formation methods, and optical component formation compositions, and from the viewpoint of further improving heat resistance and etching resistance, it is particularly preferable that the second polymer be at least one selected from the group consisting of RCA-1, RCR-1, RCR-2, RCN-1, and RCN-2 described in the examples below.

[0086] [Third Polymer] The third polymer is a polymer containing repeating units derived from at least one selected from the group consisting of aromatic hydroxy compounds represented by the following formulas (1A) and (2A), wherein the repeating units are linked to each other by direct bonds between aromatic rings. Because of this configuration, the third polymer has superior performance in terms of heat resistance, etching resistance, and other properties. [ka] (In formula (1A), R 1 R is a 2n-valent group or single bond with 1 to 60 carbon atoms. 2 Each of these is independently an alkyl group having 1 to 40 carbon atoms which may be substituted, an aryl group having 6 to 40 carbon atoms which may be substituted, an alkenyl group having 2 to 40 carbon atoms which may be substituted, an alkynyl group having 2 to 40 carbon atoms which may be substituted, an alkoxy group having 1 to 40 carbon atoms which may be substituted, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group, or a hydroxyl group, where m is independently an integer from 0 to 3 and n is an integer from 1 to 4. In formula (2A), R 2 And m have the same meaning as those explained in formula (1A) above.

[0087] The formulas (1A) and (2A) in the section on [Third Polymer] will be explained in detail below. As is clear from formulas (1A) and (2A), the third polymer has at least two hydroxyl groups in its repeating units, and therefore can also be referred to as a polycyclic polyphenol resin.

[0088] In formula (1A), R 1 This refers to a 2n-valent group or single bond with 1 to 60 carbon atoms. A 2n-valent group having 1 to 60 carbon atoms is, for example, a 2n-valent hydrocarbon group, and this hydrocarbon group may have various functional groups as substituents, as described later. Furthermore, a 2n-valent hydrocarbon group refers to an alkylene group having 1 to 60 carbon atoms when n=1, an alkanetetrayl group having 1 to 60 carbon atoms when n=2, an alkanehexyl group having 2 to 60 carbon atoms when n=3, and an alkaneoctile group having 3 to 60 carbon atoms when n=4. Examples of such 2n-valent hydrocarbon groups include groups formed by bonding a 2n+1-valent hydrocarbon group with a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group. Here, alicyclic hydrocarbon groups also include bridged alicyclic hydrocarbon groups. Examples of 2n+1 valent hydrocarbon groups include, but are not limited to, trivalent methine groups and ethyne groups. Furthermore, the 2n-valent hydrocarbon group may have a double bond, a heteroatom, and / or an aryl group having 6 to 59 carbon atoms. 1 It may also contain groups derived from compounds having a fluorene skeleton, such as fluorene and benzofluorene.

[0089] In the third polymer, the 2n-valent group may include a halogen group, a nitro group, an amino group, a hydroxyl group, an alkoxy group, a thiol group, or an aryl group having 6 to 40 carbon atoms. Furthermore, the 2n-valent group may include an ether bond, a ketone bond, an ester bond, or a double bond.

[0090] In the third polymer, the 2n-valent group preferably contains a branched hydrocarbon group or an alicyclic hydrocarbon group rather than a linear hydrocarbon group from the viewpoint of heat resistance, and more preferably contains an alicyclic hydrocarbon group. Further, in the third polymer, it is particularly preferable that the 2n-valent group has an aryl group having 6 to 60 carbon atoms.

[0091] Substituents that can be included in the 2n-valent group, the linear hydrocarbon group and the branched hydrocarbon group are not particularly limited. For example, unsubstituted methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-dodecyl group, barrel group and the like can be mentioned. Substituents that can be included in the 2n-valent group, the alicyclic hydrocarbon group and the aromatic group having 6 to 60 carbon atoms are not particularly limited. For example, unsubstituted phenyl group, naphthalene group, biphenyl group, anthracyl group, pyrenyl group, cyclohexyl group, cyclododecyl group, dicyclopentyl group, tricyclodecyl group, adamantyl group, phenylene group, naphthalenediyl group, biphenyldiyl group, anthracenediyl group, pyrenediyl group, cyclohexanediyl group, cyclododecanediyl group, dicyclopentanediyl group, tricyclodecanediyl group, adamantanediyl group, benzenetriyl group, naphthalenetriyl group, biphenyltriyl group, anthracenetriyl group, pyrenetriyl group, cyclohexanetriyl group, cyclododecanetriyl group, dicyclopentanetriyl group, tricyclodecanetriyl group, adamantanetriyl group, benzenetetrayl group, naphthalenetetrayl group, biphenyltetrayl group, anthracenetetrayl group, pyrenetetrayl group, cyclohexanetetrayl group, cyclododecanetetrayl group, dicyclopentanetetrayl group, tricyclodecanetetrayl group, adamantanetetrayl group and the like can be mentioned.

[0092] In formula (1A), R 2Each of these is independently an alkyl group having 1 to 40 carbon atoms, which may be substituted; an aryl group having 6 to 40 carbon atoms, which may be substituted; an alkenyl group having 2 to 40 carbon atoms, which may be substituted; an alkoxy group having 1 to 40 carbon atoms, which may be substituted; a halogen atom; a thiol group; an amino group; a nitro group; a cyano group; a nitro group; a heterocyclic group; a carboxyl group; or a hydroxyl group. Here, the alkyl group, etc., may be linear, branched, or cyclic.

[0093] Examples of alkyl groups having 1 to 40 carbon atoms include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-dodecyl, and barrel groups. Examples of aryl groups having 6 to 40 carbon atoms include, but are not limited to, phenyl, naphthalene, biphenyl, anthrasyl, pyrenyl, and perylene groups. Alkenyl groups having 2 to 40 carbon atoms are not limited to the following, but examples include ethynyl, propenyl, butynyl, and pentynyl groups. Examples of alkynyl groups having 2 to 40 carbon atoms include, but are not limited to, acetylene groups and ethynyl groups. Examples of alkoxy groups having 1 to 40 carbon atoms include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of heterocyclic groups include, but are not limited to, pyridine, pyrrole, pyridazine, thiophene, imidazole, furan, pyrazole, oxazole, triazole, thiazole, or benzo-fused compounds thereof.

[0094] In formula (1A), m is an independent integer between 0 and 3. From the viewpoint of solubility, m is preferably between 0 and 1, and from the viewpoint of raw material availability, m is even more preferably 0.

[0095] In formula (1A), n is an integer of 1 to 4, preferably 1 to 2. When n is an integer of 2 or more, the structural formulas within the n [ ] may be the same or different.

[0096] In formula (2A), R 2 and m have the same meanings as those described in formula (1A) above.

[0097] In the third polymer, the aromatic hydroxy compound represented by the formula (1A) or the formula (2A) can be used alone or two or more thereof can be used together. In the third polymer, from the viewpoint of heat resistance, it is preferable to employ the one represented by the formula (1A) as the aromatic hydroxy compound. Also, from the viewpoint of solubility, it is preferable to employ the one represented by the formula (2A) as the aromatic hydroxy compound.

[0098] In the third polymer, the aromatic hydroxy compound represented by the formula (1A) is preferably a compound represented by the following formula (1) from the viewpoints of兼备 of heat resistance and solubility and ease of production. [Chemical formula] (In formula (1), R 1 , R 2 , m and n have the same meanings as those described in formula (1A) above.)

[0099] In the third polymer, the aromatic hydroxy compound represented by the formula (1) is preferably an aromatic hydroxy compound represented by the following formula (1-1) from the viewpoint of ease of production. [Chemical formula] (In formula (1-1), R 1 and n have the same meanings as those described in formula (1) above.)

[0100] In the third polymer, the aromatic hydroxy compound represented by the formula (1-1) is preferably a compound represented by the following formula (1-2) from the viewpoint of ease of production. [Chemical formula] (In formula (1-2), R 1 has the same meaning as that described in the formula (1-1).)

[0101] In the formula (1A), formula (1), formula (1-1), and formula (1-2), from the viewpoint of兼备 high heat resistance and solubility, the R 1 preferably contains an aryl group having 6 to 40 carbon atoms which may have a substituent. In the third polymer, the aryl group having 6 to 40 carbon atoms is not limited to the following, for example, it may be a benzene ring, or various known condensed rings such as naphthalene, anthracene, naphthacene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, ovalene, fluorene, benzofluorene, and dibenzofluorene. In the third polymer, it is preferable from the viewpoint of heat resistance that the R 1 is various condensed rings such as naphthalene, anthracene, naphthacene, pentacene, benzopyrene, chrysene, pyrene, triphenylene, corannulene, coronene, ovalene, fluorene, benzofluorene, and dibenzofluorene. Also, it is preferable that the R 1 is naphthalene or anthracene because the n value and k value at a wavelength of 193 nm used in ArF exposure are low and the pattern transferability tends to be excellent. Further, the R 1 includes, in addition to the above-mentioned aromatic hydrocarbon rings, heterocycles such as pyridine, pyrrole, pyridazine, thiophene, imidazole, furan, pyrazole, oxazole, triazole, thiazole, or their benzo-fused ring compounds. In the third polymer, it is preferable that the R 1 is an aromatic hydrocarbon ring or a heterocycle from the viewpoint of solubility, and more preferably an aromatic hydrocarbon ring. Also, the R 1 It should be noted that the term "兼备" in the original text seems to be a misspelling or an uncommon expression. It might be intended to say "兼备" which could be translated as "兼备" or more precisely as "combining both" or "having both". The above translation is based on the best understanding of the context with the given text.From the viewpoint of solubility, this may be an aromatic hydrocarbon ring other than a group derived from a compound having a fluorene skeleton, such as fluorene or benzofluorene.

[0102] In the above formulas (1A), (1), (1-1), and (1-2), from the viewpoint of achieving even higher heat resistance and solubility, the R 1 However, R A -R B The group is represented by R, where R A This is a methine group, and the R B It is more preferable that the aryl group is an aryl group having 6 to 40 carbon atoms, which may have substituents. Examples of the aryl group include the aryl groups mentioned above, and it may also be an aryl group other than those derived from compounds having a fluorene skeleton, such as fluorene and benzofluorene.

[0103] Specific examples of aromatic hydroxy compounds represented by formulas (1A), (1), (1-1), and (1-2) are shown below. However, the aromatic hydroxy compounds in the third polymer are not limited to the compounds listed below. Furthermore, a specific example of the third polymer is a polymer that includes at least one selected from the repeating units (1A) and (2A) derived from the aromatic hydroxy compounds shown below, wherein the repeating units are linked to each other by direct bonding of aromatic rings. Examples of such polymers include RBisP-1, RBisP-2, RBisP-3, RBisP-4, and RBisP-5, which are shown in the synthesis examples described later. In addition, considering its application to a wide range of uses, such as the compositions described later, methods for producing polymers, film-forming compositions, resist compositions, resist pattern formation methods, radiation-sensitive compositions, lithography underlayer film formation compositions, lithography underlayer film production methods, circuit pattern formation methods, and optical component formation compositions, the third polymer can be at least one selected from the group consisting of RBisP-1, RBisP-2, RBisP-3, RBisP-4, RBisP-5 described in the examples described later and RBP-1 described later, in order to further improve heat resistance and etching resistance.

[0104]

Chem.

[0105]

Chem.

[0106]

Chem.

[0107]

Chem.

[0108]

Chem.

[0109]

Chem.

[0110] In the above formula, R 3 is each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms which may have a substituent, an alkynyl group having 2 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 40 carbon atoms which may have a substituent, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a nitro group, a heterocyclic group, a carboxyl group or a hydroxyl group. Further, the alkyl group may be linear, branched or cyclic.

[0111]

Chem.

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] Specific examples of aromatic hydroxy compounds represented by formula (2A) are shown below. However, the aromatic hydroxy compounds in the third polymer are not limited to the compounds listed below.

[0116] [ka]

[0117] In the third polymer, the number and ratio of each repeating unit are not particularly limited, but it is preferable to adjust them appropriately considering the application and the molecular weight values ​​described below. The third polymer can consist only of repeating units (1A) or (2A), but it may also contain other repeating units as long as it does not impair the performance according to the application. Other repeating units include, for example, repeating units having ether bonds formed by the condensation of phenolic hydroxyl groups, and repeating units having ketone structures. These other repeating units may also be directly bonded to repeating units (1A) or (2A) via aromatic rings. For example, the molar ratio [Y / X] of repeating units (1A) [Y] to the total amount [X] of the third polymer can be 0.05 to 1.00, preferably 0.45 to 1.00. The weight-average molecular weight of the third polymer is not particularly limited, but is preferably in the range of 400 to 100,000, more preferably 500 to 15,000, and even more preferably 1,000 to 12,000, in terms of having both heat resistance and solubility. The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) in the third polymer is not particularly limited in range, as the required ratio varies depending on the application. However, as polymers having a more homogeneous molecular weight, for example, those in the range of 3.0 or less are preferred, those in the range of 1.05 to 3.0 are more preferred, those in the range of 1.05 to less than 2.0 are particularly preferred, and those in the range of 1.05 to less than 1.5 are even more preferred from the viewpoint of heat resistance.

[0118] The bonding order of the repeating units in the third polymer is not particularly limited. For example, there may be two or more repeating units consisting of only one unit derived from the aromatic hydroxy compound represented by formula (1A) or formula (2A), or there may be one or more units each derived from the aromatic hydroxy compound represented by formula (1A) or formula (2A). The order may also be either block copolymerization or random copolymerization.

[0119] In the third polymer, "the repeating units are linked by direct bonding between aromatic rings" means, as an example, that the repeating units (1A) in the third polymer are linked to each other, the repeating units (2A) are linked to each other, or the repeating unit (1A) and the repeating unit (2A) (hereinafter, the repeating units (1A) and (2A) may be collectively referred to simply as "repeating unit (A)") are linked by a single bond, that is, directly linked without the intermediary of other atoms such as carbon atoms, oxygen atoms, or sulfur atoms, to the carbon atoms on the aromatic ring, which is indicated by an aryl structure in the parentheses in the formula of one repeating unit (A). Furthermore, this embodiment may include the following aspects. (1) In one repeating unit (A), R 1 and R 2 If either of them is an aryl group (for example, as mentioned above, R 1 R A -R B When the group is represented by R,1 This includes cases where the aryl group is a 2n+1 valent group having an aryl group, and the atom on the aromatic ring of the aryl group and the carbon atom on the aromatic ring of the other repeating unit (A), which is indicated by the aryl structure in parentheses in the formula, are directly bonded by a single bond. (2) In one repeating unit (A) and the other, R 1 and R 2 If either of them is an aryl group (for example, as mentioned above, R 1 R A -R B When the group is represented by R, 1 (Including the case where is a 2n+1 valent group having an aryl group), between one repeating unit (A) and the other, R 1 and R 2 In this configuration, atoms on the aromatic ring of the aryl group are directly bonded to each other by single bonds. The positions where repeating units in the third polymer are directly bonded to each other are not particularly limited. When the repeating unit is represented by the general formula (1A) or formula (2A), any one carbon atom that is not bonded to a phenolic hydroxyl group or other substituents is involved in the direct bonding between monomers. From the viewpoint of heat resistance, it is preferable that one carbon atom of any of the aromatic rings having a phenolic hydroxyl group is involved in the direct bonding between the aromatic rings. In other words, when two repeating units (1A) are bonded to one repeating unit (1A), it is preferable that each of the two aryl structures in formula (1A) is bonded to the other repeating unit. When each of the two aryl structures is bonded to the other repeating unit (1A), the positions of the carbon atoms bonded to the other repeating unit in each aryl structure may be different, or they may be at corresponding locations (for example, bonded at the 7th position of both naphthalene rings).

[0120] Furthermore, in the third polymer, it is preferable that all repeating units (1A) are bonded by direct bonding between aromatic rings, but it is also possible that repeating units (1A) bonded to other repeating units via other atoms such as oxygen or carbon are included. Although not particularly limited, from the viewpoint of fully exhibiting the effects of this embodiment, such as heat resistance and etching resistance, it is preferable that, based on bonding criteria, 50% or more, and more preferably 90% or more, of all repeating units (1A) in the third polymer are bonded to other repeating units (1A) by direct bonding between aromatic rings.

[0121] The third polymer is preferably highly soluble in the solvent, from the viewpoint of facilitating the application of wet processes. More specifically, when the solvent is propylene glycol monomethyl ether (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA), the third polymer is preferably soluble in propylene glycol monomethyl ether and / or propylene glycol monomethyl ether acetate of 1% by mass or more. Specifically, at a temperature of 23°C, the solubility in the solvent is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 20% by mass or more, and especially preferably 30% by mass or more. Here, the solubility in PGME and / or PGMEA is defined as "mass of the third polymer ÷ (mass of the third polymer + mass of the solvent) × 100 (mass%)". For example, 10 g of the third polymer is evaluated as dissolving in 90 g of PGMEA when the solubility of the third polymer in PGMEA is "10% by mass or more," and it is evaluated as not dissolving when the solubility is "less than 10% by mass."

[0122] Assuming application to at least one application selected from the group consisting of compositions, polymer manufacturing methods, film-forming compositions, resist compositions, resist pattern forming methods, radiation-sensitive compositions, lithography underlayer film forming compositions, lithography underlayer film manufacturing methods, circuit pattern forming methods, and optical component forming compositions, and from the viewpoint of further improving heat resistance and etching resistance, it is particularly preferable that the third polymer be at least one selected from the group consisting of RBisP-1, RBisP-2, RBisP-3, RBisP-4, RBisP-5, and RBP-1 as described in the examples below.

[0123] [The fourth polymer] The fourth polymer is a polymer having repeating units derived from heteroatom-containing aromatic monomers, wherein the repeating units are linked to each other by direct bonding between the aromatic rings of the heteroatom-containing aromatic monomers. Because of this configuration, the fourth polymer has superior performance in terms of heat resistance, etching resistance, and other properties.

[0124] In the fourth polymer, the position of the heteroatom in the heteroatom-containing aromatic monomer is not particularly limited, but from the viewpoint of having heat resistance, solubility, and etching resistance, it is preferable that the heteroatom constitutes an aromatic ring. That is, it is preferable that the heteroatom-containing aromatic monomer includes a heterocyclic aromatic compound.

[0125] In the fourth polymer, the heteroatom in the heteroatom-containing aromatic monomer is not particularly limited and may include, for example, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. In the fourth polymer, from the viewpoint of etching resistance, it is preferable to include a nitrogen atom, a phosphorus atom, or a sulfur atom as the heteroatom rather than an oxygen atom. That is, it is preferable that the heteroatom in the heteroatom-containing aromatic monomer contains at least one selected from the group consisting of a nitrogen atom, a phosphorus atom, and a sulfur atom. Furthermore, from the viewpoint of storage stability, it is preferable that the heteroatom in the heteroatom-containing aromatic monomer contains at least one of a nitrogen atom and a phosphorus atom.

[0126] From the viewpoint of providing both heat resistance and etching resistance, it is preferable that the heteroatom-containing aromatic monomer includes a monomer represented by the following formula (1-1), either substituted or unsubstituted, or a monomer represented by the following formula (1-2), either substituted or unsubstituted. [ka] (In the above equation (1-1), X is independently of NR 0 A group represented by a sulfur atom, an oxygen atom, or PR 0 It is a group represented by R 0 and R 1 Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. [ka] (In the above formula (1-2), Q 1 and Q 2 Q is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylylene group having 2 to 20 carbon atoms, a carbonyl group, a group represented by NRa, an oxygen atom, a sulfur atom, or a group represented by PRa, where Ra is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a halogen atom, where Q is the monomer. 1 and Q 2 If both are present, at least one of them contains a heteroatom, and in the monomer Q 1 If only Q exists, 1 It contains heteroatoms, Q 3Q is a group represented by a nitrogen atom, a phosphorus atom, or CRb, where Q is the monomer. 3 It contains heteroatoms, The aforementioned Ra and Rb are, independently, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a halogen atom.

[0127] In the fourth polymer, "substituted or unsubstituted monomers represented by the following formula (1-1)" and "substituted or unsubstituted monomers represented by the following formula (1-2)" refer to X and Q in the formulas. 1 Q 2 and Q 3 If hydrogen atoms are bonded to carbon atoms other than the carbon atoms contained in the compound, it means that at least one of those hydrogen atoms can be substituted. Unless otherwise defined, "substituents" here include, for example, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, thiol groups, heterocyclic groups, alkyl groups with 1 to 30 carbon atoms, aryl groups with 6 to 20 carbon atoms, alkoxyl groups with 1 to 30 carbon atoms, alkenyl groups with 2 to 30 carbon atoms, alkynyl groups with 2 to 30 carbon atoms, acyl groups with 1 to 30 carbon atoms, and amino groups with 0 to 30 carbon atoms.

[0128] The aforementioned equations (1-1) and (1-2) will be explained in detail below.

[0129] In equation (1-1), X is independently of NR 0 A group represented by a sulfur atom, an oxygen atom, or PR 0 It is a group represented by R 0 and R 1 Each of these is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. In equation (1-1), X is independently of NR 0 A group represented by PR, a sulfur atom, or PR 0 It is preferable that the group is represented by . Examples of substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, octyloxy, and 2-ethylhexyloxy. Halogen atoms are not limited to the following, but examples include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Examples of substituted or unsubstituted C1-C30 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, sec-butyl, n-pentyl, neopentyl, isoamyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, barrel, and 2-ethylhexyl. Examples of substituted or unsubstituted aryl groups having 6 to 30 carbon atoms include, but are not limited to, phenyl, naphthyl, biphenyl, fluorenyl, anthuryl, pyrenyl, azlenyl, acenaphthirenyl, terphenyl, phenanthuryl, and perylene groups.

[0130] In the fourth polymer, from the viewpoint of possessing both solubility and etching resistance, in formula (1-1), R 1 It is preferable that this is a substituted or unsubstituted phenyl group.

[0131] In formula (1-2), Q 1 and Q 2 Q is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylylene group having 2 to 20 carbon atoms, a carbonyl group, a group represented by NRa, an oxygen atom, a sulfur atom, or a group represented by PRa, where Ra is independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a halogen atom, where Q is the monomer. 1 and Q2 If both are present, at least one of them contains a heteroatom, and in the monomer Q 1 If only Q exists, 1 It contains heteroatoms. In formula (1-2), Q 3 Q is a group represented by a nitrogen atom, a phosphorus atom, or CRb, where Q is the monomer. 3 It contains heteroatoms. The aforementioned Ra and Rb are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a halogen atom. Examples of substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms include, but are not limited to, methylene, ethylene, n-propylene, i-propylene, n-butylene, i-butylene, t-butylene, n-pentylene, n-hexylene, n-dodecylene, valerene, methylmethylene, dimethylmethylene, and methylethylene. Examples of substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms include, but are not limited to, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclododecylene, and cyclovalerene groups. Examples of substituted or unsubstituted arylene groups having 6 to 20 carbon atoms include, but are not limited to, phenylene groups, naphthylene groups, anthrylene groups, phenanthrylene groups, pyrenylene groups, peryleneylene groups, fluorenylene groups, biphenylene groups, and the like. Examples of substituted or unsubstituted heteroarylene groups having 2 to 20 carbon atoms include, but are not limited to, thienylene groups, pyridinylene groups, and frilene groups. Examples of substituted or unsubstituted alkenylene groups having 2 to 20 carbon atoms include vinylene, propenylene, and butenylene groups. Examples of substituted or unsubstituted alkylylene groups having 2 to 20 carbon atoms include ethynylene, propynylene, and butynylene groups. Examples of substituted or unsubstituted C1-C10 alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, n-dodecyl, and barrel groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0132] The fourth polymer can improve heat resistance by directly bonding aromatic monomers containing heteroatoms. Furthermore, by including heteroatoms such as P, N, O, or S within its structural units, not only can the etching resistance of the polymer be ensured, but the increased polarity of the polymer due to the heteroatoms can also improve solvent solubility. Moreover, organic films using polymers in which aromatic monomers containing the above-mentioned heteroatoms are directly bonded within their structural units can achieve excellent film density, thereby improving the processing accuracy by etching.

[0133] From the above-mentioned viewpoint, in the fourth polymer, the heteroatom-containing aromatic monomer is preferably a substituted or unsubstituted monomer represented by the following formula (1-1), and more preferably contains at least one selected from the group consisting of indole, 2-phenylbenzoxazole, 2-phenylbenzothiazole, carbazole, and dibenzothiophene.

[0134] The fourth polymer may be a homopolymer of one heteroatom-containing aromatic monomer, or a polymer of two or more heteroatom-containing aromatic monomers. Furthermore, it may contain copolymer components other than heteroatom-containing aromatic monomers.

[0135] The fourth polymer preferably further comprises monomer-derived structural units represented by the following formula (2) from the viewpoint of providing even higher heat resistance, etching resistance, and solubility.

[0136] [ka]

[0137] In formula (2), Q4 and Q5 are single bonds, substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 20 carbon atoms, and substituted or unsubstituted alkylene groups having 2 to 20 carbon atoms. Q6 is a group represented by CRb', where Rb is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0138] Substituted or unsubstituted alkylene groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene groups having 3 to 20 carbon atoms, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, substituted or unsubstituted alkenylene groups having 2 to 20 carbon atoms, and substituted or unsubstituted alkynylene groups having 2 to 20 carbon atoms are defined in the same way as in formula (1-2) above.

[0139] In the fourth polymer, the number and ratio of each repeating unit are not particularly limited, but it is preferable to adjust them appropriately considering the application and the molecular weight values ​​described below. Furthermore, the fourth polymer can be composed only of formula (1), but it may also contain other repeating units as long as it does not impair the performance according to the application. Other repeating units include, for example, repeating units having ether bonds formed by the condensation of phenolic hydroxyl groups, and repeating units having ketone structures. These other repeating units may also be directly bonded to repeating unit (1) via aromatic rings. For example, the molar ratio [Y / X] of constituent units (A) [Y] to the total amount [X] of the fourth polymer can be 5 to 100, preferably 45 to 100. The weight-average molecular weight of the fourth polymer is not particularly limited, but is preferably in the range of 400 to 100,000, more preferably 500 to 15,000, and even more preferably 1,000 to 12,000, in terms of having both heat resistance and solubility. The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn) in the fourth polymer is not particularly limited in range, as the required ratio varies depending on the application. However, as polymers having a more homogeneous molecular weight, for example, those in the range of 3.0 or less are preferred, those in the range of 1.05 to 3.0 are more preferred, those in the range of 1.05 to less than 2.0 are particularly preferred, and those in the range of 1.05 to less than 1.5 are even more preferred from the viewpoint of heat resistance.

[0140] The bonding order of the repeating units in the fourth polymer is not particularly limited. For example, it may contain two or more repeating units derived from only one type of polycyclic aromatic monomer represented by formula (1), or it may contain one or more units each derived from two or more types of polycyclic aromatic monomers represented by formula (1). The order of bonding may be either block copolymerization or random copolymerization.

[0141] In the fourth polymer, "the repeating units are linked by direct bonding between aromatic rings" means, as an example, that in a polycyclic aromatic monomer, units (1) (or multiple repeating units represented by repeating unit (1); hereinafter, these may be collectively referred to simply as "repeating unit (A)") are directly bonded by a single bond between the carbon atom on the aromatic ring, indicated by the aryl structure in parentheses in the formula of one repeating unit (A), and the carbon atom on the aromatic ring, indicated by the aryl structure in parentheses in the formula of the other repeating unit (A), that is, directly bonded without the intermediary of other atoms such as carbon atoms, oxygen atoms, or sulfur atoms. The position where repeating units in the fourth polymer are directly bonded to each other is not particularly limited; any single carbon atom that does not have a substituent attached is involved in the direct bonding between monomers. From the viewpoint of heat resistance, it is preferable that one carbon atom in any of the heteroatom-containing condensed ring monomers is involved in the direct bonding between the aromatic rings. In other words, when two repeating units (1) are bonded to one repeating unit (1), it is preferable that each of the two aryl structures in formula (1) is bonded to the other repeating unit. When each of the two aryl structures is bonded to the other repeating unit (1), the positions of the carbon atoms bonded to the other repeating unit in each aryl structure may be different, or they may be at corresponding locations (for example, bonded at the 7-position of both naphthalene rings).

[0142] Furthermore, in the fourth polymer, it is preferable that all repeating units (1) are bonded by direct bonding between aromatic rings, but repeating units (1) that are bonded to other repeating units via other atoms such as oxygen or carbon may also be included. Although not particularly limited, from the viewpoint of fully exhibiting the effects of this embodiment, such as heat resistance and etching resistance, it is preferable that, based on bonding criteria, 50% or more, and more preferably 90% or more, of all repeating units (1) in the fourth polymer are bonded to other repeating units (1) by direct bonding between aromatic rings.

[0143] The fourth polymer is preferably highly soluble in the solvent, from the viewpoint of facilitating the application of wet processes. More specifically, the fourth polymer is preferably soluble in 1% by mass or more in one or more selected from the group consisting of propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone (CHN), cyclopentanone (CPN), ethyl lactate (EL), and methyl hydroxyisobutyrate (HBM). Specifically, the solubility in the solvent at a temperature of 23°C is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 20% by weight or more, and especially preferably 30% by weight or more. Here, the solubility in PGME, PGMEA, CHN, CPN, EL, and / or HBM is defined as "mass of the fourth polymer ÷ (mass of the fourth polymer + mass of the solvent) × 100 (mass%)". For example, 10 g of the fourth polymer is evaluated as dissolving in 90 g of PGMEA when the solubility of the fourth polymer in PGMEA is "10% by mass or more," and it is evaluated as not dissolving when the solubility is "less than 10% by mass."

[0144] Assuming application to at least one application selected from the group consisting of compositions, polymer manufacturing methods, film-forming compositions, resist compositions, resist pattern formation methods, radiation-sensitive compositions, lithography underlayer formation compositions, lithography underlayer production methods, circuit pattern formation methods, and optical component formation compositions, and from the viewpoint of further improving heat resistance and etching resistance, it is particularly preferable that the fourth polymer be at least one selected from the group consisting of RHE-1, RHE-2, RHE-3, RHE-4, RHE-5, and RHE-6 described in the examples below.

[0145] The polymer of this embodiment may further have a modified portion derived from a crosslinking-reactive compound. That is, the polymer of this embodiment having the structure described above may have a modified portion obtained by reaction with a crosslinking-reactive compound. Such (modified) polymers also have excellent heat resistance and etching resistance and can be used as coating agents for semiconductors, resist materials, and semiconductor underlayer film forming materials.

[0146] Compounds with crosslinking reactivity include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanate compounds, and unsaturated hydrocarbon group-containing compounds. These can be used individually or in combination as appropriate.

[0147] In the polymer of this embodiment, the crosslinking-reactive compound is preferably an aldehyde or a ketone. More specifically, it is preferable that the polymer is obtained by polycondensing the polymer of this embodiment having the aforementioned structure with an aldehyde or a ketone in the presence of a catalyst. For example, a novolac-type polymer can be obtained by further polycondensing the aldehyde or ketone corresponding to the desired structure under atmospheric pressure, or under pressurized pressure if necessary, in the presence of a catalyst.

[0148] Examples of the aldehydes mentioned above include, but are not limited to, methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentabenzaldehyde, butylmethylbenzaldehyde, hydroxybenzaldehyde, dihydroxybenzaldehyde, and fluoromethylbenzaldehyde. These can be used individually or in combination of two or more. Among these, methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, pentabenzaldehyde, and butylmethylbenzaldehyde are preferred from the viewpoint of providing high heat resistance.

[0149] Examples of the aforementioned ketones include, but are not limited to, acetylmethylbenzene, acetyldimethylbenzene, acetyltrimethylbenzene, acetylethylbenzene, acetylpropylbenzene, acetylbutylbenzene, acetylpentabenzene, acetylbutylmethylbenzene, acetylhydroxybenzene, acetyldihydroxybenzene, and acetylfluoromethylbenzene. These can be used individually or in combination of two or more. Among these, acetylmethylbenzene, acetyldimethylbenzene, acetyltrimethylbenzene, acetylethylbenzene, acetylpropylbenzene, acetylbutylbenzene, acetylpentabenzene, and acetylbutylmethylbenzene are preferred from the viewpoint of providing high heat resistance.

[0150] The catalyst used in the above reaction can be appropriately selected from known catalysts and is not particularly limited. Acid catalysts and base catalysts are preferably used. Inorganic acids and organic acids are widely known as such acid catalysts. Specific examples of the above acid catalysts 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 silicic acid, phosphotungstic acid, silicic acid, molybdic acid, and phosphomolybdic acid, but are not particularly limited to these. Among these, organic acids and solid acids are preferred from a manufacturing standpoint, and hydrochloric acid or sulfuric acid is preferred from a manufacturing standpoint such as ease of availability and handling. Examples of such base catalysts include pyridine and ethylenediamine as amine-containing catalysts, and metal salts, and especially potassium salts or acetate salts as non-amine basic catalysts. Suitable catalysts are not limited to potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide. Non-amine base catalysts are commercially available, for example, from EMScience or Aldrich. The catalyst can be used individually or in combination of two or more types. The amount of catalyst used can be appropriately set according to the raw materials used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but it is preferably 0.001 to 100 parts by mass per 100 parts by mass of reaction raw materials.

[0151] A reaction solvent may be used in the above reaction. The reaction solvent is not particularly limited as long as it allows the reaction between the aldehyde or ketone used and the polymer to proceed, and can be appropriately selected from known solvents. Examples include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, or mixed solvents thereof. The solvent can be used alone or in combination of two or more. The amount of these solvents used can be appropriately set depending on the type of raw materials and acid catalyst used, as well as the reaction conditions. The amount of solvent used is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of reaction materials. Furthermore, the reaction temperature in the above reaction can be appropriately selected depending on the reactivity of the reaction materials. The reaction temperature is not particularly limited, but is usually preferably in the range of 10 to 200°C. The reaction method is not particularly limited and can be selected from known methods as appropriate. Examples include charging the polymer, aldehydes or ketones, and acid catalyst all at once, or adding the aldehydes or ketones dropwise in the presence of the acid catalyst. After the polycondensation reaction is complete, the resulting compound can be isolated according to conventional methods and is not particularly limited. For example, the target compound can be obtained by employing general methods such as raising the temperature of the reaction vessel to 130-230°C and removing volatile components at approximately 1-50 mmHg to remove unreacted raw materials and acid catalyst present in the system.

[0152] [Polymer properties] The polymer of this embodiment is not limited to the following, but typically has the following properties (1) to (4). (1) The polymer of this embodiment has excellent solubility in organic solvents (especially safe solvents). For this reason, for example, if the polymer of this embodiment is used as a lithography film-forming material, lithography films can be formed by wet processes such as spin coating or screen printing. (2-1) The first, second, and third polymers have relatively high carbon concentrations and relatively low oxygen concentrations. Furthermore, because they contain phenolic hydroxyl groups in their molecules, they are useful for forming cured products through reaction with curing agents, but they can also form cured products on their own through crosslinking reactions of the phenolic hydroxyl groups during high-temperature baking. As a result, the first, second, and third polymers exhibit high heat resistance, and when used as lithography film-forming materials, film degradation during high-temperature baking is suppressed, and lithography films with excellent etching resistance to oxygen plasma etching and the like can be formed. (2-2) The fourth polymer has a relatively high carbon concentration and a relatively low oxygen concentration. Furthermore, because it has reactive active sites in its molecule, it is useful for forming cured products through reaction with a curing agent, but it can also form cured products on its own through crosslinking of the reactive active sites during high-temperature baking. As a result, the fourth polymer exhibits high heat resistance, and when used as a lithography film-forming material, it suppresses film degradation during high-temperature baking and can form lithography films with excellent etching resistance to oxygen plasma etching and the like. (3) As described above, the polymer of this embodiment can exhibit high heat resistance and etching resistance, as well as excellent adhesion to resist layers and resist interlayer materials. For this reason, when used as a lithography film-forming material, it is possible to form a lithography film with excellent resist pattern formation properties. Herein, "resist pattern formation properties" refers to the property of having no major defects in the resist pattern shape and having excellent resolution and sensitivity. (4) The polymer of this embodiment has a high refractive index due to its high aromatic ring density, and discoloration is suppressed even when heat-treated, resulting in excellent transparency. For this reason, the polymer of this embodiment is also useful as a composition for forming various optical components.

[0153] The polymer of this embodiment can be preferably applied as a lithography film-forming material due to the properties described above, and therefore it is believed that the lithography film-forming composition of this embodiment is endowed with the desired properties described above. In particular, compared to resins crosslinked with divalent organic groups or oxygen atoms, it has a higher aromatic ring density, and the carbon-carbon atoms of the aromatic rings are directly bonded together. Therefore, even with a relatively low molecular weight, it is believed to have superior performance in terms of heat resistance, etching resistance, and other properties.

[0154] <Method for producing polymers> The method for producing the polymer of this embodiment is not limited to the following, but may include, for example, a step of polymerizing one or more monomers corresponding to the repeating units in the presence of an oxidizing agent (oxidative polymerization step). The first polymer will be described in detail below as an example.

[0155] [Method for producing the first polymer] The first polymer manufacturing method is not limited to the following, but may include the oxidative polymerization step described above. When carrying out such a step, the contents of K. Matsumoto, Y. Shibasaki, S. Ando and M. Ueda, Polymer, 47, 3043 (2006) can be appropriately referred to. That is, in the oxidative polymerization of β-naphthol-type monomers, α-position CC coupling is selectively generated by an oxidative coupling reaction in which a radical oxidized by one electron due to the monomer is coupled, and regioselective polymerization can be performed by using, for example, a copper / diamine-type catalyst. The oxidizing agent in this embodiment is not particularly limited as long as it produces an oxidative coupling reaction, but metal salts containing copper, manganese, iron, cobalt, ruthenium, lead, nickel, silver, tin, chromium, or palladium, peroxides such as hydrogen peroxide or perchlorates, and organic peroxides can be used. Among these, metal salts or metal complexes containing copper, manganese, iron, or cobalt can be preferably used. Metals such as copper, manganese, iron, cobalt, ruthenium, lead, nickel, silver, tin, chromium, or palladium can also be used as oxidizing agents by reduction in the reaction system. These are included in the category of metal salts. For example, a desired polymer can be obtained by dissolving an aromatic hydroxy compound represented by general formula (1A) in an organic solvent, adding a metal salt containing copper, manganese, or cobalt, and then reacting it with, for example, oxygen or an oxygen-containing gas to carry out oxidative polymerization. According to the polymer manufacturing method by oxidative polymerization described above, molecular weight control is relatively easy, and polymers with a small molecular weight distribution can be obtained without leaving behind raw material monomers or low molecular weight components associated with high molecular weight production. Therefore, this method tends to be advantageous in terms of high heat resistance and low sublimation.

[0156] As metal salts, halides, carbonates, acetates, nitrates, or phosphates of copper, manganese, cobalt, ruthenium, chromium, and palladium can be used. The metal complex is not particularly limited and any known one can be used. Specific examples include, but are not limited to, the following: copper-containing complex catalysts include those described in Japanese Patent Publication Nos. 36-18692, 40-13423, and 49-490; manganese-containing complex catalysts include those described in Japanese Patent Publication Nos. 40-30354, 47-5111, 56-32523, 57-44625, 58-19329, and 60-83185; and cobalt-containing complex catalysts include those described in Japanese Patent Publication No. 45-23555.

[0157] Examples of organic peroxides include, but are not limited to, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, peracetic acid, perbenzoic acid, and others.

[0158] The above-mentioned oxidizing agents can be used alone or in combination. The amounts used are not particularly limited, but are preferably 0.002 to 10 moles, more preferably 0.003 to 3 moles, and even more preferably 0.005 to 0.3 moles per mole of aromatic hydroxy compound. In other words, the oxidizing agents in this embodiment can be used at low concentrations relative to the monomer.

[0159] In this embodiment, it is preferable to use a base in addition to the oxidizing agent used in the oxidative polymerization step. The base is not particularly limited and known bases can be used. Specific examples include inorganic bases such as alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal alkoxides, as well as organic bases such as primary to tertiary monoamine compounds and diamines. Each can be used individually or in combination.

[0160] The oxidation method is not particularly limited, and methods using oxygen gas or air directly are available, but air oxidation is preferred from the standpoint of safety and cost. When oxidizing with air under atmospheric pressure, it is preferable to introduce air into the reaction solvent by bubbling, from the viewpoint of improving the rate of oxidative polymerization and increasing the molecular weight of the polymer. Furthermore, the oxidation reaction in this embodiment can also be carried out under pressure, specifically 2 kg / cm³ from the viewpoint of accelerating the reaction. 2 ~15kg / cm 2 A 3 kg / cm² load is preferred, and from the standpoint of safety and controllability. 2 ~10kg / cm 2 That is even more preferable.

[0161] In this embodiment, the oxidation reaction of the aromatic hydroxy compound can be carried out in the absence of a reaction solvent, but it is generally preferable to carry out the reaction in the presence of a solvent. Any known solvent can be used as the solvent, as long as it does not hinder the acquisition of the first polymer and dissolves the catalyst to some extent. Generally, solvents such as alcohols including methanol, ethanol, propanol, and butanol; ethers including dioxane, tetrahydrofuran, or ethylene glycol dimethyl ether; amides or nitriles; ketones including acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; or a mixture of these with water can be used. Alternatively, the reaction can be carried out in a two-phase system of hydrocarbons such as benzene, toluene, or hexane that are immiscible with water, or with water.

[0162] Furthermore, the reaction conditions can be appropriately adjusted according to the substrate concentration, the type and concentration of the oxidizing agent, but the reaction temperature can be set to a relatively low temperature, preferably 5 to 150°C, and more preferably 20 to 120°C. The reaction time is preferably 30 minutes to 24 hours, and more preferably 1 hour to 20 hours. The method of stirring during the reaction is not particularly limited and may be shaking, stirring with a rotor, or stirring with a blade. This step may be carried out in either a solvent or an airflow, as long as the stirring conditions satisfy the above conditions.

[0163] [Methods for producing the second to fourth polymers] The method for producing the second to fourth polymers is not particularly limited, but for example, it may include the oxidative polymerization step described above. That is, instead of using the aromatic hydroxy compounds represented by formulas (1A) and (1B) described in the section on [First Polymer] as "monomers corresponding to the repeating units," the method may use the aromatic hydroxy compound represented by formula (1A-1) described in the section on [Second Polymer], the aromatic hydroxy compounds represented by formulas (1A) and (2A) described in the section on [Third Polymer], or the heteroatom-containing aromatic monomer described in the section on [Fourth Polymer] as "monomers corresponding to the repeating units," except that the oxidative polymerization step is carried out in the same manner as described in the section on [Method for Producing the First Polymer] above, and the second to fourth polymers can be produced.

[0164] <Composition> The polymer of this embodiment can be used as a composition for various applications. That is, the composition of this embodiment includes the polymer of this embodiment. The composition of this embodiment preferably further contains a solvent, from the viewpoint of facilitating film formation by applying a wet process. Specific examples of solvents are not particularly limited, but include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol, and 1-ethoxy-2-propanol; and aromatic hydrocarbons such as toluene, xylene, and anisole. These solvents can be used individually or in combination of two or more.

[0165] Among the above solvents, one or more selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclopentanone, ethyl lactate, and methyl hydroxyisobutyrate are particularly preferred from a safety standpoint.

[0166] The solvent content in the composition of this embodiment is not particularly limited, but from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, and even more preferably 200 to 1,000 parts by mass, per 100 parts by mass of the polymer of this embodiment.

[0167] The polymer of this embodiment is preferably obtained as a crude product by the oxidation reaction described above, and then further purified to remove any residual oxidizing agent. Specifically, from the viewpoint of preventing deterioration of the polymer over time and ensuring storage stability, it is preferable to avoid the residue of metal salts or metal complexes containing copper, manganese, iron, or cobalt, which are mainly used as metal oxidizing agents derived from the oxidizing agent. That is, the composition of this embodiment preferably contains less than 500 ppb of impurity metal for each metal species, and more preferably 1 ppb or less. Furthermore, there are no particular limitations on the impurity metal, but examples include at least one selected from a more selective group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium. Because the amount of residual metal (impurity metal content) derived from the oxidizing agent is less than 500 ppb, the solution tends to be usable without compromising storage stability.

[0168] The purification method is not particularly limited, but it includes a step of dissolving the polymer in a solvent to obtain a solution (S), and a step of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities from the polymer (first extraction step), wherein the solvent used in the step of obtaining the solution (S) includes an organic solvent that is not arbitrarily miscible with water. According to the above purification method, the content of various metals that may be present as impurities in the polymer can be reduced. More specifically, the polymer can be dissolved in an organic solvent that is arbitrarily immiscible with water to obtain a solution (S), and then the solution (S) can be brought into contact with an acidic aqueous solution for extraction. This transfers the metal components contained in the solution (S) to the aqueous phase, and then the organic phase and the aqueous phase are separated to obtain a polymer with reduced metal content.

[0169] The solvent used in the purification method described above is not particularly limited to water, but an organic solvent that can be safely applied to semiconductor manufacturing processes is preferred. Specifically, an organic solvent with a solubility in water of less than 30% at room temperature is preferred, more preferably less than 20%, and most preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times the mass of the total amount of polymer used.

[0170] Specific examples of solvents that are not arbitrarily miscible with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether; esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate are preferred, methyl isobutyl ketone, ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate are more preferred, and methyl isobutyl ketone and ethyl acetate are even more preferred. Methyl isobutyl ketone and ethyl acetate have relatively high saturation solubility of polymers and relatively low boiling points, which reduces the load in industrial solvent removal processes such as distillation or drying. These solvents can be used individually or in mixtures of two or more.

[0171] The acidic aqueous solution used in the above purification method is appropriately selected from aqueous solutions of generally known organic or inorganic compounds dissolved in water. Examples include, but are not limited to, aqueous solutions of mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or aqueous solutions of organic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. These acidic aqueous solutions can be used individually or in combination of two or more. Among these acidic aqueous solutions, it is preferable that the solution be one or more aqueous mineral acid solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or one or more aqueous organic acid solutions selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. More preferable are aqueous solutions of sulfuric acid, nitric acid, and carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and citric acid, even more preferable are aqueous solutions of sulfuric acid, oxalic acid, tartaric acid, and citric acid, and even more preferable are aqueous solutions of oxalic acid. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid are thought to coordinate with metal ions and produce a chelating effect, thus tending to remove metals more effectively. Furthermore, in line with the purpose of the purification method in this embodiment, it is preferable to use water with a low metal content, such as ion-exchanged water.

[0172] The pH of the acidic aqueous solution used in the above purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution considering its effect on the polymer. Typically, the pH range is about 0 to 5, and preferably about 0 to 3.

[0173] The amount of acidic aqueous solution used in the above purification method is not particularly limited, but it is preferable to adjust the amount used from the viewpoint of reducing the number of extractions for metal removal and ensuring operability by considering the total volume of liquid. From the above viewpoint, the amount of acidic aqueous solution used is preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the above solution (S).

[0174] In the above purification method, the metal component can be extracted from the polymer in the solution (S) by bringing the above acidic aqueous solution into contact with the above solution (S).

[0175] In the above purification method, the solution (S) may further contain an organic solvent that is optionally miscible with water. When an organic solvent that is optionally miscible with water is included, the amount of polymer charged can be increased, and the liquid-liquid properties improve, which tends to allow for purification with high kettle efficiency. The method of adding the organic solvent that is optionally miscible with water is not particularly limited. For example, it may be added to a solution containing the organic solvent beforehand, added to water or an acidic aqueous solution beforehand, or added after contacting the solution containing the organic solvent with water or an acidic aqueous solution. Among these, the method of adding it to a solution containing the organic solvent beforehand is preferred in terms of ease of operation and ease of controlling the amount of charge.

[0176] The organic solvent that is optionally miscible with water used in the purification method described above is not particularly limited, but an organic solvent that can be safely applied to semiconductor manufacturing processes is preferred. The amount of organic solvent that is optionally miscible with water used is not particularly limited as long as the solution phase and the aqueous phase are separated, but it is preferably 0.1 to 100 times the mass of the total amount of polymer used, more preferably 0.1 to 50 times, and even more preferably 0.1 to 20 times.

[0177] Specific examples of organic solvents that are optionally miscible with water used in the above purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and N-methylpyrrolidone; and aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone and propylene glycol monomethyl ether are preferred, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferred. These solvents can be used individually or in combination of two or more.

[0178] The temperature during the extraction process is typically 20 to 90°C, preferably in the range of 30 to 80°C. The extraction is carried out by thoroughly mixing the solution (S), for example by stirring, and then allowing it to stand. This causes the metal components contained in the solution (S) to migrate to the aqueous phase. Furthermore, this operation reduces the acidity of the solution, which can suppress the deterioration of the polymer.

[0179] The above mixed solution separates into a solution phase containing the polymer and solvent and an aqueous phase by standing, and the solution phase is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation of the solvent-containing solution phase and the aqueous phase. Typically, the standing time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. In addition, the extraction process can be performed only once, but it is also effective to repeat the operation of mixing, standing, and separation multiple times.

[0180] In the purification method described above, it is preferable to include a step (second extraction step) in which, after the first extraction step, the solution phase containing the polymer is further brought into contact with water to extract impurities from the polymer. Specifically, for example, it is preferable to perform the extraction treatment using an acidic aqueous solution, and then subject the solution phase containing the polymer and solvent, which has been extracted and recovered from the aqueous solution, to further extraction treatment with water. The extraction treatment with water described above is not particularly limited, but for example, it can be carried out by thoroughly mixing the solution phase and water by stirring or the like, and then allowing the resulting mixed solution to stand. After standing, the mixed solution separates into a solution phase containing the polymer and solvent and an aqueous phase, so the solution phase can be recovered by decantation or the like. Furthermore, the water used here is preferably water with a low metal content, such as ion-exchanged water, in line with the purpose of this embodiment. The extraction process can be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating multiple times. In addition, the ratio of the two substances used in the extraction process, as well as the conditions such as temperature and time, are not particularly limited, but they can be the same as in the case of the contact treatment with the acidic aqueous solution described above.

[0181] Any water that may be mixed into the solution containing the polymer and solvent obtained in this way can be easily removed by operations such as vacuum distillation. Furthermore, if necessary, the solvent can be added to the solution to adjust the polymer concentration to any desired level.

[0182] The polymer according to this embodiment can also be purified by passing a solution obtained by dissolving the polymer in a solvent through a filter. According to the polymer purification method of this embodiment, the content of various metal components in the polymer can be effectively and significantly reduced. The amounts of these metal components can be measured by the method described in the examples below. In this embodiment, "liquid passage" means that the solution moves from outside the filter, through the inside of the filter, and back to outside the filter. For example, simply bringing the solution into contact with the surface of the filter, or moving the solution outside the ion exchange resin while it is in contact with the surface (i.e., simply making contact), are excluded.

[0183] (Filter purification process (liquid passage process)) In the filter-passing step of this embodiment, the filter used to remove metal components from the solution containing the polymer and solvent can be a commercially available filter for liquid filtration. The filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, even more preferably 0.1 μm or less, even more preferably less than 0.1 μm, and most preferably 0.05 μm or less. The lower limit of the nominal pore size of the filter is not particularly limited, but is usually 0.005 μm. The nominal pore size referred to here is the nominal pore size that indicates the separation performance of the filter, and is the pore size determined by a test method determined by the filter manufacturer, such as a bubble point test, mercury intrusion test, or standard particle capture test. When using a commercially available product, it is the value listed in the manufacturer's catalog data. By setting the nominal pore size to 0.2 μm or less, the amount of metal components after passing the solution through the filter once can be effectively reduced. In this embodiment, the filter passing process may be performed two or more times in order to further reduce the content of each metal component in the solution.

[0184] The filter can take the form of a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, or a filter filled with a filter material such as nonwoven fabric, cellulose, or diatomaceous earth. Among the above, it is preferable that the filter be one or more selected from the group consisting of hollow fiber membrane filters, membrane filters, and pleated membrane filters. In particular, it is especially preferable to use a hollow fiber membrane filter due to its high filtration accuracy and large filtration area compared to other forms.

[0185] The material of the filter can be polyolefins such as polyethylene and polypropylene, polyethylene resins with functional groups having ion exchange ability due to graft polymerization, polar group-containing resins such as polyamide, polyester, and polyacrylonitrile, or fluorine-containing resins such as polyethylene fluoride (PTFE). Among the above, it is preferable that the filter medium is one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin. Furthermore, polyamide is particularly preferred from the viewpoint of reducing heavy metals such as chromium. In addition, it is preferable to use a filter made of a material other than sintered metal from the viewpoint of avoiding metal leaching from the filter medium.

[0186] Examples of polyamide filters include, but are not limited to, the following (hereinafter, registered trademarks): the Polyfix Nylon series from Kitz Microfilter Corporation, UltiPleats P-Nylon 66 and Ultipore N66 from Nippon Pall Corporation, and the LifeAssure PSN series and LifeAssure EF series from 3M Limited. Examples of polyolefin filters include, but are not limited to, the following: UltiPleats PE Clean and Ion Clean from Nippon Pall Co., Ltd., and the Protego series, Microguard Plus HC10, and Optimizer D from Nippon Integris Co., Ltd. Examples of polyester filters include, but are not limited to, the Jeraflow DFE manufactured by Central Filter Industry Co., Ltd. and the pleated type PMC manufactured by Nippon Filter Co., Ltd. Examples of polyacrylonitrile filters include, but are not limited to, the Ultrafilter AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantec Toyo Co., Ltd. Examples of fluororesin filters include, but are not limited to, Enflon HTPFR manufactured by Nippon Pall Co., Ltd. and LifeSure FA series manufactured by 3M Co., Ltd. These filters can be used individually or in combination of two or more types.

[0187] Furthermore, the filter may also contain an ion exchanger such as a cation exchange resin, or a cation charge modifier that generates a zeta potential in the filtered organic solvent solution. Examples of filters containing ion exchangers include, but are not limited to, the Protego series manufactured by Nippon Integris Co., Ltd. and the Krangraft manufactured by Kurashiki Textile Processing Co., Ltd. Furthermore, filters containing materials having a positive zeta potential, such as polyamide polyamine epichlorohydrin cation resins, include, but are not limited to, the ZetaPlus 40QSH and ZetaPlus 020GN manufactured by 3M Co., Ltd., or the LifeAssure EF series.

[0188] The method for isolating the polymer from the solution containing the obtained polymer and solvent is not particularly limited and can be carried out by known methods such as vacuum removal, separation by reprecipitation, and combinations thereof. If necessary, known treatments such as concentration, filtration, centrifugation, and drying can be performed.

[0189] [Film forming composition] The composition of this embodiment can be used for film formation applications. Specifically, because the film-forming composition of this embodiment contains the polymer of this embodiment, it can exhibit excellent heat resistance and etching resistance.

[0190] In this specification, "film" refers to a material that can be applied to, for example, lithography films or optical components (but not limited to these), and its size and shape are not particularly limited, typically having a form common to lithography films or optical components. That is, "film-forming composition" is a precursor of such a film, and is clearly distinguishable from the "film" in its form and / or composition. Furthermore, "lithography film" is a broad concept that encompasses films used for lithography applications, such as permanent resist films and lithography underlayer films.

[0191] [Uses of film-forming compositions] The film-forming composition of this embodiment contains the polymer described above, but can have various compositions depending on its specific application. Depending on the application or composition, it may be referred to as a "resist composition," a "radiation-sensitive composition," or a "lithography underlayer film-forming composition" below.

[0192] [Resist composition] The resist composition of this embodiment includes the film-forming composition of this embodiment. That is, the resist composition of this embodiment contains the polymer of this embodiment as an essential component, and considering that it is used as a resist material, it may further contain various optional components. Specifically, the resist composition of this embodiment preferably further contains at least one selected from the group consisting of solvents, acid generators, and acid diffusion control agents.

[0193] (solvent) Furthermore, the solvent that the resist composition of this embodiment may contain is not particularly limited, and various known organic solvents can be used. For example, those described in International Publication No. 2013 / 024778 can be used. These solvents can be used alone or in combination of two or more.

[0194] The solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), CHN (cyclohexanone), CPN (cyclopentanone), 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, and CHN.

[0195] In this embodiment, the amounts of the solid component (components other than the solvent in the resist composition of this embodiment) and the solvent are not particularly limited, but it is preferably 1 to 80 parts by mass of the solid component and 20 to 99 parts by mass of the solvent, more preferably 1 to 50 parts by mass of the solid component and 50 to 99 parts by mass of the solvent, even more preferably 2 to 40 parts by mass of the solid component and 60 to 98 parts by mass of the solvent, and particularly preferably 2 to 10 parts by mass of the solid component and 90 to 98 parts by mass of the solvent.

[0196] (Acid generator (C)) In the resist composition of this embodiment, it is preferable to include one or more acid generators (C) that directly or indirectly generate acid upon irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam. The acid generator (C) is not particularly limited, but for example, one described in International Publication No. 2013 / 024778 can be used. The acid generator (C) can be used alone or in combination of two or more.

[0197] The amount of acid generator (C) used is preferably 0.001 to 49% by mass of the total mass of the solid components, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass. By using within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained. In this embodiment, the method of acid generation is not limited as long as acid is generated in the system. If an excimer laser is used instead of ultraviolet rays such as g-rays and i-rays, finer processing is possible, and if an electron beam, extreme ultraviolet rays, X-rays, or ion beam is used as a high-energy beam, even finer processing is possible.

[0198] (Acid crosslinking agent (G)) In this embodiment, the resist composition may contain one or more acid crosslinking agents (G). An acid crosslinking agent (G) is a compound that can crosslink the polymer (component (A)) of this embodiment intramolecularly or intermolecularly in the presence of an acid generated from an acid generator (C). Examples of such acid crosslinking agents (G) include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") that can crosslink component (A).

[0199] Such crosslinkable groups are not particularly limited, but examples include (i) hydroxyalkyl groups such as hydroxy(C1-C6 alkyl), C1-C6 alkoxy(C1-C6 alkyl), acetoxy(C1-C6 alkyl), or groups derived therefrom; (ii) carbonyl groups such as formyl group, carboxy(C1-C6 alkyl), or groups derived therefrom; (iii) nitrogen-containing groups such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group; (iv) glycidyl group-containing groups such as glycidyl ether group, glycidyl ester group, glycidylamino group; (v) groups derived from aromatic groups such as C1-C6 allyloxy(C1-C6 alkyl) and C1-C6 aralkyloxy(C1-C6 alkyl), such as benzyloxymethyl group and benzoyloxymethyl group; and (vi) polymerizable multiple bond-containing groups such as vinyl group and isopropenyl group. In this embodiment, the crosslinkable group of the acid crosslinking agent (G) is preferably a hydroxyalkyl group and an alkoxyalkyl group, with an alkoxymethyl group being particularly preferred.

[0200] The acid crosslinking agent (G) having the above-mentioned crosslinkable group is not particularly limited, but for example, one described in International Publication No. 2013 / 024778 can be used. The acid crosslinking agent (G) can be used alone or in combination of two or more types.

[0201] In this embodiment, the amount of acid crosslinking agent (G) used is preferably 0.5 to 49% by mass of the total mass of the solid components, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass. A blending ratio of 0.5% by mass or more of the acid crosslinking agent (G) is preferable because it improves the effect of suppressing the solubility of the resist film in alkaline developer, thereby suppressing a decrease in the residual film rate and preventing swelling or meandering of the pattern. On the other hand, a blending ratio of 50% by mass or less is preferable because it suppresses a decrease in the heat resistance of the resist.

[0202] (Acid diffusion control agent (E)) In this embodiment, an acid diffusion control agent (E) may be incorporated into the resist composition, which controls the diffusion of acid generated from an acid generator by radiation irradiation within the resist film, thereby preventing undesirable chemical reactions in unexposed areas. Using such an acid diffusion control agent (E) improves the storage stability of the resist composition. It also improves resolution and suppresses linewidth changes in the resist pattern due to variations in the pre- and post-radiation aging time, resulting in extremely excellent process stability. Such an acid diffusion control agent (E) is not particularly limited, but examples include radiodegradable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

[0203] The acid diffusion control agent (E) described above is not particularly limited, but for example, those described in International Publication No. 2013 / 024778 can be used. The acid diffusion control agent (E) can be used alone or in combination of two or more types.

[0204] The amount of acid diffusion control agent (E) is preferably 0.001 to 49% by mass of the total mass of solid components, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass. Within this range, deterioration of resolution, pattern shape, and dimensional fidelity can be prevented. Furthermore, even if the settling time from electron beam irradiation to post-irradiation heating is long, the shape of the upper layer of the pattern will not deteriorate. Also, if the amount is 10% by mass or less, deterioration of sensitivity and developability of unexposed areas can be prevented. In addition, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, the resolution is improved, and changes in the line width of the resist pattern due to variations in the settling time before and after irradiation can be suppressed, resulting in extremely excellent process stability.

[0205] (Other ingredients (F)) The resist composition of this embodiment may optionally contain one or more additives as other components (F), such as dissolution accelerators, dissolution controllers, sensitizers, surfactants, and organic carboxylic acids or phosphorus oxoacids or derivatives thereof.

[0206] (Dissolution accelerator) The low molecular weight dissolution accelerator is a component that enhances the solubility of the polymer in the developer when its solubility in the developer is too low, thereby moderately increasing the dissolution rate of the compound during development. It can be used as needed. Examples of the dissolution accelerator include low molecular weight phenolic compounds, such as bisphenols and tris(hydroxyphenyl)methane. These dissolution accelerators can be used individually or in combination of two or more.

[0207] The amount of dissolution accelerator added is adjusted as appropriate depending on the type of compound used, but is preferably 0 to 49% by mass of the total mass of solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0208] (Soluble control agent) The dissolution control agent is a component that controls the solubility of the polymer in this embodiment when its solubility in the developer is too high, thereby appropriately reducing the dissolution rate during development. It is preferable that such a dissolution control agent does not undergo chemical changes during processes such as firing, radiation irradiation, and development of the resist film.

[0209] The dissolution control agents are not particularly limited, but examples include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthylketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. These dissolution control agents can be used individually or in combination of two or more. The amount of dissolution control agent is adjusted as appropriate depending on the type of compound used, but is preferably 0 to 49% by mass of the total mass of solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0210] (Sensitizer) A sensitizer is a component that absorbs the energy of irradiated radiation and transfers that energy to an acid generator (C), thereby increasing the amount of acid produced and improving the apparent sensitivity of the resist. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more.

[0211] The amount of sensitizer added is adjusted as appropriate depending on the type of compound used, but is preferably 0 to 49% by mass of the total mass of the solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0212] (Surfactants) The surfactant is a component that improves the coatability, striation, and developability of the resist composition of this embodiment. Such surfactants may be anionic surfactants, cationic surfactants, nonionic surfactants, or amphoteric surfactants. Nonionic surfactants are preferred. Nonionic surfactants have good affinity with the solvent used in the manufacture of the resist composition and are therefore more effective. Examples of nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, and higher fatty acid diesters of polyethylene glycol. Commercial products are not particularly limited, but examples include F-Top (manufactured by Gemco), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (both manufactured by Asahi Glass Co., Ltd.), Pepol (manufactured by Toho Chemical Industries, Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and Polyflow (manufactured by Kyoeisha Oil & Fat Chemical Industry Co., Ltd.).

[0213] The amount of surfactant is adjusted as appropriate depending on the type of compound used, but is preferably 0 to 49% by mass of the total mass of solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0214] (Organic carboxylic acids or phosphorus oxoacids or their derivatives) For the purpose of preventing sensitivity degradation or improving resist pattern shape, settling stability, etc., an organic carboxylic acid or phosphorus oxoacid or derivative thereof may be included as an optional component. The organic carboxylic acid or phosphorus oxoacid or derivative thereof may be used in combination with an acid diffusion control agent or used alone. Suitable organic carboxylic acids include, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid. Suitable phosphorus oxoacids or derivatives thereof include phosphoric acid, di-n-butyl phosphate, diphenyl phosphate and other phosphoric acid derivatives or their esters, phosphonic acid or its ester derivatives, phosphonic acid, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and other phosphonic acid derivatives or their esters, phosphinic acid, phenylphosphinic acid and other phosphinic acid derivatives and their ester derivatives, among which phosphonic acid is particularly preferred.

[0215] Organic carboxylic acids or phosphorus oxoacids or their derivatives can be used alone or in combination of two or more. The amount of organic carboxylic acids or phosphorus oxoacids or their derivatives is adjusted as appropriate depending on the type of compound used, but is preferably 0 to 49% by mass of the total mass of solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0216] (Other additives other than those mentioned above (dissolution accelerators, dissolution controllers, sensitizers, surfactants, and organic carboxylic acids or phosphorus oxoacids or their derivatives, etc.)) Furthermore, the resist composition of this embodiment may optionally contain one or more additives other than the above-mentioned dissolution control agent, sensitizer, surfactant, and organic carboxylic acid or phosphorus oxoacid or derivative thereof. Examples of such additives include dyes, pigments, and adhesion aids. For example, the inclusion of dyes or pigments is preferable because it makes the latent image of the exposed area visible and mitigates the effects of halation during exposure. The inclusion of adhesion aids is also preferable because it improves adhesion to the substrate. Other additives are not particularly limited, but examples include halation inhibitors, preservation stabilizers, defoamers, shape improvers, and specifically 4-hydroxy-4'-methyl chalcone.

[0217] In the resist composition of this embodiment, the total amount of optional component (F) is 0 to 99% by mass of the total mass of the solid components, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, even more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0218] [Proportion of each component in the resist composition] In the resist composition of this embodiment, the content of the polymer (component (A)) is not particularly limited, but is preferably 50 to 99.4% by mass of the total mass of the solid components (the sum of the solid components including the polymer (A), acid generator (C), acid crosslinking agent (G), acid diffusion control agent (E), and other components (F) (also referred to as "optional component (F)"), and the same applies hereinafter for the resist composition). More preferably, it is 55 to 90% by mass, even more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. With the above content, the resolution tends to improve further and the line edge roughness (LER) tends to decrease further.

[0219] In the resist composition of this embodiment, the content ratio of the polymer (component (A)), acid generator (C), acid crosslinking agent (G), acid diffusion control agent (E), and optional component (F) (component (A) / acid generator (C) / acid crosslinking agent (G) / acid diffusion control agent (E) / optional component (F)) is preferably 50-99.4% by mass / 0.001-49% by mass / 0.5-49% by mass / 0. The ratios are 0.01-49% by mass / 0-49% by mass, more preferably 55-90% by mass / 1-40% by mass / 0.5-40% by mass / 0.01-10% by mass / 0-5% by mass, even more preferably 60-80% by mass / 3-30% by mass / 1-30% by mass / 0.01-5% by mass / 0-1% by mass, and particularly preferably 60-70% by mass / 10-25% by mass / 2-20% by mass / 0.01-3% by mass / 0% by mass. The proportions of the components are selected from each range so that their sum equals 100% by mass. The above formulations tend to result in superior performance in terms of sensitivity, resolution, developability, etc. Note that "solids" refers to the components excluding the solvent, and "100% by mass of solids" means that the components excluding the solvent are 100% by mass.

[0220] The resist composition of this embodiment is typically prepared by dissolving each component in a solvent to form a homogeneous solution, and then filtering it as needed, for example, through a filter with a pore size of about 0.2 μm.

[0221] The resist composition of this embodiment may optionally contain other resins besides the polymer in this embodiment. These other resins are not particularly limited and include, for example, novolac resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers or derivatives thereof containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. The content of the above other resins is not particularly limited and is adjusted as appropriate depending on the type of component (A) 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 per 100 parts by mass of component (A).

[0222] [Physical properties of the resist composition] The resist composition of this embodiment can form an amorphous film by spin coating. It can also be applied to general semiconductor manufacturing processes. Depending on the type of developer used, either a positive-type resist pattern or a negative-type resist pattern can be produced.

[0223] In the case of a positive-type resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of this embodiment in the developer at 23°C is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and even more preferably 0.0005 to 5 Å / sec. If the dissolution rate is 5 Å / sec or less, it is insoluble in the developer and can be used as a resist. Furthermore, if the dissolution rate is 0.0005 Å / sec or higher, the resolution may be improved. This is presumed to be because the change in solubility of component (A) before and after exposure increases the contrast at the interface between the exposed area that dissolves in the developer and the unexposed area that does not dissolve in the developer. In addition, there is an effect of reducing LER and defects.

[0224] In the case of a negative-type resist pattern, the dissolution rate of the amorphous film formed by spin-coating the resist composition of this embodiment in the developer at 23°C is preferably 10 Å / sec or higher. A dissolution rate of 10 Å / sec or higher makes it easily soluble in the developer and more suitable for use as a resist. Furthermore, a dissolution rate of 10 Å / sec or higher may also improve resolution. This is presumed to be because the microscopic surface portions of component (A) dissolve, reducing the LER. It also has the effect of reducing defects.

[0225] The above dissolution rate can be determined by immersing the amorphous film in the developer solution at 23°C for a predetermined time, and measuring the film thickness before and after immersion by known methods such as visual inspection, cross-sectional observation with an ellipsometer, or scanning electron microscope.

[0226] In the case of a positive-type resist pattern, the dissolution rate in the developer at 23°C of the portion of the amorphous film formed by spin-coating the resist composition of this embodiment with radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray is preferably 10 Å / sec or higher. A dissolution rate of 10 Å / sec or higher makes the resist easily soluble in the developer and more suitable for use as a resist. Furthermore, a dissolution rate of 10 Å / sec or higher may also improve resolution. This is presumed to be because the microscopic surface portion of component (A) dissolves, reducing the LER. It also has the effect of reducing defects.

[0227] In the case of a negative-type resist pattern, the dissolution rate in the developer at 23°C of the portion of the amorphous film formed by spin-coating the resist composition of this embodiment with radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-rays is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and even more preferably 0.0005 to 5 Å / sec. If the dissolution rate is 5 Å / sec or less, it is insoluble in the developer and can be used as a resist. Furthermore, if the dissolution rate is 0.0005 Å / sec or higher, the resolution may be improved. This is presumed to be because the change in solubility of component (A) before and after exposure increases the contrast at the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer. It also has the effect of reducing LER and defects.

[0228] [Radiation sensitive composition] The radiation-sensitive composition of this embodiment is a radiation-sensitive composition containing the film-forming composition of this embodiment, a diazonaphthoquinone photoactive compound (B), and a solvent, wherein the content of the solvent is 20 to 99 parts by mass per 100 parts by mass of the total amount of the radiation-sensitive composition, and the content of components other than the solvent is 1 to 80 parts by mass per 100 parts by mass of the total amount of the radiation-sensitive composition. In other words, the radiation-sensitive composition of this embodiment may contain the polymer of this embodiment, the diazonaphthoquinone photoactive compound (B), and the solvent as essential components, and may further contain various optional components considering its radiation-sensitive properties.

[0229] The radiation-sensitive composition of this embodiment contains a polymer (component (A)) and is used in combination with a diazonaphthoquinone photoactive compound (B). Therefore, it is useful as a substrate for positive-type resists that becomes a compound readily soluble in developer when irradiated with g-rays, h-rays, i-rays, KrF excimer lasers, ArF excimer lasers, extreme ultraviolet light, electron beams, or X-rays. Although the properties of component (A) do not change significantly with g-rays, h-rays, i-rays, KrF excimer lasers, ArF excimer lasers, extreme ultraviolet light, electron beams, or X-rays, the diazonaphthoquinone photoactive compound (B), which is poorly soluble in developer, changes into a readily soluble compound, allowing a resist pattern to be created during the development process.

[0230] The glass transition temperature of the polymer (component (A)) contained in the radiation-sensitive composition of this embodiment is preferably 100°C or higher, more preferably 120°C or higher, even more preferably 140°C or higher, and particularly preferably 150°C or higher. The upper limit of the glass transition temperature of component (A) is not particularly limited, but for example, it is 600°C. When the glass transition temperature of component (A) is within the above range, it has heat resistance that can maintain the pattern shape in the semiconductor lithography process, and tends to improve performance such as high resolution.

[0231] The crystallization heat generated by differential scanning calorimetry of the glass transition temperature of component (A) contained in the radiation-sensitive composition of this embodiment is preferably less than 20 J / g. Furthermore, the (crystallization temperature)-(glass transition temperature) is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 130°C or higher. When the crystallization heat generated is less than 20 J / g, or when the (crystallization temperature)-(glass transition temperature) is within the above range, the radiation-sensitive composition is easily formed by spin coating, the film-forming properties necessary for resist can be maintained for a long period of time, and resolution tends to improve.

[0232] In this embodiment, the crystallization heat, crystallization temperature, and glass transition temperature can be determined by differential scanning calorimetry using a Shimadzu DSC / TA-50WS. Approximately 10 mg of the sample is placed in an unsealed aluminum container and heated above the melting point in a nitrogen gas stream (50 mL / min) at a heating rate of 20°C / min. After rapid cooling, the sample is heated again above the melting point in a nitrogen gas stream (30 mL / min) at a heating rate of 20°C / min. After further rapid cooling, the sample is heated again to 400°C in a nitrogen gas stream (30 mL / min) at a heating rate of 20°C / min. The temperature at the midpoint of the step-like change in the baseline (where the specific heat is halved) is defined as the glass transition temperature (Tg), and the temperature of the subsequent exothermic peak is defined as the crystallization temperature. The amount of heat released is determined from the area of ​​the region enclosed by the exothermic peak and the baseline, and this is defined as the crystallization heat.

[0233] The component (A) contained in the radiation-sensitive composition of this embodiment preferably has low sublimation properties at atmospheric pressure, at temperatures of 100°C or less, preferably 120°C or less, more preferably 130°C or less, even more preferably 140°C or less, and particularly preferably 150°C or less. Low sublimation properties indicate that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, even more preferably 1% or less, and particularly preferably 0.1% or less. Low sublimation properties prevent contamination of the exposure equipment by outgassing during exposure. Furthermore, it is possible to obtain a good pattern shape with low roughness.

[0234] The component (A) contained in the radiation-sensitive composition of this embodiment is selected from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and is dissolved in a solvent that exhibits the highest solubility for component (A) at 23°C, preferably at least 1% by mass, more preferably at least 5% by mass, and even more preferably at least 10% by mass, and more preferably at 23°C at least 20% by mass, and particularly preferably at least 20% by mass in PGMEA, PGME, and CHN, and in a solvent that exhibits the highest solubility for component (A). By satisfying the above conditions, it becomes possible to use the composition in semiconductor manufacturing processes in actual production.

[0235] (Diazonaphthoquinone photoactive compound (B)) The diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition of this embodiment is a diazonaphthoquinone substance that includes polymeric and non-polymeric diazonaphthoquinone photoactive compounds, and is not particularly limited as long as it is commonly used as a photosensitive component (photosensitive agent) in positive-type resist compositions, and one or more types can be arbitrarily selected and used.

[0236] Preferred photosensitive agents include compounds obtained by reacting naphthoquinone diazidesulfonic acid chloride, benzoquinone diazidesulfonic acid chloride, etc., with a low-molecular-weight or high-molecular-weight compound having a functional group capable of condensation with these acid chlorides. The functional group capable of condensation with the acid chloride is not particularly limited, but examples include hydroxyl groups and amino groups, with hydroxyl groups being particularly preferred. Compounds capable of condensation with acid chlorides containing hydroxyl groups are not particularly limited, but examples include hydroquinone, resorcinol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2',3,4,6'-pentahydroxybenzophenone, etc. Examples include cybenzophenones, hydroxyphenylalkanes such as bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, and bis(2,4-dihydroxyphenyl)propane, and hydroxytriphenylmethanes such as 4,4',3”,4”-tetrahydroxy-3,5,3',5'-tetramethyltriphenylmethane and 4,4',2”,3”,4”-pentahydroxy-3,5,3',5'-tetramethyltriphenylmethane.

[0237] Furthermore, preferred acid chlorides such as naphthoquinone diazide sulfonate chloride and benzoquinone diazide sulfonate chloride include, for example, 1,2-naphthoquinone diazide-5-sulfonyl chloride and 1,2-naphthoquinone diazide-4-sulfonyl chloride.

[0238] The radiation-sensitive composition of this embodiment is preferably prepared by, for example, dissolving each component in a solvent at the time of use to form a homogeneous solution, and then filtering it as needed, for example, through a filter with a pore size of about 0.2 μm.

[0239] (solvent) The solvents that can be used in the radiation-sensitive composition of this embodiment are not particularly limited, but examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, cyclopentanone, 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate. Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone are preferred. The solvent may be used alone or in combination of two or more.

[0240] The solvent content is 20 to 99 parts by mass, preferably 50 to 99 parts by mass, more preferably 60 to 98 parts by mass, and particularly preferably 90 to 98 parts by mass, per 100 parts by mass of the total amount of the radiation-sensitive composition.

[0241] Furthermore, the content of components other than the solvent (solid components) is 1 to 80 parts by mass, preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and particularly preferably 2 to 10 parts by mass, per 100 parts by mass of the total amount of the radiation-sensitive composition.

[0242] [Characteristics of radiation-sensitive compositions] The radiation-sensitive composition of this embodiment can form an amorphous film by spin coating. It can also be applied to general semiconductor manufacturing processes. Depending on the type of developer used, either a positive-type resist pattern or a negative-type resist pattern can be produced.

[0243] In the case of a positive-type resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment in the developer at 23°C is preferably 5 Å / sec or less, more preferably 0.05 to 5 Å / sec, and even more preferably 0.0005 to 5 Å / sec. If the dissolution rate is 5 Å / sec or less, it is insoluble in the developer and can be used as a resist. Furthermore, if the dissolution rate is 0.0005 Å / sec or higher, the resolution may be improved. This is presumed to be because the change in solubility of the polymer (component (A)) of this embodiment before and after exposure increases the contrast at the interface between the exposed area that dissolves in the developer and the unexposed area that does not dissolve in the developer. It also has the effect of reducing LER and defects.

[0244] In the case of a negative-type resist pattern, the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment in the developer at 23°C is preferably 10 Å / sec or higher. A dissolution rate of 10 Å / sec or higher makes it easily soluble in the developer and more suitable for resist. Furthermore, a dissolution rate of 10 Å / sec or higher may also improve resolution. This is presumed to be because the microscopic surface portions of component (A) dissolve, reducing the LER. It also has the effect of reducing defects.

[0245] The above dissolution rate can be determined by immersing the amorphous film in the developer solution at 23°C for a predetermined time, and measuring the film thickness before and after immersion by visual inspection, ellipsometer, or known method such as the QCM method.

[0246] In the case of a positive-type resist pattern, the dissolution rate of the exposed portion of an amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment with radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-rays, or after heating at 20 to 500°C (preferably 50 to 500°C), in the developer at 23°C is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and even more preferably 100 to 1000 Å / sec. A dissolution rate of 10 Å / sec or more makes it easily soluble in the developer and more suitable for resist. Furthermore, a dissolution rate of 10000 Å / sec or less may improve resolution. This is presumed to be because the microscopic surface portion of component (A) dissolves, reducing the LER. It also has the effect of reducing defects. In the case of a negative-type resist pattern, the dissolution rate in the exposed portion of an amorphous film formed by spin-coating the radiation-sensitive composition of this embodiment with radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam, or X-rays, or after heating at 20-500°C (preferably 50-500°C), at 23°C is preferably 5 Å / sec or less, more preferably 0.05-5 Å / sec, and even more preferably 0.0005-5 Å / sec. If the dissolution rate is 5 Å / sec or less, it is insoluble in the developer and can be used as a resist. Furthermore, if the dissolution rate is 0.0005 Å / sec or higher, the resolution may be improved. This is presumed to be because the change in solubility of component (A) before and after exposure increases the contrast at the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer. It also has the effect of reducing LER and defects.

[0247] (The proportion of each component in the radiation-sensitive composition) In the radiation-sensitive composition of this embodiment, the content of the polymer of this embodiment (component (A)) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, even more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass, based on the total mass of solid components (the sum of the polymer of this embodiment, the diazonaphthoquinone photoactive compound (B), and other components (D), and the same applies hereinafter for the radiation-sensitive composition). When the content of the polymer of this embodiment is within the above range, a highly sensitive pattern with low roughness can be obtained in the radiation-sensitive composition of this embodiment.

[0248] In the radiation-sensitive composition of this embodiment, the content of the diazonaphthoquinone photoactive compound (B) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, even more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass, based on the total mass of the solid components. When the content of the diazonaphthoquinone photoactive compound (B) in the radiation-sensitive composition of this embodiment is within the above range, a highly sensitive pattern with low roughness can be obtained.

[0249] (Other ingredients (D)) The radiation-sensitive composition of this embodiment may optionally contain one or more additives other than the solvent, the polymer of this embodiment, and the diazonaphthoquinone photoactive compound (B), such as the acid generator, acid crosslinking agent, acid diffusion control agent, dissolution accelerator, dissolution control agent, sensitizer, surfactant, organic carboxylic acid, or phosphorus oxoacid or derivative thereof. In relation to the radiation-sensitive composition of this embodiment, the other component (D) may be referred to as optional component (D).

[0250] The content ratio ((A) / (B) / (D)) of the polymer (component (A)), the diazonaphthoquinone photoactive compound (B), and the optional component (D) of this embodiment is preferably 1-99% by mass / 99-1% by mass / 0-98% by mass, more preferably 5-95% by mass / 95-5% by mass / 0-49% by mass, even more preferably 10-90% by mass / 90-10% by mass / 0-10% by mass, particularly preferably 20-80% by mass / 80-20% by mass / 0-5% by mass, and most preferably 25-75% by mass / 75-25% by mass / 0% by mass, based on 100% by mass of the solid content of the radiation-sensitive composition.

[0251] The proportion of each component is selected from the ranges such that the sum of the proportions equals 100% by mass. When the proportion of each component in the radiation-sensitive composition of this embodiment is within the above range, it exhibits excellent performance in terms of roughness, sensitivity, resolution, and other properties.

[0252] The radiation-sensitive composition of this embodiment may contain resins other than the polymer of this embodiment. Examples of such other resins include novolac resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers or derivatives thereof that contain acrylic acid, vinyl alcohol, or vinylphenol as monomer units. The amount of other resins is adjusted as appropriate depending on the type of polymer of this embodiment 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, per 100 parts by mass of the polymer of this embodiment.

[0253] [Method for producing amorphous films] The method for producing an amorphous film according to this embodiment includes the step of forming an amorphous film on a substrate using the above-mentioned radiation-sensitive composition.

[0254] [Method for forming a resist pattern] In this embodiment, the resist pattern can be formed using the resist composition of this embodiment or the radiation-sensitive composition of this embodiment. Alternatively, as will be described later, the resist pattern can also be formed using the lithography underlayer film forming composition of this embodiment.

[0255] [Method for forming a resist pattern using a resist composition] A method for forming a resist pattern using the resist composition of this embodiment comprises the steps of: forming a resist film on a substrate using the resist composition of this embodiment described above; exposing at least a portion of the formed resist film; and developing the exposed resist film to form a resist pattern. The resist pattern in this embodiment can also be formed as an upper resist in a multilayer process.

[0256] [Method for forming a resist pattern using a radiation-sensitive composition] The resist pattern formation method using the radiation-sensitive composition of this embodiment includes the steps of: forming a resist film on a substrate using the radiation-sensitive composition; exposing at least a portion of the formed resist film; and developing the exposed resist film to form a resist pattern. In detail, the operation can be the same as the resist pattern formation method using the resist composition described below.

[0257] The following describes the conditions for implementing the resist pattern formation method that may be common to both the case using the resist composition of this embodiment and the case using the radiation-sensitive composition of this embodiment. The method for forming the resist pattern is not particularly limited, but examples include the following. First, a resist film is formed by applying the resist composition of this embodiment onto a conventionally known substrate using a coating means such as rotary coating, casting, or roll coating. Conventionally known substrates are not particularly limited, and examples include substrates for electronic components or those on which a predetermined wiring pattern is formed. More specifically, although not particularly limited, examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. The material for the wiring pattern is not particularly limited, but examples include copper, aluminum, nickel, and gold. In addition, an inorganic and / or organic film may be provided on the aforementioned substrate as needed. The inorganic film is not particularly limited, but examples include an inorganic anti-reflective film (inorganic BARC). The organic film is not particularly limited, but examples include an organic anti-reflective film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.

[0258] Next, the coated substrate is heated as needed. The heating conditions vary depending on the composition of the resist, but are preferably 20 to 250°C, and more preferably 20 to 150°C. Heating is preferable because it can improve the adhesion of the resist to the substrate. Then, the resist film is exposed to radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray, and ion beam to form a desired pattern. The exposure conditions are appropriately selected according to the composition of the resist. In this embodiment, heating after radiation is preferable in order to stably form high-precision fine patterns during exposure.

[0259] Next, the exposed resist film is developed with a developer to form a predetermined resist pattern. As the developer, it is preferable to select a solvent with a solubility parameter (SP value) close to that of component (A). Polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, or hydrocarbon solvents, or alkaline aqueous solutions can be used. Examples of such solvents and alkaline aqueous solutions include those described in International Publication No. 2013 / 024778.

[0260] The above solvents may be mixed in multiple quantities, or mixed with other solvents or water within a range that maintains performance. Here, from the viewpoint of further enhancing the desired effects of this embodiment, the water content of the entire developer solution is less than 70% by mass, preferably less than 50% by mass, more preferably less than 30% by mass, even more preferably less than 10% by mass, and particularly preferably substantially water-free. That is, the content of the organic solvent in the developer solution is 30% by mass or more and 100% by mass or less, preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, relative to the total amount of the developer solution.

[0261] In particular, a developer containing at least one solvent selected from ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is preferred in order to improve the resist performance such as the resolution and roughness of the resist pattern.

[0262] A suitable amount of surfactant may be added to the developing solution as needed. While the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and / or silicone-based surfactants can be used. Examples of these fluorine and / or silicone-based surfactants include those described in Japanese Patent Publication No. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 7-230165, 8-62834, 9-54432, 9-5988, U.S. Patent No. 5405720, 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, and 5824451, and are preferably nonionic surfactants. The nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicone-based surfactant.

[0263] The amount of surfactant used is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total amount of the developing solution.

[0264] The development method is not particularly limited, but for example, it can be applied to immerse the substrate in a tank filled with developer for a certain period of time (dip method), develop by piling up the developer on the substrate surface using surface tension and letting it remain still for a certain period of time (paddle method), spray the developer onto the substrate surface (spray method), or continuously dispense the developer onto a substrate rotating at a constant speed while scanning the developer dispensing nozzle at a constant speed (dynamic dispensing method). There is no particular limit to the time for developing the pattern, but it is preferably 10 to 90 seconds.

[0265] Alternatively, after the development process, a step may be performed to stop the development process while replacing the solvent with another solvent.

[0266] It is preferable that the development process includes a step of washing with a rinsing solution containing an organic solvent.

[0267] The rinsing solution used in the rinsing step after development is not particularly limited as long as it does not dissolve the resist pattern hardened by crosslinking, and a solution containing a general organic solvent or water can be used. Preferably, the rinsing solution contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, after development, a washing step is performed using a rinsing solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents. Even more preferably, after development, a washing step is performed using a rinsing solution containing an alcohol solvent or an ester solvent. Even more preferably, after development, a washing step is performed using a rinsing solution containing a monohydric alcohol. Particularly preferably, after development, a washing step is performed using a rinsing solution containing a monohydric alcohol with 5 or more carbon atoms. The time for rinsing the pattern is not particularly limited, but is preferably 10 to 90 seconds.

[0268] Here, monohydric alcohols used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols, and are not particularly limited, but examples include those described in International Publication No. 2013 / 024778. Particularly preferred monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol.

[0269] The above components may be mixed in multiple quantities, or they may be mixed with other organic solvents before use.

[0270] The water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By reducing the water content to 10% by mass or less, better developing characteristics can be obtained.

[0271] The rinse solution can also be used with an appropriate amount of surfactant added.

[0272] In the rinsing process, the developed wafer is cleaned using a rinsing solution containing the above-mentioned organic solvent. The cleaning method is not particularly limited, but for example, a method of continuously applying the rinsing solution onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or a method of spraying the rinsing solution onto the substrate surface (spray method) can be applied. Among these, it is preferable to perform the cleaning using the rotary coating method, and after cleaning, rotate the substrate at a rotational speed of 2000 rpm to 4000 rpm to remove the rinsing solution from the substrate.

[0273] A patterned wiring board can be obtained by etching after forming a resist pattern. Etching can be carried out by known methods such as dry etching using plasma gas and wet etching using alkaline solutions, cupric chloride solutions, ferric chloride solutions, etc.

[0274] After forming the resist pattern, plating can also be performed. Examples of the above plating methods include copper plating, solder plating, nickel plating, and gold plating.

[0275] The residual resist pattern after etching can be removed with an organic solvent. The organic solvent is not particularly limited, but examples include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). The removal method is not particularly limited, but examples include immersion and spraying. Furthermore, the wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate and may have small-diameter through-holes.

[0276] The wiring substrate obtained in this embodiment can also be formed by a method in which a resist pattern is formed, a metal is deposited in a vacuum, and then the resist pattern is dissolved in a solution, i.e., the lift-off method.

[0277] [Composition for forming lower layer film for lithography] The lithography underlayer film-forming composition of this embodiment includes the film-forming composition of this embodiment. That is, the lithography underlayer film-forming composition of this embodiment contains the polymer of this embodiment as an essential component, and may further contain various optional components, taking into consideration that it will be used as a lithography underlayer film-forming material. Specifically, the lithography underlayer film-forming composition of this embodiment preferably further contains at least one selected from the group consisting of solvents, acid generators, and crosslinking agents.

[0278] In this embodiment, the polymer content is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, even more preferably 50 to 100% by mass, and particularly preferably 100% by mass, based on the total solid content in the lithography underlayer film forming composition, from the viewpoint of coatability and quality stability.

[0279] When the lithography underlayer film-forming composition of this embodiment contains a solvent, the polymer content in this embodiment is not particularly limited, but is preferably 1 to 33 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 3 to 20 parts by mass, per 100 parts by mass of the total amount including the solvent.

[0280] The lithography underlayer film forming composition of this embodiment can be applied to wet processes and has excellent heat resistance and etching resistance. Furthermore, because the lithography underlayer film forming composition of this embodiment contains the polymer of this embodiment, film degradation during high-temperature baking is suppressed, and an underlayer film with excellent etching resistance to oxygen plasma etching and the like can be formed. In addition, the lithography underlayer film forming composition of this embodiment has excellent adhesion to the resist layer, so an excellent resist pattern can be obtained. Note that the lithography underlayer film forming composition of this embodiment may contain already known lithography underlayer film forming materials, etc., to the extent that the desired effects of this embodiment are not impaired.

[0281] (solvent) As the solvent used in the lithography underlayer film forming composition of this embodiment, any known solvent can be used as appropriate, as long as it can at least dissolve the polymer of this embodiment.

[0282] Specific examples of solvents are not limited to those described in International Publication No. 2013 / 024779. These solvents can be used individually or in combination of two or more.

[0283] Among the solvents mentioned above, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, and anisole are particularly preferred from a safety standpoint.

[0284] The solvent content is not particularly limited, but from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass, more preferably 200 to 5,000 parts by mass, and even more preferably 200 to 1,000 parts by mass, per 100 parts by mass of polymer in this embodiment.

[0285] (Crosslinking agent) The lithography underlayer film-forming composition of this embodiment may contain a crosslinking agent as needed, from the viewpoint of suppressing intermixing, etc. The crosslinking agent usable in this embodiment is not particularly limited, but for example, those described in International Publication Nos. 2013 / 024778, 2013 / 024779, and 2018 / 016614 can be used. In this embodiment, the crosslinking agent can be used alone or in combination of two or more.

[0286] Specific examples of crosslinking agents usable in this embodiment include, but are not limited to, phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, isocyanate compounds, and azide compounds. These crosslinking agents can be used individually or in combination of two or more. Among these, benzoxazine compounds, epoxy compounds, or cyanate compounds are preferred, and benzoxazine compounds are more preferred from the viewpoint of improving etching resistance. Melamine compounds and urea compounds are more preferred from the viewpoint of having good reactivity. Examples of melamine compounds include the compound represented by formula (a) (Nicalac MW-100LM (trade name), manufactured by Sanwa Chemical Co., Ltd.) and the compound represented by formula (b) (Nicalac MX270 (trade name), manufactured by Sanwa Chemical Co., Ltd.).

[0287] [ka]

[0288] From the viewpoint of improving etching resistance, phenol compounds containing condensed aromatic rings are more preferred. Furthermore, from the viewpoint of improving planarity, phenol compounds containing methylol groups are more preferred. Known phenol compounds can be used, and are not particularly limited.

[0289] From the viewpoint of improving planarity, methylol group-containing phenol compounds used as crosslinking agents are preferred if they are represented by the following formulas (11-1) or (11-2). [ka]

[0290] In the crosslinking agent represented by general formula (11-1) or (11-2), V is a single bond or an n-valent organic group, R2 and R4 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R3 and R5 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n is an integer from 2 to 10, and r is each independently an integer from 0 to 6.

[0291] Specific examples of general formulas (11-1) or (11-2) include compounds represented by the following formulas. However, general formulas (11-1) or (11-2) are not limited to compounds represented by the following formulas.

[0292] [ka]

[0293] [ka]

[0294] [ka]

[0295] The epoxy compound can be any known compound and is not particularly limited, but preferably, in terms of heat resistance and solubility, it is an epoxy resin that is solid at room temperature, such as epoxy resins obtained from phenol aralkyl resins or biphenyl aralkyl resins.

[0296] The cyanate compound can be any known compound having two or more cyanate groups in one molecule, and there are no particular limitations on such compounds. In this embodiment, preferred cyanate compounds include those in which the hydroxyl groups of a compound having two or more hydroxyl groups in one molecule are substituted with cyanate groups. Furthermore, cyanate compounds having aromatic groups are preferred, and those in which the cyanate group is directly bonded to the aromatic group can be suitably used. Such cyanate compounds are not particularly limited, but examples include those in which a hydroxyl group is substituted with a cyanate group, such as bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethylbisphenol F, bisphenol A novolac resin, brominated bisphenol A, brominated phenol novolac resin, trifunctional phenol, tetrafunctional phenol, naphthalene-type phenol, biphenyl-type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, phosphorus-containing phenol, etc. Furthermore, the above-mentioned cyanate compounds may be in any form, such as monomers, oligomers, or resins.

[0297] While known amino compounds can be used and are not particularly limited, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, and 4,4'-diaminodiphenyl ether are preferred from the viewpoint of heat resistance and raw material availability.

[0298] While known benzoxazine compounds can be used and are not particularly limited, Pd-type benzoxazines obtained from bifunctional diamines and monofunctional phenols are preferred from the viewpoint of heat resistance.

[0299] While known melamine compounds can be used and are not particularly limited, hexamethylmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylmelamine are methoxymethylated, or mixtures thereof are preferred from the viewpoint of raw material availability.

[0300] The guanamine compound can be any known compound and is not particularly limited, but tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof is preferred from the viewpoint of heat resistance.

[0301] While known glycoluryl compounds can be used and are not particularly limited, tetramethylol glycoluryl and tetramethoxyglycoluryl are preferred from the viewpoint of heat resistance and etching resistance.

[0302] The urea compound can be any known compound and is not particularly limited, but tetramethylurea and tetramethoxymethylurea are preferred from the viewpoint of heat resistance.

[0303] Furthermore, in this embodiment, a crosslinking agent having at least one allyl group may be used from the viewpoint of improving crosslinkability. Among these, allylphenols such as 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3-allyl-4-hydroxyphenyl)propane, bis(3-allyl-4-hydroxyphenyl)sulfone, bis(3-allyl-4-hydroxyphenyl)sulfide, and bis(3-allyl-4-hydroxyphenyl)ether are preferred.

[0304] In the lithography underlayer film-forming composition of this embodiment, the content of the crosslinking agent is not particularly limited, but is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the polymer in this embodiment. By setting the content within the above preferred range, the occurrence of mixing with the resist layer tends to be suppressed, the anti-reflective effect is enhanced, and the film-forming ability after crosslinking tends to be improved.

[0305] (Crosslinking promoter) The lithography underlayer film forming composition of this embodiment may, if necessary, contain a crosslinking accelerator to promote the crosslinking and curing reactions.

[0306] The aforementioned crosslinking accelerator is not particularly limited as long as it promotes the crosslinking and curing reactions, but examples include amines, imidazoles, organophosphines, Lewis acids, etc. These crosslinking accelerators can be used individually or in combination of two or more. Among these, imidazoles or organophosphines are preferred, and from the viewpoint of lowering the crosslinking temperature, imidazoles are more preferred.

[0307] The aforementioned crosslinking accelerator can be any known one and is not particularly limited, but examples include those described in International Publication No. 2018 / 016614. From the viewpoint of heat resistance and curing acceleration, 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole are particularly preferred.

[0308] The crosslinking accelerator is typically contained in an amount of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, based on a total mass of 100 parts by mass of the composition.

[0309] (Radical polymerization initiator) The lithography underlayer film forming composition of this embodiment may optionally contain a radical polymerization initiator. 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 may be at least one selected from the group consisting of, for example, ketone-based photopolymerization initiators, organic peroxide-based polymerization initiators, and azo-based polymerization initiators.

[0310] Such radical polymerization initiators are not particularly limited, and conventionally used ones can be used as appropriate. For example, those described in International Publication No. 2018 / 016614 can be cited. Among these, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and t-butylcumyl peroxide are particularly preferred from the viewpoint of raw material availability and storage stability.

[0311] The radical polymerization initiator used in this embodiment may be one of these used alone, or two or more used in combination, or it may be used in combination with other known polymerization initiators.

[0312] (Acid generator) The lithography underlayer film forming composition of this embodiment may contain an acid generator as needed, from the viewpoint of further promoting the thermal crosslinking reaction. Known acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and any of these can be used.

[0313] The acid generator is not particularly limited, but for example, one described in International Publication No. 2013 / 024779 can be used. In this embodiment, the acid generator can be used alone or in combination of two or more types.

[0314] In the lithography underlayer film forming composition of this embodiment, the content of the acid generator is not particularly limited, but is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 40 parts by mass, per 100 parts by mass of the polymer in this embodiment. By setting the content within the above preferred range, the amount of acid generated tends to increase, which tends to enhance the crosslinking reaction, and the occurrence of mixing with the resist layer tends to be suppressed.

[0315] (Basic compounds) Furthermore, the lithography underlayer film-forming composition of this embodiment may contain a basic compound from the viewpoint of improving storage stability, etc.

[0316] Basic compounds act as quenchers for acids, preventing trace amounts of acid generated by the acid generator from advancing the crosslinking reaction. Examples of such basic compounds include, but are not limited to, primary, secondary, or tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, and imide derivatives.

[0317] The basic compound used in this embodiment is not particularly limited, but for example, one described in International Publication No. 2013 / 024779 can be used. In this embodiment, the basic compound can be used alone or in combination of two or more.

[0318] In the lithography underlayer film-forming composition of this embodiment, the content of the basic compound is not particularly limited, but is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of the polymer in this embodiment. By keeping it within the above preferred range, storage stability tends to be improved without excessively impairing the crosslinking reaction.

[0319] (Other additives) Furthermore, the lithography underlayer film-forming composition of this embodiment may contain other resins and / or compounds that do not fall under the polymer of this embodiment, for the purpose of imparting thermosetting properties or controlling absorbance. Examples of such other resins and / or compounds include, but are not particularly limited to, naphthol resins, xylene resin naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth)acrylate, dimethacrylate, trimethacrylate, tetramethacrylate, resins containing heterocyclic rings such as vinylnaphthalene, polyacenaphthylene, biphenyl rings such as phenanthrenequinone and fluorene, thiophene, indene, etc., or resins that do not contain aromatic rings; rosin-based resins, cyclodextrins, adamantane(poly)ol, tricyclodecane(poly)ol and their derivatives, etc., or resins or compounds containing alicyclic structures. The known additives mentioned above are not limited to the following, but include, for example, UV absorbers, surfactants, colorants, and nonionic surfactants.

[0320] [Method for forming a lithography underlayer] The method for forming a lithography underlayer film (manufacturing method) of this embodiment includes the step of forming an underlayer film on a substrate using the lithography underlayer film forming composition of this embodiment.

[0321] [Method for forming resist patterns using a composition for forming an underlayer film for lithography] The resist pattern formation method using the lithography underlayer film formation composition of this embodiment includes the steps of forming an underlayer film on a substrate using the lithography underlayer film formation composition of this embodiment (A-1), and forming at least one photoresist layer on the underlayer film (A-2). The resist pattern formation method may also include the step of irradiating a predetermined area of ​​the photoresist layer with radiation and developing it to form a resist pattern (A-3).

[0322] [Method for forming circuit patterns using a composition for forming an underlayer film for lithography] The circuit pattern formation method using the lithography underlayer formation composition of this embodiment comprises the steps of: forming an underlayer on a substrate using the lithography underlayer formation composition of this embodiment (B-1); forming an intermediate layer on the underlayer using a resist intermediate layer material containing silicon atoms (B-2); forming at least one photoresist layer on the intermediate layer (B-3); irradiating a predetermined area of ​​the photoresist layer with radiation after step (B-3) to develop and form a resist pattern (B-4); etching the intermediate layer using the resist pattern as a mask after step (B-4) to form an intermediate layer pattern (B-5); etching the underlayer using the obtained intermediate layer pattern as an etching mask to form an underlayer pattern (B-6); and etching the substrate using the obtained underlayer pattern as an etching mask to form a pattern on the substrate (B-7).

[0323] The lithography underlayer film of this embodiment is formed from the lithography underlayer film forming composition of this embodiment, but the method of formation is not particularly limited, and known methods can be applied. For example, the underlayer film can be formed by applying the lithography underlayer film forming composition of this embodiment to a substrate by known coating or printing methods such as spin coating or screen printing, and then removing it by volatilizing the organic solvent.

[0324] When forming the lower layer film, it is preferable to bake it in order to suppress the mixing phenomenon with the upper layer resist and to promote the crosslinking reaction. In this case, the bake temperature is not particularly limited, but is preferably in the range of 80 to 450°C, and more preferably in the range of 200 to 400°C. The bake time is also not particularly limited, but is preferably in the range of 10 to 300 seconds. The thickness of the lower layer film can be appropriately selected according to the required performance and is not particularly limited, but is usually preferably around 30 to 20,000 nm, and more preferably 50 to 15,000 nm.

[0325] After fabricating the lower layer film, in the case of a two-layer process, it is preferable to fabricate a silicon-containing resist layer or a single-layer resist containing ordinary hydrocarbons on top of it, and in the case of a three-layer process, it is preferable to fabricate a silicon-containing intermediate layer on top of it, and a silicon-free single-layer resist layer on top of that. In this case, known photoresist materials can be used to form these resist layers.

[0326] After fabricating a base layer on a substrate, in the case of a two-layer process, a silicon-containing resist layer or a single-layer resist containing ordinary hydrocarbons can be fabricated on the base layer. In the case of a three-layer process, a silicon-containing intermediate layer can be fabricated on the base layer, and a silicon-free single-layer resist layer can be fabricated on the silicon-containing intermediate layer. In these cases, the photoresist material for forming the resist layer can be appropriately selected from known materials and is not particularly limited.

[0327] For silicon-containing resist materials used in two-layer processes, a positive-type photoresist material is preferably used, from the viewpoint of oxygen gas etching resistance, in which a silicon atom-containing polymer such as a polysilsesquioxane derivative or vinylsilane derivative is used as the base polymer, and further containing an organic solvent, an acid generator, and optionally a basic compound. Here, known polymers used in this type of resist material can be used as the silicon atom-containing polymer.

[0328] For a three-layer process, a polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer. By giving the intermediate layer an anti-reflective effect, reflection tends to be effectively suppressed. For example, in a 193nm exposure process, if a material containing many aromatic groups and having high substrate etching resistance is used as the lower layer, the k value tends to increase and substrate reflection tends to increase. However, by suppressing reflection with the intermediate layer, substrate reflection can be reduced to 0.5% or less. While not limited to the following, polysilsesquioxane that can be crosslinked with acid or heat and into which phenyl groups or light-absorbing groups having silicon-silicon bonds are introduced is preferably used for 193nm exposure.

[0329] Furthermore, an intermediate layer formed by the Chemical Vapor Deposition (CVD) method can also be used. While not limited to the following, a highly effective intermediate layer as an anti-reflective coating produced by the CVD method is known, for example, a SiON film. Generally, forming the intermediate layer by wet processes such as spin coating or screen printing is simpler and more cost-effective than the CVD method. In the three-layer process, the top resist can be either positive or negative, and the same type of single-layer resist commonly used can be used.

[0330] Furthermore, the underlayer film in this embodiment can also be used as an anti-reflective film for ordinary single-layer resists or as a base material for suppressing pattern deformation. Since the underlayer film in this embodiment has excellent etching resistance for base processing, it can also be expected to function as a hard mask for base processing.

[0331] When forming a resist layer using the above-mentioned photoresist material, a wet process such as spin coating or screen printing is preferably used, similar to the process used to form the underlying film. After applying the resist material by spin coating or the like, pre-baking is usually performed, preferably at 80-180°C for 10-300 seconds. Subsequently, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain the resist pattern. The thickness of the resist film is not particularly limited, but is generally preferred to be 30-500 nm, and more preferably 50-400 nm.

[0332] Furthermore, the exposure light should be appropriately selected depending on the photoresist material being used. Generally, high-energy rays with wavelengths of 300 nm or less can be used, specifically excimer lasers at 248 nm, 193 nm, and 157 nm, soft X-rays, electron beams, and X-rays at 3 to 20 nm.

[0333] The resist pattern formed by the above method has pattern distortion suppressed by the underlayer film in this embodiment. Therefore, by using the underlayer film in this embodiment, a finer pattern can be obtained, and the amount of exposure required to obtain that resist pattern can be reduced.

[0334] Next, etching is performed using the obtained resist pattern as a mask. In a two-layer process, gas etching is preferably used for etching the lower layer film. As for gas etching, etching using oxygen gas is preferred. In addition to oxygen gas, inert gases such as He and Ar, or CO, CO2, NH3, SO2, N2, NO 2、 It is also possible to add H2 gas. Furthermore, without using oxygen gas, CO, CO2, NH3, N2, NO 2、 Gas etching can also be performed using only H2 gas. The latter gas is particularly preferred for sidewall protection to prevent undercutting of the pattern sidewalls.

[0335] On the other hand, gas etching is also preferably used for etching the intermediate layer in the three-layer process. The same gas etching methods as those described in the two-layer process above can be applied. In particular, it is preferable to process the intermediate layer in the three-layer process using a fluorocarbon-based gas to mask the resist pattern. Subsequently, as described above, the underlying film can be processed by using the intermediate layer pattern as a mask and performing, for example, oxygen gas etching.

[0336] In this case, when forming an inorganic hard mask intermediate layer, a silicon oxide film, silicon nitride film, or silicon oxynitride film (SiON film) is formed by methods such as CVD or atomic layer deposition (ALD). The method for forming the nitride film is not limited to the following, but for example, the method described in Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377 can be used. A photoresist film can be formed directly on such an intermediate layer, but an organic anti-reflective coating (BARC) may be formed on the intermediate layer by spin coating, and then a photoresist film may be formed on top of that.

[0337] A polysilsesquioxane-based intermediate layer is also preferably used as an intermediate layer. By giving the resist intermediate layer film an anti-reflective effect, reflection tends to be effectively suppressed. The specific material of the polysilsesquioxane-based intermediate layer is not limited to the following, but for example, those described in Japanese Patent Publication No. 2007-226170 and Japanese Patent Publication No. 2007-226204 can be used.

[0338] Furthermore, etching of the substrate can also be performed by conventional methods. For example, if the substrate is SiO2 or SiN, etching can be performed mainly with fluorocarbon gases, while etching can be performed mainly with chlorine-based or bromine-based gases for p-Si, Al, or W. When etching the substrate with fluorocarbon gases, the silicon-containing resist in a two-layer resist process and the silicon-containing intermediate layer in a three-layer resist process are stripped simultaneously with the substrate processing. On the other hand, when etching the substrate with chlorine-based or bromine-based gases, the silicon-containing resist layer or silicon-containing intermediate layer is stripped separately, and generally, dry etching stripping with fluorocarbon gas is performed after the substrate processing.

[0339] The underlying film in this embodiment is characterized by excellent etching resistance of these substrates. The substrate can be appropriately selected from known materials and is not particularly limited, but examples include Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc. The substrate may also be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such films to be processed include various low-k films and stopper films thereon, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc., and are usually made of a different material from the base material (support). The thickness of the substrate to be processed or the film to be processed is not particularly limited, but is usually preferably around 50 to 1,000,000 nm, and more preferably 75 to 500,000 nm.

[0340] [Permanent Resistant Film] Furthermore, a permanent resist film can also be fabricated using the film-forming composition of this embodiment. A permanent resist film formed by applying the film-forming composition of this embodiment to a substrate is suitable as a permanent film that remains in the final product after a resist pattern is formed as needed. Specific examples of permanent films are not particularly limited, but include, for example, solder resists, package materials, underfill materials, package adhesive layers for circuit elements, and adhesive layers between integrated circuit elements and circuit boards in semiconductor devices, and thin-film transistor protective films, liquid crystal color filter protective films, black matrices, and spacers in thin-film displays. In particular, permanent films made from the film-forming composition of this embodiment have excellent heat resistance and moisture resistance, as well as the extremely advantageous feature of low contamination by sublimation components. Especially in display materials, it becomes a material that combines high sensitivity, high heat resistance, and moisture absorption reliability with minimal image quality degradation due to important contamination.

[0341] When the film-forming composition of this embodiment is used for resist permanent film applications, in addition to the curing agent, various additives such as other resins, surfactants, dyes, fillers, crosslinking agents, and dissolution accelerators can be added as needed and dissolved in an organic solvent to produce a resist permanent film composition.

[0342] When the film-forming composition of this embodiment is intended for use as a permanent resist film, the composition can be prepared by blending the above-mentioned components and mixing them using a stirrer or the like. Furthermore, if the film-forming composition of this embodiment contains fillers or pigments, the composition can be prepared by dispersing or mixing them using a dispersion device such as a dissolver, homogenizer, or three-roll mill.

[0343] [Composition for forming optical components] The film-forming composition of this embodiment can also be used for forming optical components (or optical parts). That is, the optical component-forming composition of this embodiment contains the film-forming composition of this embodiment. In other words, the optical component-forming composition of this embodiment contains the polymer of this embodiment as an essential component. Here, "optical component" (or "optical part") refers to film-like or sheet-like parts, as well as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, field-of-view control lenses, contrast-enhancing lenses, etc.), phase difference films, electromagnetic shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, and photosensitive optical waveguides. The polymer of this embodiment is useful for these optical component-forming applications. Considering that the optical component-forming composition of this embodiment is used as an optical component-forming material, it may further contain various optional components. Specifically, it is preferable that the optical component-forming composition of this embodiment further contains at least one selected from the group consisting of solvents, acid generators, and crosslinking agents. Specific examples of components that can be used as solvents, acid generators, and crosslinking agents are the same as those that can be included in the lithography underlayer film forming composition of this embodiment described above, and their mixing ratios can be appropriately set considering the specific application. [Examples]

[0344] The following describes the embodiment in more detail with reference to examples and comparative examples, but the embodiment is not limited to these. In the following examples, the examples relating to compound group 1 will be referred to as "Example Group 1," the examples relating to compound group 2 as "Example Group 2," the examples relating to compound group 3 as "Example Group 3," and the examples relating to compound group 4 as "Example Group 4." The example numbers assigned to each of the following examples are individual example numbers for each example group. That is, for example, Example 1 of the example relating to compound group 1 (Example Group 1) will be distinguished as being different from Example 1 of the example relating to compound group 2 (Example Group 2).

[0345] The analysis and evaluation methods for the polymer in this embodiment were as follows.

[0346] (Structural analysis) 1 H-NMR measurements were performed using a Bruker "Advance600II spectrometer" under the following conditions. Frequency: 400MHz Solvent: d6-DMSO Internal standard: TMS Measurement temperature: 23℃

[0347] (molecular weight measurement) LC-MS analysis was performed using an Acquity UPLC / MALDI-Synapt HDMS manufactured by Water. (Molecular weight in terms of polystyrene) Gel permeation chromatography (GPC) analysis was used to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in polystyrene equivalents, and then the degree of dispersion (Mw / Mn) was calculated. Equipment: Shodex GPC-101 (manufactured by Showa Denko Corporation) Columns: KF-80M x 3 Eluent: THF 1mL / min Temperature: 40℃

[0348] (Measurement of film thickness) The film thickness of the resin film created using the polymer was measured using the interferometric film thickness meter "OPTM-A1" (manufactured by Otsuka Electronics Co., Ltd.).

[0349] [Example Group 1] (Synthesis Example 1) Synthesis of ANT-1 In a 500 mL container equipped with a stirrer, condenser, and burette, 25 g (105 mmol) of 1,4,9,10-tetrahydroxyanthracene and 10.1 g (20 mmol) of monobutyl copper phthalate were charged. 100 mL of 1-butanol was added as the solvent, and the reaction mixture was stirred at 100 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and after stirring at room temperature, the mixture was neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. By drying the obtained solid, 38.0 g of the target resin (ANT-1), having the structure represented by the following formula, was obtained. The obtained resin was measured for polystyrene-equivalent molecular weight using the method described above, and the results were Mn: 1212, Mw: 1864, and Mw / Mn: 1.54. When the obtained resin was subjected to NMR measurement under the above measurement conditions, the following peaks were found, confirming that it has the chemical structure shown in the following equation. δ(ppm)9.1~10.3(4H,OH), 6.4~8.5(4H,Ph-H)

[0350] [ka]

[0351] (Synthesis Examples 2-5) Synthesis of ANT-2-ANT-4 and PYL-1 Instead of 1,4,9,10-tetrahydroxyanthracene, 1,8,9-trihydroxyanthracene, 2,6-dihydroxyanthracene, 2-hydroxyanthracene, and 1-hydroxypylene were used, and the procedure was otherwise carried out in the same manner as in Synthesis Example 1, yielding the target compounds (ANT-2), (ANT-3), (ANT-4), and (PYL-1), represented by the following formulas.

[0352] [ka]

[0353] The results of measuring the polystyrene-equivalent molecular weight of the resins obtained in Synthesis Examples 2 to 5 using the method described above are shown below. Furthermore, when the obtained resins were subjected to NMR measurement under the same measurement conditions, the following peaks were found, confirming that they have the chemical structure shown in the formula below. (ANT-2)Mn:1121, Mw:1682, Mw / Mn:1.50 δ(ppm)9.1~10.3(3H,OH), 6.6~8.0(5H,Ph-H) (ANT-3)Mn:1042, Mw:1448, Mw / Mn:1.39 δ(ppm)9.2(2H,OH), 7.2~8.4(6H,Ph-H) (ANT-4)Mn:934, Mw:1252, Mw / Mn:1.34 δ(ppm)9.2(1H,OH), 7.2~8.4(7H,Ph-H) (PYL-5)Mn:718, Mw:886, Mw / Mn:1.23 δ(ppm)9.7(1H,OH), 4.6~4.8(2H,Ph-H), 7.5~7.8(7H,Ph-H)

[0354] (Comparative Synthesis Example 1) In a 100 ml container equipped with a stirrer, condenser, and burette, 10 g (21 mmol) of BisN-2, 0.7 g (42 mmol) of paraformaldehyde, 50 mL of glacial acetic acid, and 50 mL of PGME were charged. 8 mL of 95% sulfuric acid was added, and the reaction mixture was stirred at 100°C for 6 hours. Next, the reaction mixture was concentrated, 1000 mL of methanol 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 to obtain 7.2 g of the target resin (NBisN-1) having the structure shown in the following formula. The obtained resin was measured for polystyrene-equivalent molecular weight using the method described above, and the results were Mn: 1278, Mw: 1993, and Mw / Mn: 1.56. When the obtained resin was subjected to NMR measurement under the above measurement conditions, the following peaks were found, confirming that it has the chemical structure shown in the following equation. δ(ppm)9.7(2H,OH), 7.2~8.5(17H,Ph-H), 6.6(1H,CH), 4.1(2H,-CH2) [ka]

[0355] (Comparative Synthesis Example 2) A 10 L four-necked flask with a removable bottom was prepared, equipped with a Liebig condenser, thermometer, and stirring blades. Into this flask, 1.09 kg (7 mol, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of 1,5-dimethylnaphthalene, 2.1 kg (28 mol as formaldehyde, manufactured by Mitsubishi Gas Chemical Co., Ltd.) of 40% formalin aqueous solution, and 0.97 mL (98% sulfuric acid, manufactured by Kanto Chemical Co., Ltd.) were charged under a nitrogen atmosphere. The reaction was carried out under atmospheric pressure at 100°C under reflux for 7 hours. Subsequently, 1.8 kg of ethylbenzene (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction mixture as a diluent. After standing, the aqueous phase was removed. Further neutralization and washing with water were performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were removed by distillation under reduced pressure to obtain 1.25 kg of light brown solid dimethylnaphthaleneformaldehyde resin.

[0356] Next, a 0.5 L four-necked flask equipped with a Liebig condenser, thermometer, and stirring blade was prepared. Into this four-necked flask, 100 g (0.51 mol) of the obtained dimethylnaphthaleneformaldehyde resin and 0.05 g of p-toluenesulfonic acid were charged under a nitrogen stream. The mixture was heated to 190°C for 2 hours and then stirred. Subsequently, 52.0 g (0.36 mol) of 1-naphthol was added, and the mixture was further heated to 220°C for 2 hours. After solvent dilution, neutralization and washing with water were performed, and the solvent was removed under reduced pressure to obtain 126.1 g of a dark brown solid modified resin (CR-1). Representative substructures of the resin (CR-1) are shown below. These substructures are bonded by methylene groups, but some are also bonded via ether bonds, etc. The obtained resin (CR-1) had a Mn of 885, a Mw of 2220, and a Mw / Mn ratio of 2.51.

[0357] [ka]

[0358] [Examples 1-5] Table 1 shows the results of evaluating the heat resistance of the resins obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Example 1 using the evaluation method described below.

[0359] <Measurement of thermal decomposition temperature> Using the EXSTAR6000TG / DTA instrument manufactured by SII Nanotechnology, approximately 5 mg of the sample was placed in an unsealed aluminum container and heated to 700°C at a heating rate of 10°C / min in a nitrogen gas (30 mL / min) stream. The temperature at which a 10% wt% loss of heat was observed was defined as the thermal decomposition temperature (Tg), and the heat resistance was evaluated according to the following criteria. Rating A: Pyrolysis temperature of 405°C or higher Rating B: Pyrolysis temperature is 320°C or higher Rating C: Pyrolysis temperature below 320°C

[0360] [Table 1]

[0361] As is clear from Table 1, the resins used in Examples 1 to 5 exhibited good heat resistance, while the resin used in Comparative Example 1 was found to have poor heat resistance.

[0362] [Examples 1'-5', Comparative Example 1'] (Preparation of compositions for forming underlayer films for lithography) Lithography underlayer film formation compositions were prepared to have the compositions shown in Table 2. Next, these lithography underlayer film formation compositions were rotary coated onto silicon substrates, and then baked in a nitrogen atmosphere at 240°C for 60 seconds, followed by baking at 400°C for 120 seconds, to produce underlayer films with thicknesses of 200 to 250 nm.

[0363] Next, etching tests were conducted under the conditions shown below to evaluate etching resistance. The evaluation results are shown in Table 2.

[0364] [Etching test] Etching equipment: RIE-10NR manufactured by Samco International Corporation Output: 50W Pressure: 20 Pa Time: 2 min Etching gas Ar gas flow rate:CF4 gas flow rate:O2 gas flow rate = 50:5:5 (sccm)

[0365] (Evaluation of etching resistance) The etching resistance was evaluated using the following procedure. First, a novolac underlayer film was prepared under the same conditions as above, except that novolac (PSM4357, manufactured by Gun-ei Chemical Co., Ltd.) was used. The etching test described above was performed on this novolac underlayer film, and the etching rate was measured.

[0366] Next, the underlayer films of Examples 1' to 5' and Comparative Example 1' were prepared under the same conditions as the underlayer film of novolac, and the etching test described above was performed in the same manner, and the etching rate was measured. The etching resistance was evaluated using the following evaluation criteria, with the etching rate of the novolac underlayer film as the reference. [Evaluation Criteria] A: The etching rate is less than -20% compared to the underlying novolac film. B: Etching rate is -20% to 0% compared to the underlying novolac film. C: Etching rate is more than +0% compared to the underlying novolac film.

[0367] [Table 2]

[0368] In Examples 1’ to 5’, it was found that an etching rate superior to that of the novolak underlayer film and the resin of Comparative Example 1’ was exhibited. On the other hand, it was found that the resin of Comparative Example 1’ had an equivalent etching rate compared to the novolak underlayer film.

[0369] The metal content and solution storage stability before and after purification of the polycyclic polyphenol resin (composition containing the same) were evaluated by the following methods. (Measurement of various metal contents) Using ICP-MS, the metal content in the propylene glycol monomethyl ether acetate (PGMEA) solution of various resins obtained in the following Examples and Comparative Examples was measured under the following measurement conditions. Apparatus: AG8900 manufactured by Agilent Temperature: 25 °C Environment: Class 100 clean room

[0370] (Evaluation of storage stability) The turbidity (HAZE) of the PGMEA solution obtained in the following Examples and Comparative Examples after holding at 23 °C for 240 hours was measured using a color difference and turbidity meter, and the storage stability of the solution was evaluated according to the following criteria. Apparatus: Color difference and turbidity meter COH400 (manufactured by Nippon Denshoku Industries Co., Ltd.) Optical path length: 1 cm Using a quartz cell [Evaluation criteria] 0 ≦ HAZE ≦ 1.0: Good 1.0 < HAZE ≦ 2.0: Fair 2.0 < HAZE: Poor

[0371] (Example 6) Purification of ANT-1 with an acid 150 g of a 1000 mL four-necked flask (bottomless type) containing ANT-1 dissolved in cyclohexanone (10% by mass), obtained in Synthesis Example 1, was placed in the flask and heated to 80°C while stirring. Next, 37.5 g of oxalic acid aqueous solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This separated the solution into an oil phase and an aqueous phase, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes, after which the aqueous phase was removed. After repeating this operation three times, residual water and cyclohexanone were concentrated and removed by reducing the pressure inside the flask to below 200 hPa while heating to 80°C. Subsequently, the solution was diluted with EL grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Ltd.) and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of ANT-1 with reduced metal content.

[0372] (Reference Example 1) Purification of ANT-1 using ultrapure water The procedure was carried out in the same manner as in Example 6, except that ultrapure water was used instead of oxalic acid aqueous solution, and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of ANT-1.

[0373] The metal content of various metals was measured by ICP-MS in a 10% by mass cyclohexanone solution of ANT before treatment, and in the solutions obtained in Example 6 and Reference Example 1. The measurement results are shown in Table 3.

[0374] (Example 7) Acidic purification of ANT-2 In a 1000 mL four-necked flask (bottomless type), 140 g of a solution (10% by mass) of ANT-2 dissolved in cyclohexanone, obtained in Synthesis Example 2, was placed and heated to 60°C while stirring. Next, 37.5 g of oxalic acid aqueous solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This separated the solution into an oil phase and an aqueous phase, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes, after which the aqueous phase was removed. After repeating this operation three times, residual water and cyclohexanone were concentrated and removed by reducing the pressure inside the flask to below 200 hPa while heating to 80°C. Subsequently, the solution was diluted with EL grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Ltd.) and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of ANT-2 with reduced metal content.

[0375] (Reference Example 2) Purification of ANT-2 using ultrapure water The procedure was carried out in the same manner as in Example 7, except that ultrapure water was used instead of oxalic acid aqueous solution, and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of ANT.

[0376] The metal content of various metals was measured by ICP-MS in the 10% by mass cyclohexanone solution of ANT-2 before treatment, and in the solutions obtained in Example 7 and Reference Example 2. The measurement results are shown in Table 3.

[0377] (Example 8) Purification by filtering In a Class 1000 clean booth, 500 g of a 10% by mass solution of the resin (ANT-1) obtained in Synthesis Example 1 dissolved in cyclohexanone was placed in a 1000 mL four-necked flask (bottomless type). Subsequently, the air inside the vessel was removed by reduced pressure, nitrogen gas was introduced to return the pressure to atmospheric pressure, and the oxygen concentration inside was adjusted to less than 1% by aeration with nitrogen gas at a rate of 100 mL / min. The solution was then heated to 30°C while stirring. The solution was withdrawn through the bottom valve and passed through a nylon hollow fiber membrane filter with a nominal pore size of 0.01 μm (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix Nylon Series) at a flow rate of 100 mL / min via a fluororesin pressure-resistant tube using a diaphragm pump. The content of various metals in the obtained ANT-1 solution was measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same method was used hereafter). The measurement results are shown in Table 3.

[0378] (Example 9) Except for using a polyethylene (PE) hollow fiber membrane filter with a nominal pore size of 0.01 μm (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix), the solution was passed through the filter in the same manner as in Example 8, and the content of various metals in the resulting ANT-1 solution was measured by ICP-MS. The measurement results are shown in Table 3.

[0379] (Example 10) Except for using a nylon hollow fiber membrane filter with a nominal pore size of 0.04 μm (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix), the liquid was passed through the filter in the same manner as in Example 8, and the various metal contents of the obtained ANT-1 were measured by ICP-MS. The measurement results are shown in Table 3.

[0380] (Example 11) Except for using a Zeta Plus filter 40QSH (manufactured by 3M Co., Ltd., with ion exchange capability) with a nominal pore size of 0.2 μm, the solution was passed through in the same manner as in Example 8, and the content of various metals in the resulting ANT-1 solution was measured by ICP-MS. The measurement results are shown in Table 3.

[0381] (Example 12) Except for using a ZetaPlus filter 020GN (manufactured by 3M Co., Ltd., with ion exchange capabilities, and differing from the ZetaPlus filter 40QSH in filtration area and filter media thickness) with a nominal pore size of 0.2 μm, the solution was passed through the filter in the same manner as in Example 8, and the resulting ANT-1 solution was analyzed under the following conditions. The measurement results are shown in Table 3.

[0382] (Example 13) Except for using the resin (ANT-2) obtained in Synthesis Example 2 instead of the resin (ANT-1) in Example 8, the solution was passed through in the same manner as in Example 8, and the content of various metals in the resulting ANT-2 solution was measured by ICP-MS. The measurement results are shown in Table 3.

[0383] (Example 14) Except for using the resin (ANT-2) obtained in Synthesis Example 2 instead of the resin (ANT-1) in Example 9, the solution was passed through in the same manner as in Example 9, and the content of various metals in the resulting ANT-2 solution was measured by ICP-MS. The measurement results are shown in Table 3.

[0384] (Example 15) Except for using the resin (ANT-2) obtained in Synthesis Example 2 instead of the compound (ANT-1) in Example 10, the solution was passed through in the same manner as in Example 10, and the content of various metals in the resulting ANT-2 solution was measured by ICP-MS. The measurement results are shown in Table 3.

[0385] (Example 16) Except for using the resin (ANT-2) obtained in Synthesis Example 2 instead of the compound (ANT-1) in Example 11, the solution was passed through in the same manner as in Example 11, and the content of various metals in the resulting ANT-2 solution was measured by ICP-MS. The measurement results are shown in Table 3.

[0386] (Example 17) Except for using the resin (ANT-2) obtained in Synthesis Example 2 instead of the compound (ANT-1) in Example 12, the solution was passed through in the same manner as in Example 12, and the content of various metals in the resulting ANT-2 solution was measured by ICP-MS. The measurement results are shown in Table 3.

[0387] (Example 18) Acid washing and filter flushing combination 1 In a Class 1000 clean booth, 140 g of a 10% by mass cyclohexanone solution of ANT-1 with reduced metal content, obtained in Example 6, was placed in a 300 mL four-necked flask (bottomless type). Subsequently, the air inside the vessel was removed by reduced pressure, nitrogen gas was introduced to return the pressure to atmospheric pressure, and the oxygen concentration inside was adjusted to less than 1% by aeration with nitrogen gas at a rate of 100 mL / min. The solution was then heated to 30°C while stirring. The solution was withdrawn through the bottomless valve and passed through a fluororesin pressure-resistant tube at a flow rate of 10 mL / min using a diaphragm pump through an ion exchange filter (manufactured by Nippon Pall Co., Ltd., product name: Ion Clean Series) with a nominal pore size of 0.01 μm. After that, the recovered solution was returned to the 300 mL four-necked flask, the filter was changed to a high-density PE filter (manufactured by Nippon Integris Co., Ltd.) with a nominal pore size of 1 nm, and the pumping was performed in the same manner. The various metal contents of the obtained cyclohexanone solution were measured by ICP-MS. The oxygen concentration was measured using the OM-25MF10 oxygen meter manufactured by AS ONE Corporation (the same method was used hereafter). The measurement results are shown in Table 3.

[0388] (Example 19) Acid washing and filter flushing combination 2 In a Class 1000 clean booth, 140 g of the 10% by mass PGMEA solution of ANT-1 with reduced metal content obtained in Example 6 was placed in a 300 mL four-necked flask (bottomless type). Subsequently, the air inside the vessel was removed by reduced pressure, nitrogen gas was introduced to return the pressure to atmospheric pressure, and the oxygen concentration inside was adjusted to less than 1% by aeration with nitrogen gas at a rate of 100 mL per minute. The mixture was then heated to 30°C while stirring. The above solution was extracted through a bottom valve and passed through a fluororesin pressure-resistant tube at a flow rate of 10 mL per minute using a diaphragm pump through a nylon hollow fiber membrane filter (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix) with a nominal pore size of 0.01 μm. The recovered solution was then returned to the 300 mL four-necked flask, the filter was replaced with a high-density PE filter (manufactured by Nippon Integris Co., Ltd.) with a nominal pore size of 1 nm, and the pumping process was repeated. The various metal contents of the obtained ANT-1 solution were measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same method was used hereafter). The measurement results are shown in Table 3.

[0389] (Example 20) Acid washing and filter flushing 3 The same procedure as in Example 18 was followed, except that the 10% by mass cyclohexanone solution of ANT-1 used in Example 18 was replaced with the 10% by mass cyclohexanone solution of ANT-2 obtained in Example 7. The 10% by mass cyclohexanone solution of ANT-2 with reduced metal content was recovered. The content of various metals in the obtained solution was measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same method was used hereafter). The measurement results are shown in Table 3.

[0390] (Example 21) Acid washing and filter flushing 4 The same procedure as in Example 19 was followed, except that the 10% by mass cyclohexanone solution of ANT-1 used in Example 19 was replaced with the 10% by mass cyclohexanone solution of ANT-2 obtained in Example 7, and the 10% by mass cyclohexanone solution of ANT-2 with reduced metal content was recovered. The content of various metals in the obtained solution was measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same applies below). The measurement results are shown in Table 3.

[0391] [Table 3] TIFF0007859316000075.tif59170

[0392] As shown in Table 3, it was confirmed that reducing the metals derived from the oxidizing agent through various purification methods improved the storage stability of the resin solution in this embodiment. In particular, by using an acid washing method and an ion exchange filter or nylon filter, ionic metals can be effectively reduced, and by using a high-precision, high-density polyethylene particulate filter in combination, a dramatic metal removal effect can be obtained.

[0393] [Examples 22-27, Comparative Example 3] (Heat resistance and resist performance) Table 4 shows the results of the heat resistance tests and resist performance evaluations performed using the resins obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Example 1.

[0394] (Preparation of resist composition) Using the resins synthesized above, resist compositions were prepared according to the formulations shown in Table 4. Of the components of the resist compositions in Table 4, the following were used for the acid generator (C), acid diffusion control agent (E), and solvent. Acid generator (C) P-1: Triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Chemical Co., Ltd.) Acid crosslinking agent (G) C-1: Nikalac MW-100LM (Sanwa Chemical Co., Ltd.) Acid diffusion control agent (E) Q-1: Trioctylamine (Tokyo Chemical Industries, Ltd.) solvent S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industries, Ltd.)

[0395] (Method for evaluating the resist performance of a resist composition) A uniform resist composition was rotary coated onto a clean silicon wafer, and then pre-exposure baked (PB) in an oven at 110°C to form a 60 nm thick resist film. The resulting resist film was irradiated with an electron beam using an electron beam lithography system (ELS-7500, manufactured by Elionix Corporation) with a 1:1 line-and-space setting at 50 nm intervals. After irradiation, the resist film was heated at a predetermined temperature for 90 seconds and developed by immersion in a 2.38 mass% tetramethylammonium hydroxide (TMAH) alkaline developer for 60 seconds. Subsequently, the resist film was washed with ultrapure water for 30 seconds and dried to form a positive-type resist pattern. The line-and-space pattern of the formed resist pattern was observed using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) to evaluate the reactivity of the resist composition to electron beam irradiation.

[0396] [Table 4]

[0397] Regarding the evaluation of the resist pattern, in Examples 22 to 27, good resist patterns were obtained by irradiating with an electron beam using a 1:1 line-and-space setting with 50 nm spacing. Line edge roughness was considered good if the pattern's unevenness was less than 5 nm. On the other hand, a good resist pattern could not be obtained in Comparative Example 3.

[0398] As described above, when a resin that satisfies the requirements of this embodiment is used, it exhibits higher heat resistance and can impart a better resist pattern shape compared to the resin of Comparative Example 3 (NBisN-1) that does not satisfy these requirements. Similar effects are observed with resins other than those described in the examples, as long as they satisfy the requirements of this embodiment.

[0399] [Examples 28-32, Comparative Example 4] (Preparation of radiation-sensitive compositions) The components listed in Table 5 were prepared to form a homogeneous solution. This homogeneous solution was then filtered through a Teflon® membrane filter with a pore size of 0.1 μm to prepare radiation-sensitive compositions. Each of the prepared radiation-sensitive compositions was evaluated as follows.

[0400] [Table 5]

[0401] In Comparative Example 4, the following was used as the resist substrate (component (A)). PHS-1: Polyhydroxystyrene Mw=8000 (Sigma-Aldrich) Furthermore, the following was used as the photoactive compound (B). B-1: Naphthoquinone diazide-based photosensitive agent with the following chemical structure formula (G) (4NT-300, Toyo Gosei Kogyo Co., Ltd.) Furthermore, the following was used as a solvent. S-1: Propylene glycol monomethyl ether (Tokyo Chemical Industries, Ltd.) [ka]

[0402] (Evaluation of the resist performance of radiation-sensitive compositions) The radiation-sensitive composition obtained above was rotary coated onto a clean silicon wafer and then pre-bake (PB) in an oven at 110°C to form a 200 nm thick resist film. The resist film was exposed to ultraviolet light using an ultraviolet exposure apparatus (Mikasa MA-10 mask aligner). An ultra-high pressure mercury lamp was used as the ultraviolet lamp (relative intensity ratio of g-line:h-line:i-line:j-line = 100:80:90:60). After irradiation, the resist film was heated at 110°C for 90 seconds and developed by immersion in a TMAH 2.38 mass% alkaline developer for 60 seconds. Subsequently, the resist film was washed with ultrapure water for 30 seconds and dried to form a 5 μm positive-type resist pattern.

[0403] The lines and spaces obtained in the formed resist pattern were observed using a scanning electron microscope (Hitachi High-Technologies Corporation S-4800). Line edge roughness was considered good if the pattern's surface irregularities were less than 5 nm.

[0404] When using the radiation-sensitive compositions in Examples 28 to 32, a good resist pattern with a resolution of 5 μm was obtained. Furthermore, the roughness of the pattern was also low and excellent.

[0405] On the other hand, when the radiation-sensitive composition in Comparative Example 4 was used, a good resist pattern with a resolution of 5 μm was obtained. However, the roughness of that pattern was large and poor.

[0406] As described above, the radiation-sensitive compositions in Examples 28 to 32 were found to have less roughness and to be able to form a resist pattern with a better shape compared to the radiation-sensitive composition in Comparative Example 4. Other radiation-sensitive compositions not described in the examples will show similar effects as long as they satisfy the requirements of this embodiment described above.

[0407] Furthermore, the resins obtained in Synthesis Examples 1 to 5 were evaluated as having relatively low molecular weight and low viscosity, and therefore, as lithography underlayer film forming materials using these resins, their embedding properties and film surface flatness were evaluated as being relatively advantageous. In addition, the thermal decomposition temperature for all of them was 405°C or higher (evaluation A), and they were evaluated as having high heat resistance, so they can be used even under high-temperature baking conditions. To confirm these points, the following evaluations were conducted assuming underlayer film applications.

[0408] [Examples 33-38, Comparative Examples 5-6] (Preparation of compositions for forming underlayer films for lithography) Lithography underlayer formation compositions were prepared to have the compositions shown in Table 6. Next, these lithography underlayer formation compositions were rotary coated onto silicon substrates, and then baked at 240°C for 60 seconds, followed by 400°C for 120 seconds, to produce underlayer films with a thickness of 200 nm. The following acid generators, crosslinking agents, and organic solvents were used. Acid generator: Ditertically butyldiphenyliodonium nonafluoromethanesulfonate (DTDPI), manufactured by Midori Chemical Co., Ltd. Crosslinking agent: Nikalac MX270 (Nikalac), manufactured by Sanwa Chemical Co., Ltd. Organic solvents: Cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA) Novolac: PSM4357, manufactured by Gun-ei Chemical Co., Ltd.

[0409] Next, etching tests were conducted under the conditions shown below to evaluate etching resistance. The evaluation results are shown in Table 6.

[0410] [Etching test] Etching equipment: RIE-10NR manufactured by Samco International Corporation Output: 50W Pressure: 20 Pa Time: 2 min Etching gas Ar gas flow rate:CF4 gas flow rate:O2 gas flow rate = 50:5:5 (sccm)

[0411] (Evaluation of etching resistance) The etching resistance was evaluated using the following procedure. First, a novolac underlayer film was prepared under the same conditions as above, except that novolac (PSM4357, manufactured by Gun-ei Chemical Co., Ltd.) was used. The etching test described above was performed on this novolac underlayer film, and the etching rate was measured.

[0412] Next, the underlayer films of Examples 33-38 and Comparative Examples 5-6 were prepared under the same conditions as the underlayer film of novolac, and the etching tests described above were performed in the same manner, and the etching rates were measured. The etching resistance was evaluated using the following evaluation criteria, with the etching rate of the novolac underlayer film as the baseline. [Evaluation Criteria] A: The etching rate is less than -20% compared to the underlying novolac film. B: Etching rate is -20% to 0% compared to the underlying novolac film. C: Etching rate is more than +0% compared to the underlying novolac film.

[0413] [Table 6]

[0414] Examples 33-38 showed superior etching rates compared to the novolac underlayer film and the resins of Comparative Examples 5-6. On the other hand, the resins of Comparative Example 5 or Comparative Example 6 showed etching rates equivalent to or inferior to those of the novolac underlayer film.

[0415] [Examples 39-44, Comparative Example 7] Next, the lithography underlayer formation compositions used in Examples 33 to 38 and Comparative Example 5 were applied to an 80 nm thick, 60 nm line-and-space SiO2 substrate, and baked at 240°C for 60 seconds to form a 90 nm underlayer.

[0416] (Evaluation of implantability) The implantability was evaluated using the following procedure. A cross-section of the film obtained under the above conditions was cut out and observed using an electron microscope to evaluate its implantability. The evaluation results are shown in Table 7.

[0417] [Evaluation Criteria] A: The underlying film is embedded without defects in the uneven areas of the 60nm line-and-space SiO2 substrate. C: Defects exist in the uneven areas of the 60nm line-and-space SiO2 substrate, and the underlying film is not embedded.

[0418] [Table 7]

[0419] Examples 39-44 showed good embedding performance. On the other hand, in Comparative Example 7, defects were observed in the uneven areas of the SiO2 substrate, indicating poor embedding performance.

[0420] [Examples 45-50] Next, the lithography underlayer formation compositions used in Examples 33-38 were applied to a SiO2 substrate with a thickness of 300 nm, and baked at 240°C for 60 seconds, and then at 400°C for 120 seconds, to form an underlayer with a thickness of 85 nm. An ArF resist solution was applied to this underlayer, and a photoresist layer with a thickness of 140 nm was formed by baking at 130°C for 60 seconds.

[0421] The ArF resist solution used was prepared by combining 5 parts by mass of the compound of formula (16) below, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 2 parts by mass of tributylamine, and 92 parts by mass of PGMEA.

[0422] The compound represented by formula (16) below was prepared as follows: 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy-γ-butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, and 0.38 g of azobisisobutyronitrile were dissolved in 80 mL of tetrahydrofuran to prepare the reaction solution. This reaction solution was polymerized under a nitrogen atmosphere at a reaction temperature of 63°C for 22 hours, after which the reaction solution was added dropwise to 400 mL of n-hexane. The resulting resin was coagulated and purified, the resulting white powder was filtered, and dried overnight under reduced pressure at 40°C to obtain the compound represented by formula (16) below.

[0423] [ka] (In formula (16), the values ​​40, 40, and 20 represent the ratios of each constituent unit and do not represent the block copolymer.)

[0424] Next, the photoresist layer was exposed using an electron beam lithography system (ELS-7500, 50 keV, manufactured by Elionix Corporation), 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-type resist pattern.

[0425] [Comparative Example 8] A photoresist layer was directly formed on the SiO2 substrate in the same manner as in Example 39, except that no underlying film was formed, to obtain a positive-type resist pattern.

[0426] [evaluation] For each of Examples 45-50 and Comparative Example 8, the shape of the obtained 45 nmL / S (1:1) and 80 nmL / S (1:1) resist patterns was observed using a Hitachi S-4800 electron microscope. The shape of the resist pattern after development was evaluated as good if there was no pattern distortion and good rectangularity, and poor if not. Furthermore, the minimum line width that resulted in no pattern distortion and good rectangularity was used as an evaluation index for resolution. Additionally, the minimum electron beam energy required to draw a good pattern shape was used as an evaluation index for sensitivity. The results are shown in Table 8.

[0427] [Table 8]

[0428] As is clear from Table 8, the resist patterns in Examples 45-50 were found to be significantly superior in both resolution and sensitivity compared to Comparative Example 8. Furthermore, the resist pattern shape after development was also confirmed to be stable and rectangular, without any pattern distortion. In addition, the difference in the resist pattern shape after development indicated that the lithography underlayer forming materials in Examples 33-38 had good adhesion to the resist material.

[0429] [Example 51] The lithography underlayer film-forming composition used in Example 39 was applied to a SiO2 substrate with a thickness of 300 nm, and baked at 240°C for 60 seconds, and then at 400°C for 120 seconds, to form an underlayer film with a thickness of 90 nm. A silicon-containing intermediate layer material was applied to this underlayer film, and baked at 200°C for 60 seconds, to form an intermediate layer film with a thickness of 35 nm. Furthermore, the ArF resist solution was applied to this intermediate layer film, and baked at 130°C for 60 seconds, to form a photoresist layer with a thickness of 150 nm. As the silicon-containing intermediate layer material, a silicon atom-containing polymer described in Japanese Patent Application Publication No. 2007-226170 <Synthesis Example 1> was used.

[0430] Next, the photoresist layer was mask-exposed using an electron beam lithography system (ELS-7500, 50 keV, manufactured by Elionix Corporation), 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-type resist pattern of 45 nm / S (1:1).

[0431] Subsequently, using a RIE-10NR manufactured by Samco International, the obtained resist pattern was used as a mask to perform dry etching of the silicon-containing interlayer film (SOG). Following this, the obtained silicon-containing interlayer film pattern was used as a mask to perform dry etching of the underlying film, and then the obtained underlying film pattern was used as a mask to perform dry etching of the SiO2 film.

[0432] The etching conditions for each are as follows: Etching conditions for resist patterns onto the resist interlayer film Output: 50W Pressure: 20 Pa 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 interlayer patterns into the resist underlayer. Output: 50W Pressure: 20 Pa Time: 2 min Etching gas Ar gas flow rate:CF4 gas flow rate:O2 gas flow rate = 50:5:5 (sccm) SiO 2 Etching conditions for films Output: 50W Pressure: 20 Pa Time: 2 min Etching gas Ar gas flow rate: C5F 12 Gas flow rate: C2F6 Gas flow rate: O2 Gas flow rate =50:4:3:1(sccm)

[0433] [evaluation] When the pattern cross-section (shape of the SiO2 film after etching) of Example 37 obtained as described above was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., it was confirmed that the example using the underlying film that satisfies the requirements of this embodiment had a rectangular shape for the SiO2 film after etching in multilayer resist processing, and no defects were observed, indicating good quality.

[0434] <Evaluation of the properties of resin films (single resin films)> <Creation of resin film> (Example A01) Using PGMEA as the solvent, the resin ANT-1 from Synthesis Example 1 was dissolved to prepare a resin solution with a solid content concentration of 10% by mass (resin solution from Example A01). The prepared resin solution was deposited onto a 12-inch silicon wafer using a spin coater LithiusPro (manufactured by Tokyo Electron Corporation). After deposition, the film was deposited while adjusting the rotation speed to achieve a film thickness of 200 nm. The substrate was then baked at 250°C for 1 minute to create a laminated substrate made of the resin from Synthesis Example 1. The prepared substrate was further baked using a hot plate capable of high-temperature processing at 350°C for 1 minute to obtain a cured resin film. In this process, curing was determined if the change in film thickness before and after immersion of the obtained cured resin film in a cyclohexanone bath for 1 minute was 3% or less. If curing was deemed insufficient, the curing temperature was changed in 50°C increments to investigate the optimal curing temperature, and the bake treatment was performed at the lowest temperature within the curing temperature range. <Evaluation of optical properties> The fabricated resin film was evaluated for its optical properties (refractive index n and extinction coefficient k as optical constants) using a VUV-VASE spectroscopic ellipsometry device (JAWoollam).

[0435] (Examples A02 to A05 and Comparative Example A01) A resin film was prepared in the same manner as in Example A01, except that the resin used was changed from ANT-1 to the resins shown in Table 9, and the optical properties were evaluated. [Evaluation criteria] refractive index n A: 1.4 or higher C: Less than 1.4 [Evaluation Criteria] Extinction coefficient k A: Less than 0.5 C:0.5 or more

[0436] [Table 9]

[0437] The results from Examples A01 to A05 show that the film-forming composition containing the polycyclic polyphenol resin in this embodiment can form a resin film with a high n value and a low k value at a wavelength of 193 nm used for ArF lithography.

[0438] <Heat resistance evaluation of cured films> (Example B01) The resin film prepared in Example A01 was evaluated for heat resistance using a lamp annealing furnace. The heat treatment conditions involved continuous heating at 450°C under a nitrogen atmosphere, and the rate of change in film thickness was measured at 4 minutes and 10 minutes after the start of heating. Additionally, heating was continued at 550°C under a nitrogen atmosphere, and the rate of change in film thickness was measured at 4 minutes and 10 minutes after the start of heating. These rate of change in film thickness were evaluated as indicators of the heat resistance of the cured film. The film thickness before and after the heat resistance test was measured using an interferometer, and the ratio of the change in film thickness to the film thickness before the heat resistance test was calculated as the rate of change in film thickness (percentage). [Evaluation Criteria] A: Film thickness change rate is less than 10% B: Film thickness change rate is 10% to 15% C: Film thickness change rate exceeds 15%

[0439] (Examples B02 to B05 and Comparative Examples B01 to B02) The heat resistance evaluation was carried out in the same manner as in Example B01, except that the resin used was changed from ANT-1 to the resins shown in Table 10.

[0440] [Table 10]

[0441] (Example C01) <PE-CVD Film Deposition Evaluation> A thermal oxidation treatment was performed on a 12-inch silicon wafer, and a resin film with a thickness of 100 nm was fabricated on the substrate having the obtained silicon oxide film by the same method as in Example A01 using the resin solution of Example A01. On the resin film, using a film deposition apparatus TELINDY (manufactured by Tokyo Electron Limited), TEOS (tetraethylsiloxane) was used as a raw material, and a silicon oxide film with a thickness of 70 nm was deposited at a substrate temperature of 300°C. For the wafer with the cured film on which the fabricated silicon oxide film was laminated, a defect inspection was further performed using KLA-Tencor SP-5, and the number of defects in the deposited oxide film was evaluated using the number of defects of 21 nm or more as an index. A Number of defects ≤ 20 B 20 ≤ Number of defects ≤ 50 C 50 ≤ Number of defects ≤ 100 D 100 ≤ Number of defects ≤ 1000 E 1000 ≤ Number of defects ≤ 5000 F 5000 ≤ Number of defects

[0442] <SiN Film> On the cured film fabricated on the substrate having a silicon oxide film thermally oxidized to a thickness of 100 nm on a 12-inch silicon wafer by the same method as above, using a film deposition apparatus TELINDY (manufactured by Tokyo Electron Limited), SiH4 (monosilane) and ammonia were used as raw materials, and a SiN film with a thickness of 40 nm, a refractive index of 1.94, and a film stress of -54 MPa was deposited at a substrate temperature of 350°C. For the wafer with the cured film on which the fabricated SiN film was laminated, a defect inspection was further performed using KLA-Tencor SP-5, and the number of defects in the deposited oxide film was evaluated using the number of defects of 21 nm or more as an index. A Number of defects ≤ 20 B 20 ≤ Number of defects ≤ 50 C 50 ≤ Number of defects ≤ 100 D 100 ≤ Number of defects ≤ 1000 E 1000 ≤ Number of defects ≤ 5000 F = 5000 or less number of defects

[0443] (Examples C02 to C05 and Comparative Examples C01 to C02) The heat resistance evaluation was carried out in the same manner as in Example C01, except that the resin used was changed from ANT-1 to the resins shown in Table 11.

[0444] [Table 11]

[0445] The silicon oxide or SiN films formed on the resin films of Examples C01 to C05 had 50 or fewer defects with a size of 21 nm or larger (rated B or higher), which was shown to be fewer than the number of defects in Comparative Examples C01 or C02.

[0446] (Example D01) <Etching evaluation after high-temperature treatment> A 12-inch silicon wafer was subjected to thermal oxidation treatment, and a resin film with a thickness of 100 nm was fabricated on the substrate having the resulting silicon oxide film using the resin solution of Example A01, in the same manner as in Example A01. The resin film was then subjected to annealing treatment by heating on a hot plate capable of high-temperature processing under a nitrogen atmosphere at 600°C for 4 minutes, and a wafer was created in which the annealed resin film was laminated. The fabricated annealed resin film was cut off, and the carbon content was determined by elemental analysis. Furthermore, a 12-inch silicon wafer was subjected to thermal oxidation treatment, and a resin film with a thickness of 100 nm was fabricated on the substrate having the resulting silicon oxide film using the resin solution of Example A01 in the same manner as in Example A01. This resin film was then annealed by heating at 600°C for 4 minutes under a nitrogen atmosphere to form a new resin film. The substrate was then etched using an etching apparatus TELIUS (manufactured by Tokyo Electron Corporation) under conditions using CF4 / Ar as the etching gas and under conditions using Cl2 / Ar as the etching gas, and the etching rate was evaluated. For the etching rate evaluation, a 200 nm thick resin film prepared by annealing SU8 (manufactured by Nippon Kayaku Co., Ltd.) at 250°C for 1 minute was used as a reference, and the rate ratio of the etching rate to that of SU8 was determined as a relative value and evaluated.

[0447] (Examples D02 to D05 and Comparative Examples D01 to D02) The heat resistance evaluation was carried out in the same manner as in Example D01, except that the resin used was changed from ANT-1 to the resins shown in Table 12.

[0448] [Table 12]

[0449] <Evaluation of etching defects in multilayer films> The polycyclic polyphenol resins obtained in the synthesis examples were evaluated for quality before and after purification. Specifically, the resin films formed on wafers using the polycyclic polyphenol resins were transferred to the substrate by etching, and then evaluated for defects. A 12-inch silicon wafer was subjected to thermal oxidation treatment to obtain a substrate having a silicon oxide film with a thickness of 100 nm. A polycyclic polyphenol resin solution was then deposited on this substrate by adjusting the spin-coating conditions to achieve a thickness of 100 nm. After baking at 150°C for 1 minute, followed by baking at 350°C for 1 minute, a laminated substrate was fabricated in which the polycyclic polyphenol resin was laminated on the silicon with the thermal oxidation film. Using a TELIUS etching system (manufactured by Tokyo Electron Corporation), the resin film was etched under CF4 / O2 / Ar conditions to expose the substrate on the oxide film surface. Further etching was performed under conditions of etching the oxide film to 100 nm with a CF4 / Ar gas composition ratio to create an etched wafer. The number of defects larger than 19 nm was measured on the prepared etched wafers using a defect inspection system SP5 (manufactured by KLA-tencor), and this was performed as a defect evaluation for etching processes on multilayer films. A. Number of defects ≤ 20 B 20 ≤ Number of defects ≤ 50 C 50 ≤ Number of defects ≤ 100 D 100 pieces ≤ number of defects ≤ 1000 pieces E = 1000 units ≤ number of defects ≤ 5000 units F = 5000 or less number of defects

[0450] (Example E01) Acidic purification of ANT-1 150 g of a 10% by mass solution of ANT-1 dissolved in cyclohexanone, obtained in Synthesis Example 1, was placed in a 1000 mL four-necked flask (bottomless type), and heated to 80°C while stirring. Next, 37.5 g of oxalic acid aqueous solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This separated the oil phase and aqueous phase, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was added to 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, residual water and cyclohexanone were concentrated and removed by reducing the pressure inside the flask to below 200 hPa while heating to 80°C. Subsequently, the solution was diluted with EL grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Ltd.), and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of ANT-1 with reduced metal content. After preparing solution samples by filtering the prepared polycyclic polyphenol resin solution through a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris Co., Ltd. under conditions of 0.5 MPa, etching defect evaluation was performed on the multilayer film.

[0451] (Example E02) Acidic purification of ANT-2 In a 1000 mL four-necked flask (bottomless type), 140 g of a solution (10% by mass) of ANT-2 dissolved in cyclohexanone, obtained in Synthesis Example 2, was placed and heated to 60°C while stirring. Next, 37.5 g of oxalic acid aqueous solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This separated the solution into an oil phase and an aqueous phase, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes, after which the aqueous phase was removed. After repeating this operation three times, residual water and cyclohexanone were concentrated and removed by reducing the pressure inside the flask to below 200 hPa while heating to 80°C. Subsequently, the solution was diluted with EL grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Ltd.) and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of ANT-2 with reduced metal content. After preparing solution samples by filtering the prepared polycyclic polyphenol resin solution through a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris Co., Ltd. under conditions of 0.5 MPa, etching defect evaluation was performed on the multilayer film.

[0452] (Example E03) Purification by filtering In a Class 1000 clean booth, 500g of a 10% by mass solution of the resin (ANT-1) obtained in Synthesis Example 1 dissolved in cyclohexanone was placed in a 1000mL four-necked flask (bottomless type). Subsequently, the air inside the flask was removed by reduced pressure, nitrogen gas was introduced to return the pressure to atmospheric pressure, and the oxygen concentration inside was adjusted to less than 1% by aeration with nitrogen gas at a rate of 100mL per minute. The solution was then heated to 30°C while stirring. The solution was withdrawn through the bottomless valve and passed through a fluororesin pressure-resistant tube at a flow rate of 100mL per minute using a diaphragm pump to a nylon hollow fiber membrane filter with a nominal pore size of 0.01μm (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix Nylon Series) under pressure filtration conditions of 0.5MPa. The filtered resin solution was diluted with EL-grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Ltd.) and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of ANT-1 with reduced metal content. The prepared polycyclic polyphenol resin solution was filtered using a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris Co., Ltd. under conditions of 0.5 MPa to prepare solution samples, and etching defect evaluation was performed on the multilayer film. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the same method was used hereafter).

[0453] (Example E04) As a purification process using filters, an IONKLEEN filter manufactured by Nippon Pall, a nylon filter manufactured by Nippon Pall, and a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris were connected in series in this order to construct a filter line. Except for using the fabricated filter line instead of a 0.1 μm nylon hollow fiber membrane filter, the solution was passed through by pressure filtration at a filtration pressure of 0.5 MPa, in the same manner as in Example E03. By diluting with EL grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Ltd.) and adjusting the concentration to 10% by mass, a cyclohexanone solution of ANT-1 with reduced metal content was obtained. After preparing a solution sample by pressure filtration of the prepared polycyclic polyphenol resin solution using a UPE filter with a nominal pore size of 3 nm manufactured by Nippon Integris at a filtration pressure of 0.5 MPa, etching defect evaluation was performed on the laminated film.

[0454] (Example E05) The solution sample prepared in Example E01 was further pressure-filtered using the filter line prepared in Example E04 to a filtration pressure of 0.5 MPa to create a new solution sample, after which etching defect evaluation was performed on the laminated film.

[0455] (Example E06) After preparing a solution sample of ANT-2, which was created in Synthesis Example 2, using the same method as in Example E05, etching defect evaluation was performed on the multilayer film.

[0456] (Example E07) After preparing a solution sample of ANT-3, which was created in Synthesis Example 3, using the same method as in Example E05, etching defect evaluation was performed on the multilayer film. The evaluation results for Examples E01 to E07 are shown in Table 13. [Table 13]

[0457] [Examples 52-57 and Comparative Example 9] A lithography underlayer film-forming material solution and an optical component-forming composition having the same composition as those prepared in each of Examples 33-38 and Comparative Example 5 were applied to a SiO2 substrate with a thickness of 300 nm, and baked at 260°C for 300 seconds to form an optical component film with a thickness of 100 nm. Next, refractive index and transparency tests were performed at a wavelength of 633 nm using a vacuum ultraviolet multi-incidence angle ellipsometer (VUV-VASE) manufactured by J.A. Woo-Lam Japan, and the refractive index and transparency were evaluated according to the following criteria. The evaluation results are shown in Table 14.

[0458] [Criteria for evaluating refractive index] A: Refractive index of 1.65 or higher C: Refractive index less than 1.65

[0459] [Transparency Evaluation Criteria] A: Absorption constant is less than 0.03 C: Absorption constant is 0.03 or higher

[0460] [Table 14]

[0461] The optical component-forming compositions of Examples 52-57 were found to have not only a high refractive index but also a low absorption coefficient and excellent transparency. On the other hand, the composition of Comparative Example 9 was found to have inferior performance as an optical component.

[0462] [Example Group 2]

[0463] (Synthesis Example 1) Synthesis of RCA-1 In a 500 mL container equipped with a stirrer, condenser, and burette, 32.45 g (50 mmol) of 4-t-butylcalix[4]arene (manufactured by Tokyo Chemical Industry Co., Ltd., formula (CA-1)) and 10.1 g (20 mmol) of monobutyl copper phthalate were charged. 100 mL of 1-butanol was added as a solvent, and the reaction mixture was stirred at 100 °C for 6 hours. After cooling, the precipitate was filtered, and the resulting crude product was dissolved in 100 mL of ethyl acetate. Next, 5 mL of hydrochloric acid was added, and after stirring at room temperature, the mixture was neutralized with sodium bicarbonate. The ethyl acetate solution was concentrated, and 200 mL of methanol was added to precipitate the reaction product. After cooling to room temperature, the product was separated by filtration. By drying the obtained solid, 20.4 g of the target resin (RCA-1) having the structure represented by the following formula was obtained. The molecular weight of the obtained resin was measured in polystyrene equivalent under the aforementioned measurement conditions, and the results showed that Mn was 2424, Mw was 3466, and Mw / Mn was 1.43. When the obtained resin was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, confirming that it has the chemical structure shown in the following formula (RCA-1). δ(ppm)(d6-DMSO): 10.2(4H,OH), 7.1~7.3(6H,Ph-H), 3.5~4.3(8H,CH), 1.2(36H,-CH3) [ka] [ka]

[0464] (Synthesis Examples 2-5) Synthesis of RCR-1, RCR-2, RCN-1, and RCN-2 The procedure was carried out in the same manner as in Synthesis Example 1, except that the compound represented by the following formula (CR-1), the compound represented by the following formula (CR-2), the compound represented by the following formula (CN-1), or the compound represented by the following formula (CN-2) was used instead of 4-t-butylcalix[4]arene (manufactured by Tokyo Chemical Industry Co., Ltd., formula (CA-1)), and the target compounds (RCR-1), (RCR-2), (RCN-1), and (RCN-2), represented by the following formulas, were obtained, respectively. The compounds represented by the following formulas (CR-1), (CR-2), (CN-1), and (CN-2) were obtained with reference to Synthesis Example 1 and Synthesis Example 4 described in International Publication No. 2011 / 024957, respectively. Specifically, the compound represented by formula (CR-1) was synthesized based on Synthesis Example 4 described in International Publication No. 2011 / 024957. The compound represented by formula (CR-2) was synthesized using 4-cyanobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 4-isopropylbenzaldehyde in Synthesis Example 1 described in International Publication No. 2011 / 024957. The compound represented by formula (CN-1) was synthesized using 1,6-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of resorcinol and 4-hydroxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 4-isopropylbenzaldehyde in Synthesis Example 1 described in International Publication No. 2011 / 024957. The compound represented by formula (CN-2) was synthesized in Synthesis Example 1 described in International Publication No. 2011 / 024957, using 1,6-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of resorcinol, and 4-cyanobenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 4-isopropylbenzaldehyde.

[0465] The obtained resin (RCR-1) was measured for molecular weight in polystyrene equivalent under the above measurement conditions, and the results showed that Mn was 2228, Mw was 3355, and Mw / Mn was 1.51. Furthermore, when the obtained resin (RCR-1) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, confirming that it has the chemical structure of formula (RCR-1). δ(ppm)(d6-DMSO): 8.4~8.5 (8H,OH), 6.0~6.8 (22H,Ph-H), 5.5~5.6 (4H,CH), 0.8~1.9 (44H,-cyclohexyl group)

[0466] The obtained resin (RCR-2) was measured for molecular weight in polystyrene equivalent under the above measurement conditions, and the results showed that Mn was 2108, Mw was 3305, and Mw / Mn was 1.57. Furthermore, when the obtained resin (RCR-2) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, confirming that it has the chemical structure of formula (RCR-2). δ(ppm)(d6-DMSO): 8.4~8.5(8H,OH), 6.0~6.8(22H,Ph-H), 5.5~5.6(4H,CH)

[0467] The obtained resin (RCN-1) was measured for molecular weight in polystyrene equivalent under the above measurement conditions, and the results showed that Mn was 2208, Mw was 3652, and Mw / Mn was 1.65. Furthermore, when the obtained resin (RCN-1) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, confirming that it has the chemical structure of formula (RCN-1). δ(ppm)(d6-DMSO):9.0~9.6(12H,OH), 5.9~8.7(34H,Ph-H,CH)

[0468] The obtained resin (RCN-2) was measured for polystyrene-equivalent molecular weight under the above measurement conditions, and the results showed that Mn was 2302, Mw was 3754, and Mw / Mn was 1.63. Furthermore, when the obtained resin (RCN-2) was subjected to NMR measurement under the above measurement conditions, the following peaks were detected, confirming that it has the chemical structure of formula (RCN-2). δ(ppm)(d6-DMSO):9.2~9.6(8H,OH), 5.9~8.7(34H,Ph-H,CH)

[0469] [ka]

[0470] [ka]

[0471] [ka]

[0472] [ka]

[0473] [ka]

[0474] [Examples 1-5 and Comparative Example 1] The resins RCA-1, RCR-1, RCR-2, RCN-1, and RCN-2 obtained in Synthesis Examples 1 to 5 described above were used to evaluate their heat resistance according to the evaluation method shown below. In addition, the resin obtained in Comparative Synthesis Example 1 of Example Group 1 was designated as NBisN-2 (hereinafter, in Example Group 2, it may be abbreviated as "resin obtained in Comparative Synthesis Example 1"), and its heat resistance was evaluated in the same manner as above. The results are shown in Table 15.

[0475] <Measurement of thermal decomposition temperature> Using the EXSTAR6000TG / DTA instrument (product name) manufactured by SII Nanotechnology Co., Ltd., approximately 5 mg of the sample was placed in an unsealed aluminum container and heated to 700°C at a heating rate of 10°C / min in a nitrogen gas (30 mL / min) stream. The temperature at which a 10% wt% loss in thermal energy was observed was defined as the thermal decomposition temperature (Tg), and the heat resistance was evaluated according to the following criteria. Rating A: Pyrolysis temperature of 410°C or higher Evaluation B: Pyrolysis temperature is between 320°C and 410°C. Rating C: Pyrolysis temperature below 320°C

[0476] [Table 15]

[0477] As shown in Table 15, the resins used in Examples 1 to 5 were confirmed to have good heat resistance. On the other hand, the resin used in Comparative Example 1 was confirmed to have poor heat resistance.

[0478] [Examples 6-10 and Comparative Example 2] (Preparation of compositions for forming lithographic underlayer films) A lithography underlayer film-forming composition was prepared to have the composition shown in Table 16. In Table 16, the numbers in parentheses indicate the amount (parts by mass) of each component. Next, each of these lithography underlayer formation compositions was rotary coated onto a silicon substrate, and then heated in a nitrogen atmosphere at 240°C for 60 seconds, followed by baking at 400°C for 120 seconds to produce lithography underlayers with a thickness of 200-250 nm.

[0479] Next, etching tests were performed on each underlying film under the conditions shown below, and the etching rate was measured. The etching resistance was then evaluated using the following procedure. The evaluation results are shown in Table 16.

[0480] [Etching test] Etching equipment: RIE-10NR (product name) manufactured by Samco Co., Ltd. Output: 50W Pressure: 20 Pa Time: 2 min Etching gas: Ar gas flow rate: CF4 gas flow rate: O2 gas flow rate = 50:5:5 (sccm)

[0481] (Evaluation of etching resistance) The etching resistance was evaluated using the following procedure. First, a lithography underlayer film formation composition was prepared in the same manner as in Example 6 of Table 16, except that a novolac resin (PSM4357 (trade name) manufactured by Gun-ei Chemical Industry Co., Ltd.) was used instead of the resin (RCA-1) obtained in Synthesis Example 1. Then, an underlayer film of novolac resin was prepared using this composition under the same conditions as described above. An etching test was performed on this novolac resin underlayer film under the same conditions as described above, and the etching rate was measured. Using the etching rate of this novolac resin underlayer film as a reference, the etching resistance of each underlayer film of Examples 6 to 10 and Comparative Example 2 was evaluated according to the following evaluation criteria.

[0482] [Evaluation Criteria] A: The etching rate is less than -20% compared to the underlying film of novolac resin. B: The etching rate is -20% to 0% compared to the underlying film of novolac resin. C: The etching rate is greater than +0% compared to the underlying film of novolac resin.

[0483] [Table 16]

[0484] As shown in Table 16, it was found that Examples 6 to 10 exhibited superior etching rates compared to the underlayer film of the novolac resin and the resin of Comparative Example 2. The etching rate of the resin of Comparative Example 2 was equivalent to that of the underlayer film of the novolac resin.

[0485] [Examples 11-26 and Reference Examples 1-4] The amount of residual metal in polycyclic polyphenol resins before and after purification, and the storage stability of compositions containing polycyclic polyphenol resins and solutions were evaluated using the following methods.

[0486] (Measurement of residual metal content) Using an ICP-MS (Inductively Coupled Plasma Mass Spectrometer), the metal residue amounts (ppb) in cyclohexanone solutions of various resins obtained by the following Examples and Reference Examples were measured under the following measurement conditions. Apparatus: AG8900 (trade name) manufactured by Agilent Technologies, Inc. Temperature: 25°C Environment: Class 1000 clean room (US Federal Standard)

[0487] (Storage Stability Evaluation) The turbidity (HAZE) of the cyclohexanone solutions obtained by the following Examples and Reference Examples was measured using a color difference and turbidity meter after holding at 23°C for 240 hours, and the storage stability of the solutions was evaluated according to the following criteria. Apparatus: Color difference and turbidity meter COH400 (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.) Optical path length: 1 cm Using a quartz cell [Evaluation Criteria] 0 ≦ HAZE ≦ 1.0: Good 1.0 < HAZE ≦ 2.0: Passable 2.0 < HAZE: Poor

[0488] (Example 11) Purification of RCA-1 with Acid A solution (10% by mass) of the resin (RCA-1) obtained in Synthesis Example 1 dissolved in cyclohexanone was charged into a 1000 mL four-necked flask (bottom-drained type) in an amount of 150 g, and heated to 80°C while stirring. Then, 37.5 g of an oxalic acid aqueous solution (pH 1.3) was added, stirred for 5 minutes, and left standing for 30 minutes. As a result, it was separated into an oil phase and an aqueous phase, so the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was charged into the obtained oil phase, stirred for 5 minutes, left standing for 30 minutes, and the aqueous phase was removed. After repeating this operation three times, while heating to 80°C, the inside of the flask was depressurized to 200 hPa or less to concentrate and distill off the residual moisture and cyclohexanone. Then, it was diluted with EL grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Inc.) and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of RCA-1 with reduced metal residue amount.

[0489] (Reference Example 2) Purification of RCA-1 with ultrapure water The procedure was carried out in the same manner as in Example 11, except that ultrapure water was used instead of an aqueous oxalic acid solution, and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of RCA-1.

[0490] The residual amounts of various metals were measured by ICP-MS in the 10% by mass cyclohexanone solution of RCA-1 before treatment (Reference Example 1), and in the solutions obtained in Example 11 and Reference Example 2. The measurement results are shown in Table 17. In Table 17, "Cr," "Fe," "Cu," and "Zn" represent chromium, iron, copper, and zinc, respectively, and were the metals detected as residual metals in the solutions.

[0491] (Example 12) Acidic purification of RCR-2 In a 1000 mL four-necked flask (bottomless type), 140 g of a solution (10% by mass) of the resin (RCR-2) obtained in Synthesis Example 2 dissolved in cyclohexanone was placed and heated to 60°C while stirring. Next, 37.5 g of aqueous oxalic acid solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. After that, the oil phase and aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was placed in 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, residual water and cyclohexanone were concentrated and removed by reducing the pressure inside the flask to below 200 hPa while heating to 80°C. Then, the solution was diluted with EL grade cyclohexanone (reagent manufactured by Kanto Chemical Co., Ltd.) and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of RCR-2 with reduced metal residue.

[0492] (Reference Example 3) Purification of RCR-2 using ultrapure water The procedure was carried out in the same manner as in Example 12, except that ultrapure water was used instead of an aqueous oxalic acid solution, and the concentration was adjusted to 10% by mass to obtain a cyclohexanone solution of RCR-2.

[0493] The residual amounts of various metals were measured by ICP-MS for the 10% by mass cyclohexanone solution of RCR-2 before treatment (Reference Example 4), and the solutions obtained in Example 12 and Reference Example 3. The measurement results are shown in Table 17.

[0494] (Example 13) Purification by filtering In a Class 1000 clean booth, 500 g of a 10% by mass solution of the resin (RCA-1) obtained in Synthesis Example 1 dissolved in cyclohexanone was placed in a 1000 mL four-necked flask (bottomless type). Subsequently, the air inside the vessel was removed by reduced pressure, nitrogen gas was introduced to return the pressure to atmospheric pressure, and the oxygen concentration inside was adjusted to less than 1% by aeration with nitrogen gas at a rate of 100 mL / min. The solution was then heated to 30°C while stirring. The solution was withdrawn through the bottomless valve and passed through a nylon hollow fiber membrane filter with a nominal pore size of 0.01 μm (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix Nylon Series) at a flow rate of 100 mL / min using a diaphragm pump via a pressure-resistant tube made of fluororesin. The residual amounts of various metals in the obtained RCA-1 cyclohexanone solution were measured by ICP-MS. The oxygen concentration was measured using an oxygen concentration meter "OM-25MF10" (product name) manufactured by AS ONE Corporation (the same method was used hereafter). The measurement results are shown in Table 17.

[0495] (Example 14) The solution was passed through the filter in the same manner as in Example 13, except that a polyethylene (PE) hollow fiber membrane filter with a nominal pore size of 0.01 μm (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix) was used. The amount of various metal residues in the obtained cyclohexanone solution of RCA-1 was measured by ICP-MS. The measurement results are shown in Table 17.

[0496] (Example 15) The solution was passed through the membrane in the same manner as in Example 13, except that a nylon hollow fiber membrane filter with a nominal pore size of 0.04 μm (manufactured by Kitz Microfilter Co., Ltd., product name: Polyfix) was used. The amount of various metal residues in the obtained cyclohexanone solution of RCA-1 was measured by ICP-MS. The measurement results are shown in Table 17.

[0497] (Example 16) The solution was passed through the filter in the same manner as in Example 13, except that a Zeta Plus filter 40QSH (manufactured by 3M Ltd., with ion exchange capability) with a nominal pore size of 0.2 μm was used. The amount of various metal residues in the obtained cyclohexanone solution of RCA-1 was measured by ICP-MS. The measurement results are shown in Table 17.

[0498] (Example 17) The solution was passed through the filter in the same manner as in Example 13, except that a ZetaPlus filter 020GN (manufactured by 3M Co., Ltd., with ion exchange capabilities, differing from the ZetaPlus filter 40QSH in filtration area and filter media thickness) with a nominal pore size of 0.2 μm was used. The amount of various metal residues in the obtained cyclohexanone solution of RCA-1 was measured by ICP-MS. The measurement results are shown in Table 17.

[0499] (Example 18) The procedure was the same as in Example 13, except that the resin obtained in Synthesis Example 2 (RCR-2) was used instead of the resin (RCA-1) used in Example 13. The amount of various metal residues in the obtained cyclohexanone solution of RCR-2 was measured by ICP-MS. The measurement results are shown in Table 17.

[0500] (Example 19) The procedure was the same as in Example 14, except that the resin obtained in Synthesis Example 2 (RCR-2) was used instead of the resin (RCA-1) in Example 13. The amount of various metal residues in the obtained cyclohexanone solution of RCR-2 was measured by ICP-MS. The measurement results are shown in Table 17.

[0501] (Example 20) The procedure was the same as in Example 15, except that the resin (RCR-2) obtained in Synthesis Example 2 was used instead of the compound (RCA-1) in Example 13. The amount of various metal residues in the obtained cyclohexanone solution of RCR-2 was measured by ICP-MS. The measurement results are shown in Table 17.

[0502] (Example 21) The procedure was the same as in Example 16, except that the resin (RCR-2) obtained in Synthesis Example 2 was used instead of the compound (RCA-1) in Example 13. The amount of various metal residues in the obtained cyclohexanone solution of RCR-2 was measured by ICP-MS. The measurement results are shown in Table 17.

[0503] (Example 22) The solution was passed through in the same manner as in Example 17, except that the resin (RCR-2) obtained in Synthesis Example 2 was used instead of the compound (RCA-1) in Example 13. The amount of various metal residues in the obtained RCR-2 cyclohexanone solu...

Claims

1. A method for producing a polymer having repeating units derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds represented by formulas (1A) and (1B), wherein the repeating units are linked to each other by direct bonding of aromatic rings, A monomer corresponding to the repeating unit, comprising the step of polymerizing one or more of these monomers in the presence of an oxidizing agent, A method for producing a polymer, wherein the oxidizing agent is a metal salt or metal complex containing at least one selected from the group consisting of copper, manganese, iron, cobalt, ruthenium, chromium, nickel, tin, lead, silver, and palladium. 【Chemistry 1】 (In formulas (1A) and (1B), R is independently one of the following: an optionally substituted alkyl group having 1 to 40 carbon atoms, an optionally substituted aryl group having 6 to 40 carbon atoms, an optionally substituted alkenyl group having 2 to 40 carbon atoms, an optionally substituted alkoxy group having 1 to 40 carbon atoms, a halogen atom, a thiol group, an amino group, a nitro group, a cyano group, a heterocyclic group, a carboxyl group, or a hydroxyl group, and at least one of the R groups is a hydroxyl group, and m is independently one of the following integers from 1 to 10.)

2. The method for producing a polymer according to claim 1, wherein the aromatic hydroxy compounds represented by formulas (1A) and (1B) are, respectively, aromatic hydroxy compounds represented by formulas (2A) and (2B). 【Chemistry 2】 (In equations (2A) and (2B), m 1 m is an integer between 0 and 10. 2 m is an integer between 0 and 10, and at least one m 1 or m 2 (This is an integer greater than or equal to 1.)

3. The method for producing a polymer according to claim 1, wherein the aromatic hydroxy compounds represented by formulas (1A) and (1B) are, respectively, aromatic hydroxy compounds represented by formulas (3A) and (3B). 【Transformation 3】 (In formulas (3A) and (3B), m 1' (This is an integer between 1 and 10.)

4. A method for producing a polymer according to any one of claims 1 to 3, wherein the polymer further comprises a modified portion derived from a crosslinking-reactive compound.

5. A method for producing a polymer according to any one of claims 1 to 4, wherein the weight-average molecular weight of the polymer is 400 to 100,000.

6. A method for producing a polymer according to any one of claims 1 to 5, wherein the solubility of the polymer in 1-methoxy-2-propanol and / or propylene glycol monomethyl ether acetate is 1% by mass or more.

7. A method for producing a polymer according to claim 6, wherein the solubility is 10% by mass or more.

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