composition

Abstract

The purpose of the present invention is to provide a composition capable of forming a lithographic film having excellent EUV and EB sensitivity. A composition according to the present invention comprises a compound represented by formula (A1) and a compound represented by formula (B1).

Description

composition

[0001] The present invention relates to a composition.

[0002] In recent years, advances in lithography technology have led to rapid advances in miniaturization of semiconductors (patterns) and pixels in the manufacture of semiconductor elements and liquid crystal display elements. A common method for miniaturizing pixels is to shorten the wavelength of the exposure light source. Specifically, while ultraviolet light, typically g-line and i-line, has traditionally been used, far-ultraviolet exposure using KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) has now become the norm for mass production, and extreme ultraviolet (EUV) lithography (13.5 nm) is also being increasingly adopted. Electron beams (EB) are also used to form fine patterns.

[0003] Conventional resist materials for lithography are polymeric materials capable of forming amorphous films, such as polymethyl methacrylate, and polymeric materials such as polyhydroxystyrene or polyalkyl methacrylate having an acid-dissociable group (see, for example, Non-Patent Document 1 below).

[0004] Shinji Okazaki and 8 others, "40 Years of Lithography Technology," S&T Publishing, December 9, 2016

[0005] However, for resins and the like that use polymeric materials, there is still a demand for improvements in sensitivity to EUV and EB, and in exposure defects that occur when a lithography film such as a resist film is formed.

[0006] The present invention has been made in view of the above problems, and has as its object to provide a composition capable of forming a lithography film having excellent EUV and EB sensitivity.

[0007] As a result of extensive research to solve the above problems, the present inventors have found that a composition containing a compound represented by a specific formula (1) and a compound represented by a specific formula (2) can form a lithography film having excellent EUV and EB sensitivity, thereby completing the present invention.

[0008] The present invention includes the following embodiments: [1] A composition comprising a compound represented by the following formula (A1) and a compound represented by the following formula (B1).

[0009]

[0010] (In formula (A1), each R independently represents an organic group that is not a functional group, and R 1 each independently represent a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups; each A independently represents a group having a protecting group; each Z independently represents an iodine atom or a hydroxy group; each r1 to r3 independently represent an integer of 0 to 3; and each r4 independently represent an integer of 1 to 4, provided that the sum of r1 to r4 represents an integer of 1 to 4.

[0011]

[0012] (In formula (B1), each R′ independently represents an organic group that is not a functional group, and R 1 Each A' independently represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups; each A' independently represents a group having a protecting group; each Z' independently represents an iodine atom or a hydroxy group; each X independently represents a single bond, a carbonyl group, or a divalent oxygen atom; n1 represents an integer of 1 to 4; r 1’ ~r 3’ each independently represents an integer of 0 to 3; 4’ Each independently represents an integer of 1 to 4, provided that formula (B1) has at least one formyl group. 1’ ~r 4’ The sum of these represents an integer of 1 to 4.

[0013] [2] The composition according to [1], wherein the compound represented by formula (A1) includes a compound represented by the following formula (A2), and the compound represented by formula (B1) includes one or more compounds selected from the group consisting of a compound represented by the following formula (B2), a compound represented by the following formula (B3), and a compound represented by the following formula (B4):

[0014]

[0015] (In formula (A2), R, R 1 and Z are defined the same as in formula (A1). r1 and r2 each independently represent an integer of 0 to 2, and r4 each independently represent an integer of 1 to 3, provided that the sum of r1, r2, and r4 represents an integer of 1 to 3.

[0016]

[0017] (In formula (B2), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 2; 4’ are each independently an integer of 1 to 3. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 3.

[0018]

[0019] (In formula (B3), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 3; 4’ are each independently an integer of 1 to 4. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 4.

[0020]

[0021] (In formula (B4), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 2; 4’ are each independently an integer of 1 to 3. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 3.

[0022] [3] The composition according to [2], wherein the compound represented by formula (A2) includes at least one compound selected from the group consisting of a compound represented by formula (A3), a compound represented by formula (A4), and a compound represented by formula (A5):

[0023]

[0024] (In formula (A3), p represents an integer of 1 to 3.)

[0025]

[0026] (In formula (A4), p represents an integer of 1 to 3.)

[0027]

[0028] (In formula (A5), p represents an integer of 1 to 4.)

[0029] [4] The composition according to [2] or [3], wherein the compound represented by formula (A2) includes one or more compounds selected from the group consisting of a compound represented by formula (A6), a compound represented by formula (A7), a compound represented by formula (A8), a compound represented by formula (A9), and a compound represented by formula (A10):

[0030]

[0031] [5] The composition according to [4], wherein the compound represented by formula (A2) includes one or more compounds selected from the group consisting of compounds represented by formula (A6) and compounds represented by formula (A7).

[0032] [6] The composition according to any one of [1] to [5], wherein the content of the compound represented by formula (B1) in the composition is 1 ppm by mass or more and 10,000 ppm by mass or less.

[0033] [7] The composition according to any one of [1] to [6], which exhibits a sensitizing effect upon irradiation with radiation.

[0034] [8] The composition according to any one of [1] to [7], wherein the content of metal impurities is less than 1 ppm.

[0035] [9] The composition according to any one of [1] to [8], which is for use in lithography.

[0036] According to the present invention, it is possible to provide a composition capable of forming a lithography film having excellent EUV and EB sensitivity.

[0037] Hereinafter, an embodiment of the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, "X to Y" includes the end values ​​X and Y.

[0038] [Composition] The composition of the present embodiment contains a compound represented by the following formula (A1) (hereinafter also simply referred to as "compound (A1)") and a compound represented by the following formula (B1) (hereinafter also simply referred to as "compound (B1)").

[0039]

[0040] In formula (A1), each R independently represents an organic group that is not a functional group, and R 1 each independently represent a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups, each A independently represents a group having a protecting group, each Z independently represents an iodine atom or a hydroxy group, each r1 to r3 independently represents an integer of 0 to 3, and each r4 independently represents an integer of 1 to 4, provided that the sum of r1 to r4 is an integer of 1 to 4.

[0041]

[0042] In formula (B1), each R′ independently represents an organic group that is not a functional group, and R 1 Each A' independently represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups; each A' independently represents a group having a protecting group; each Z' independently represents an iodine atom or a hydroxy group; each X independently represents a single bond, a carbonyl group, or a divalent oxygen atom; n1 represents an integer of 1 to 4; r 1’ ~r 3’each independently represents an integer of 0 to 3; 4’ Each independently represents an integer of 1 to 4, provided that formula (B1) has at least one formyl group. 1’ ~r 4’ The sum of these represents an integer of 1 to 4.

[0043] The composition having such a structure enables the composition to form a lithography film having excellent EUV and EB sensitivity. Although the reason for this is not clear, the inventors presume it to be as follows. However, the reason is not limited to this.

[0044] In the composition, because compound (A1) and compound (B1) contain iodine atoms, the composition has a very high absorption rate of radiation such as EUV and can exhibit a sensitizing effect upon radiation exposure. Furthermore, compound (A1) and compound (B1) also contain formyl groups. When a compound contains a formyl group, the compound is stabilized in the composition due to reaction between the formyl group and the substrate (resin) or condensation between formyl groups. A composition containing such a compound facilitates film formation, enabling more stable film formation for lithography, such as resist films. Furthermore, compound (A1) and compound (B1) contain benzene rings and have a high content of aromatic rings. As a result, the composition has relatively high heat resistance, making it less susceptible to heat damage even in semiconductor manufacturing processes that involve a relatively large number of heating steps. Compound (A1) and compound (B1) are structurally very similar, while compound (B1) is bulkier than compound (A1). Therefore, by using compound (A1) and compound (B1), the crystallinity of compound (A1) and the crystallinity of compound (B1) can be moderately inhibited in the composition. Therefore, the solubility stability in organic solvents is increased, making film formation easier. As a result, it is estimated that the composition of this embodiment reduces film defects and can suitably form a film for lithography that is excellent in sensitivity to radiation such as EUV.

[0045] When compound (A1) and / or compound (B1) further contains a hydroxy group, the composition containing such a compound has higher dissolution stability, which is thought to be effective in suppressing the generation of fine particles, and therefore tends to more effectively form a film for lithography with fewer film defects and better EUV and EB sensitivity.

[0046] [Compound Represented by Formula (A1)] The composition contains a compound represented by the above formula (A1). In formula (A1), R represents an organic group that is not a functional group. Examples of the organic group include alkyl groups having 1 to 30 carbon atoms.

[0047] Examples of alkyl groups having 1 to 30 carbon atoms include linear and branched alkyl groups. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, sec-hexyl, tert-hexyl, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl.

[0048] The alkyl group is preferably a methyl group, an ethyl group, or a propyl group (including isomers, the same applies hereinafter). When compound (A1) contains such an alkyl group, defects in the film tend to be further reduced, and a film for lithography having superior EUV and EB sensitivity tends to be more suitably formed.

[0049] In formula (A1), R 1 represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups. Examples of the polymerizable unsaturated bond include an ethylenic double bond and a triple bond. 1When the compound contains the compound, defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity tends to be more suitably formed.

[0050] R １ is a functional group and is not an alkyl group. １ Examples of the alkyl group include an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a halogen atom other than an iodine atom, a nitro group, an amino group, a thiol group, and a cyano group.

[0051] Among these groups, groups that can have a substituent may have a substituent. Unless otherwise defined, "substituted" means that one or more hydrogen atoms in the functional group are substituted with a substituent. Examples of "substituents" include halogen atoms, hydroxy groups, cyano groups, nitro groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, amino groups having 0 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, acyl groups having 1 to 30 carbon atoms (preferably alkyloyloxy groups having 1 to 20 carbon atoms and aryloyloxy groups having 7 to 30 carbon atoms), alkoxycarbonyl groups having 2 to 20 carbon atoms, and alkylsilyl groups having 1 to 20 carbon atoms. These groups may be substituted within a substituent or a group having a substituent, or may be substituted with another R １ Suitable examples of the group that may form a ring structure include a glycidyl group, a cyclic acetal group, and a group in which two adjacent hydroxyl groups are protected by an acetal protecting group structure.

[0052] R １are preferably an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group. More preferably, they are an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or a hydroxyalkyl group having 1 to 30 carbon atoms. More preferred are alkoxy groups having 1 to 30 carbon atoms, aldehyde groups having 1 to 30 carbon atoms, carboxy groups having 1 to 30 carbon atoms, carboxylic acid ester groups having 2 to 10 carbon atoms, and alkoxyalkyl groups having 2 to 30 carbon atoms, still more preferred are alkoxy groups having 1 to 30 carbon atoms, and aldehyde groups having 1 to 30 carbon atoms, and even more preferred are alkoxy groups having 1 to 30 carbon atoms. １ When the compound contains such a group, there is a tendency that the film has fewer defects and is more suitable for forming a film for lithography that has better EUV and EB sensitivity.

[0053] Examples of alkoxy groups having 1 to 30 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy. The alkoxy group may be linear, branched, or cyclic. Of these, preferred alkoxy groups are methoxy and ethoxy. R １ When the compound contains such a group, there is a tendency that the film has fewer defects and is more suitable for forming a film for lithography that has better EUV and EB sensitivity.

[0054] The aldehyde group having 1 to 30 carbon atoms includes a formyl group (*-CHO) and a *-R ２ In this specification, the symbol "*" in a group indicates a bonding site. ２Examples of the aldehyde group include a linear or branched alkyl group having a total of 1 to 20 carbon atoms. The alkyl group may refer to the above. The alkyl group may have a substituent. The above may be referred to for the substituent. Among them, the aldehyde group is preferably a formyl group. R １ When the compound contains such a group, there is a tendency that the film has fewer defects and is more suitable for forming a film for lithography that has better EUV and EB sensitivity.

[0055] Examples of the carboxy group having 1 to 30 carbon atoms include an acetate group, a propionate group, and a butyrate group.

[0056] Examples of the carboxylic acid ester group having 2 to 10 carbon atoms include a methyl ester group, an ethyl ester group, an n-propyl ester group, an isopropyl ester group, an n-butyl ester group, a tert-butyl ester group, an octyl ester group, a 2-ethylhexyl ester group, a dodecyl ester group, an octadecyl ester group, and a docosyl ester group.

[0057] The alkoxyalkyl group having 2 to 30 carbon atoms or the hydroxyalkyl group having 1 to 30 carbon atoms is more preferably —CH ２ -OR ２ It is shown by R ２ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkyl group may refer to the above. Examples of the aryl group include a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthryl group. The alkyl group or the aryl group may have a substituent. Examples of the substituent include an alkoxy group. Therefore, the -OR ２ R ２ For example, in one embodiment, ２ -OC ２ H ５ It is possible.

[0058] Examples of halogen atoms other than iodine atoms include fluorine atoms, chlorine atoms, and bromine atoms. In this specification, I represents an iodine atom.

[0059] In formula (A1), A represents a group having a protecting group. In this specification, a protecting group refers to a group that dissociates under specific conditions, and is also referred to as a dissociable group. The protecting group is preferably an acid-dissociable group that dissociates in the presence of an acid. Preferred examples of such groups include a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group. Since A becomes a functional group by removing the protecting group, R １ It is a type of.

[0060] The group having a protecting group is preferably a group in which a hydroxy group or a carboxyl group is protected with an acid-labile group. ａ -O-R ｂ Examples of the group include groups represented by the following formula: ａ is a linear or branched alkylene group having 1 to 3 carbon atoms. ｂ Examples of the alkylene group include a monovalent linear or branched alkyl group having 1 to 3 carbon atoms, a cyclic alkyl group, or a divalent cyclic alkyl group that forms a ring together with the adjacent oxygen atom. Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group. Examples of the alkyl group may refer to the above. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.

[0061] In formula (A1), Z represents an iodine atom or a hydroxy group. Formula (A1) preferably contains both an iodine atom and a hydroxy group as Z, since this tends to further reduce film defects and more favorably form a film for lithography that is more excellent in EUV and EB sensitivity.

[0062] In formula (A1), R, R 1 , A, and Z are bonded to any available positions. In formula (A1), an iodine atom, a formyl group, R, R 1 Groups other than A and Z are hydrogen atoms. １Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. ２ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1. ３ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. ４ Each independently represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2. １ ~r ４ The sum of r is an integer between 1 and 4 and is equal to or less than the valence of benzene minus 2. １ ~r ４ When the number is within the above range, defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity can be more suitably formed.

[0063] [Compound Represented by Formula (A2)] The compound represented by formula (A1) preferably contains a compound represented by the following formula (A2) (hereinafter also simply referred to as "compound (A2)"). When the composition contains compound (A2) as compound (A1), there is a tendency that defects in the film are further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.

[0064]

[0065] In formula (A2), R, R 1 and Z are defined the same as in formula (A1). r1 and r2 each independently represent an integer of 0 to 2, and r4 each independently represent an integer of 1 to 3, provided that the sum of r1, r2, and r4 represents an integer of 1 to 3.

[0066] In formula (A2), R, R 1 In formula (A2), at least one hydrogen atom is bonded, but an iodine atom, a formyl group, R, R 1and groups other than Z are hydrogen atoms. Each r1 independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0. ２ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1. ４ are each independently an integer of 1 to 3, preferably 1 or 2, and more preferably 2. The sum of r1, r2, and r4 is an integer of 1 to 3 and is equal to or less than the "valence of benzene minus 3." When the numbers of r1, r2, and r4 are within the above ranges, film defects tend to be further reduced, and a film for lithography having better EUV and EB sensitivity tends to be more suitably formed.

[0067] [Compounds Represented by Formulas (A3) to (A5)] It is more preferable that the compound represented by formula (A2) contains one or more compounds selected from the group consisting of a compound represented by formula (A3) below (hereinafter also referred to simply as "compound (A3)"), a compound represented by formula (A4) below (hereinafter also referred to simply as "compound (A4)"), and a compound represented by formula (A5) below (hereinafter also referred to simply as "compound (A5)"). When the composition contains one or more compounds selected from the group consisting of compound (A3), compound (A4), and compound (A5) as compound (A1) or (A2), film defects are further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be more suitably formed. Note that in formulas (A3) to (A5), groups other than iodine atoms, formyl groups, methoxy groups, and hydroxy groups are hydrogen atoms. In formulae (A3) to (A5), the iodine atom is bonded to any available position.

[0068]

[0069] In formula (A3), p represents an integer of 1 to 3. p is preferably 1 or 2, and more preferably 1, since this tends to further reduce defects in the film and more suitably form a film for lithography that is more excellent in EUV and EB sensitivity.

[0070]

[0071] In formula (A4), p represents an integer of 1 to 3. p is preferably 1 or 2, and more preferably 1, since this tends to further reduce defects in the film and more suitably form a film for lithography that is more excellent in EUV and EB sensitivity.

[0072]

[0073] In formula (A5), p represents an integer of 1 to 4. Since there is a tendency that defects in the film are further reduced and a film for lithography having further excellent EUV and EB sensitivity can be further suitably formed, p is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0074] [Compounds Represented by Formula (A3') and Compounds Represented by Formula (A4')] It is further preferred that the compound represented by Formula (A2) comprises one or more compounds selected from the group consisting of compounds represented by the following Formula (A3') (hereinafter also referred to simply as "compounds (A3')") and compounds represented by the following Formula (A4') (hereinafter also referred to simply as "compounds (A4')"). When the composition comprises one or more compounds selected from the group consisting of compounds (A3') and (A4') as compounds (A1) or (A2), film defects are further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be further preferably formed. In Formulas (A3') and (4'), groups other than iodine atoms, formyl groups, methoxy groups, and hydroxy groups are hydrogen atoms. In Formulas (A3') to (4'), the iodine atom is bonded to any available position.

[0075]

[0076] In formula (A3′), p represents an integer of 1 to 3. p is preferably 1 or 2, and more preferably 1, since this tends to further reduce film defects and more suitably form a film for lithography that is more excellent in EUV and EB sensitivity.

[0077]

[0078] In formula (A4′), p represents an integer of 1 to 3. p is preferably 1 or 2, and more preferably 1, since this tends to further reduce film defects and more suitably form a film for lithography that is more excellent in EUV and EB sensitivity.

[0079] [Compounds Represented by Formulae (A6) to (A10)] It is even more preferable that the compound represented by formula (A2) includes one or more compounds selected from the group consisting of a compound represented by formula (A6) below (hereinafter also referred to simply as "compound (A6)"), a compound represented by formula (A7) below (hereinafter also referred to simply as "compound (A7)"), a compound represented by formula (A8) below (hereinafter also referred to simply as "compound (A8)"), a compound represented by formula (A9) below (hereinafter also referred to simply as "compound (A9)"), and a compound represented by formula (A10) below (hereinafter also referred to simply as "compound (A10)"), and it is even more preferable that the compound represented by formula (A2) includes one or more compounds selected from the group consisting of compound (A6) and compound (A7). When the composition contains, as compound (A1) or (A2), one or more selected from the group consisting of compound (A6), compound (A7), compound (A8), compound (A9), and compound (A10), defects in the film tend to be further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be even more suitably formed. When the composition contains, as compound (A1) or (A2), one or more selected from the group consisting of compound (A6) and compound (A7), defects in the film tend to be even further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be even more suitably formed.

[0080]

[0081] The content of the compound represented by formula (A1) is preferably 90.0 parts by mass or more and 99.9 parts by mass or less, and more preferably 93.0 parts by mass or more and 99.8 parts by mass or less, per 100 parts by mass of the composition. When the content of compound (A1) is within the above range, defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity tends to be more suitably formed.

[0082] [Compound Represented by Formula (B1)] The composition contains a compound represented by the above formula (B1). In formula (B1), R' represents an organic group that is not a functional group. For R', reference may be made to R in formula (A1) above. The organic group is preferably a methyl group, an ethyl group, or a propyl group (including isomers; the same applies hereinafter). When compound (B1) contains such an alkyl group as the organic group, film defects tend to be further reduced, and a film for lithography having superior EUV and EB sensitivity tends to be more suitably formed.

[0083] In formula (B1), R 1 R' represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups. 1 ' is R in the above formula (A1). 1 The compound (B1) may be R 1 When the compound contains ', defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity can be more suitably formed.

[0084] R １ ' is preferably an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group. More preferably, it is an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or a hydroxyalkyl group having 1 to 30 carbon atoms. Even more preferably, it is an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 30 carbon atoms, and even more preferably, it is an alkoxy group having 1 to 30 carbon atoms, or an aldehyde group having 1 to 30 carbon atoms. R １When "" contains such a group, there is a tendency that the defects in the film are further reduced, and a film suitable for lithography, which has superior EUV and EB sensitivity, can be formed.

[0085] The alkoxy group having 1 to 30 carbon atoms is preferably a methoxy group or an ethoxy group. １ When "" contains such a group, there is a tendency that the defects in the film are further reduced, and a film suitable for lithography, which has superior EUV and EB sensitivity, can be formed.

[0086] The aldehyde group having 1 to 30 carbon atoms is preferably a formyl group. １ When "" contains such a group, there is a tendency that the defects in the film are further reduced, and a film suitable for lithography, which has superior EUV and EB sensitivity, can be formed.

[0087] In formula (B1), A′ represents a group having a protecting group, and A in formula (A1) above may be referred to as A′.

[0088] The group having a protecting group is preferably a group in which a hydroxy group or a carboxyl group is protected with an acid-labile group. For such a group, the group having a protecting group in the above formula (A1) may be referred to.

[0089] In formula (B1), Z′ represents an iodine atom or a hydroxy group. Formula (B1) preferably contains both an iodine atom and a hydroxy group as Z′, since this tends to further reduce film defects and more favorably form a film for lithography that is more excellent in EUV and EB sensitivity.

[0090] In formula (B1), X represents a single bond, a carbonyl group, or a divalent oxygen atom. The single bond means that the repeating units are bonded by a single bond. The carbonyl group means a divalent functional group represented by "*-C(=O)-*". The divalent oxygen atom means an ether bond represented by "*-O-*".

[0091] In formula (B1), R', R 1 In formula (B1), the iodine atom, the formyl group, R′, R1 Groups other than A', Z', and X are hydrogen atoms.

[0092] n1 represents an integer of 1 to 4. n1 is preferably an integer of 1 to 3, and more preferably 1 or 2. When n1, which is the number of repeating units of compound (B1), is within the above range, defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.

[0093] r １’ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. ２’ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1. ３’ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. ４’ Each independently represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2. １’ ~r ４’ The sum of r is an integer between 1 and 4 and is equal to or less than the valence of benzene minus 2. １’ ~r ４’ When the number is within the above range, defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity can be more suitably formed.

[0094] Formula (B1) has at least one formyl group. At least one formyl group is bonded to any available position in formula (B1). The number of formyl groups is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and even more preferably an integer of 1 to 3. When the number of formyl groups in compound (B1) is within the above range, film defects tend to be further reduced, and a film for lithography having better EUV and EB sensitivity tends to be more suitably formed.

[0095] [Compounds Represented by Formulas (B2) to (B4)] The compound represented by formula (B1) preferably contains one or more compounds selected from the group consisting of a compound represented by the following formula (B2) (hereinafter also simply referred to as "compound (B2)"), a compound represented by the following formula (B3) (hereinafter also simply referred to as "compound (B3)"), and a compound represented by the following formula (B4) (hereinafter also simply referred to as "compound (B4)"). When the composition contains, as compound (B1), one or more compounds selected from the group consisting of compound (B2), compound (B3), and compound (B4), defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed. Note that, in formulas (B2) to (B4), an iodine atom, a formyl group, R', R 1 Groups other than Z′ and Z′ are hydrogen atoms. In formulae (B2) to (B4), the formyl group is bonded to any available position.

[0096]

[0097] In formula (B2), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 2; 4’ are each independently an integer of 1 to 3. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 3.

[0098] In formula (B2), R', R 1 In the formula (B2), one hydrogen atom is bonded, but an iodine atom, a formyl group, R', R 1 Groups other than Z′ and Z′ are hydrogen atoms. n1 represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2. １’ Each independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0. ２’ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1.４’ Each independently represents an integer of 1 to 3, preferably 1 or 2, and more preferably 2. 1’ , r 2’ , and r 4’ The sum of n1, r is an integer of 1 to 3 and is equal to or less than the valence of benzene minus 3. 1’ , r 2’ , and r 4’ When the number is within the above range, defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity can be more suitably formed.

[0099]

[0100] In formula (B3), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 3; 4’ are each independently an integer of 1 to 4. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 4.

[0101] In formula (B3), R', R 1 In the formula (B3), the iodine atom, the carbonyl group, the formyl group, R′, R 1 Groups other than Z′ and Z′ are hydrogen atoms. n1 represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2. 1’ Each independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0. ２’ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1. ４’ Each independently represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2. 1’ , r 2’ , and r 4’The sum of n1, r is an integer between 1 and 4 and is equal to or less than the valence of benzene minus 2. 1’ , r 2’ , and r 4’ When the number is within the above range, defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity can be more suitably formed.

[0102]

[0103] In formula (B4), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 2; 4’ are each independently an integer of 1 to 3. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 3.

[0104] In formula (B4), R', R 1 In the formula (B4), an iodine atom, an ether bond, a formyl group, R′, R 1 Groups other than Z′ and Z′ are hydrogen atoms. n1 represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2. 1’ Each independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0. ２’ Each independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1. ４’ Each independently represents an integer of 1 to 3, preferably 1 or 2, and more preferably 2. 1’ , r 2’ , and r 4’ The sum of n1, r is an integer of 1 to 3 and is equal to or less than the valence of benzene minus 3. 1’ , r 2’ , and r 4’ When the number is within the above range, defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity can be more suitably formed.

[0105] [Compounds Represented by Formulas (B5) to (B26)] The compound represented by formula (B1) more preferably contains one or more compounds selected from the group consisting of compounds represented by the following formulas (B5) to (B26) (hereinafter also simply referred to as "compound (B5)." The same applies to compounds represented by formulas (B6) to (B26).) When the composition contains, as compound (B1), one or more compounds selected from the group consisting of compounds (B5) to (B26), defects in the film are further reduced, and a film for lithography having even better EUV and EB sensitivity tends to be more suitably formed.

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] The content of the compound represented by formula (B1) is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.2 parts by mass or more and 7.0 parts by mass or less, per 100 parts by mass of the composition. When the content of compound (B1) is within the above range, defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity tends to be more suitably formed.

[0112] In order to further improve etching defects, the content of the compound represented by formula (B1) in the composition is preferably 4,000 ppm by mass or more and 8,000 ppm by mass or less. In order to achieve better stability over time, the content of the compound represented by formula (B1) in the composition is preferably 1 ppm by mass or more and 3,000 ppm by mass or less, more preferably 2 ppm by mass or more and 30 ppm by mass or less.

[0113] [Method for Producing a Compound Represented by Formula (A1) and a Compound Represented by Formula (B1)] Compounds (A1) and (B1) can be produced by any method as long as the effects thereof are not impaired. However, a production method including a step of introducing an iodine atom and a formyl group into a compound having a benzene ring is preferred. Note that commercially available products may be used as the compound having a formyl group on the benzene ring, such as benzaldehyde. Furthermore, such compounds can be obtained, for example, by oxidizing a compound having a hydroxy group on the benzene ring, such as phenol, using various formyl agents, or by introducing carbon monoxide using a strong acid. Examples of compounds having a benzene ring include benzene, benzaldehyde, hydroxybenzaldehyde, vanillin, and ethyl vanillin. The step of introducing an iodine atom into such a compound having a benzene ring can be carried out, for example, by reacting the compound having a benzene ring with iodine I. ２ under acidic or alkaline conditions. This reaction can produce compound (A1) and / or (B1). The production ratio of these compounds can be adjusted by the reaction conditions. In particular, lowering the reaction temperature or shortening the reaction time tends to increase the amount of compound (A1) and decrease the amount of compound (B1). Increasing the reaction temperature or lengthening the reaction time tends to decrease the amount of compound (A1) and increase the amount of compound (B1). A preferred method for producing compound (A1) and / or (B1) is to combine a compound having a benzene ring with a functional group capable of substituting an iodine atom by a substitution reaction, and, if necessary, R １ Another method for producing the compound (A1) and / or (B1) comprises a step of iodinating a raw material containing a compound having a benzene ring and, if necessary, R １ The method may include an iodination step of introducing iodine into a raw material containing the above compound as a radical, cation, or anion. Note that a method of introducing an iodine atom into compound (A1) or (B1) as Z or Z′, respectively, can also be carried out in the same manner.

[0114] (Iodination Step) The iodination step can be appropriately selected from the following methods: a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like; a method of reacting iodine chloride in an organic solvent (e.g., JP 2012-180326 A, JP 2000-256231 A, JP 2010-159233 A, J. Chem. Soc. 636, 1943); and a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A).

[0115] The iodinating agent is not particularly limited, but examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, and hydrogen iodide (including hydroiodic acid and aqueous hydrogen iodide solutions). In the iodination step, the ratio of the iodinating agent to the substrate is preferably 1.2 molar or more, more preferably 1.5 molar or more, and even more preferably 2.0 molar or more.

[0116] The iodination introduction reaction can be carried out by reacting at least an iodinating agent with a substrate. For example, a target compound can be obtained under known iodine introduction reaction conditions using the methods described in non-patent documents such as Adv. Synth. Catal. 2007, 349, 1159-1172, Organic Letters; Vol. 6; (2004); pp. 2785-2788, "Organic Synthesis of Bromine and Iodine Compounds: Reagents and Synthesis Methods" (edited by Suzuki Hitomi, published by Manac Corporation Research Institute, Maruzen Publishing), and patent documents such as US Pat. No. 5,300,506, US Pat. No. 5,434,154, US Pat. No. 2009 / 281114, EP No. 1,439,164, and WO 2006 / 101318. Examples of iodinating agents that can be used include, but are not limited to, iodine compounds, iodine monochloride, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetra-normal-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodine fluoride, tert-butylhypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetylhypoiodide, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenylphosphate-methyl iodide, iodine-thallium(I) acetate, 1-chloro-2-iodoethane, and iodine-copper(II) acetate.

[0117] One or more additives can be added to the iodination reaction for the purpose of promoting the reaction or suppressing by-products. Examples of additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate; bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate; oxidizing agents such as cerium (IV) ammonium nitrate and sodium peroxodisulfate; inorganic compounds such as sodium chloride, potassium chloride, mercury (II) oxide, and cerium oxide; organic compounds such as acetic anhydride; and porous substances such as zeolites. In the iodination step, the ratio of the additive to the iodinating agent is preferably 0.5 molar amounts, more preferably 0.5 to 2.0 molar amounts, and even more preferably 0.5 to 1.5 molar amounts.

[0118] In the iodination step, iodine is preferably introduced into the benzene ring using at least an iodine source and an oxidizing agent. Using an iodine source and an oxidizing agent is preferred from the viewpoints of reaction efficiency and improved purity. Examples of the iodination source include the iodinating agents described above. Examples of the oxidizing agent include iodic acid, periodic acid, hydrogen peroxide, and other additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, silver trifluoroacetate, and cerium (IV) ammonium nitrate (CAN)). Furthermore, for phenols having a carboxylic acid group or a nitro group, the iodination reaction can also be carried out using an iodine source such as iodine combined with a silver salt or fuming sulfuric acid to form an iodine cation species. Furthermore, for other relatively inert aromatic compounds, the iodination reaction can be carried out by combining an iodine source with an inorganic salt to form hypoiodous acid and an iodine cation species. Examples of inorganic salts that can be used include potassium peroxodisulfate, etc. A method of introducing iodine into an aliphatic alcohol group by a substitution reaction can also be used as appropriate. Examples of iodinating agents that can be used as appropriate include hydrogen halides, phosphorus halides, sulfonyl halides (a combination of NaI / acetone), thionyl halides, trimethylsilane halides, Vilsmeier reagents, and the Abbel reaction (a combination of triphenylphosphine and an iodine source).

[0119] The reaction in the iodination step can be carried out neat without a solvent, but examples of usable reaction solvents include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; alkyl-based solvents such as hexane, cyclohexane, heptane, pentane, and octane; aromatic hydrocarbon-based solvents such as benzene and toluene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether-based solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid; dimethylformamide; dimethyl sulfoxide; and water.

[0120] The reaction temperature of the iodination step is not particularly limited and may be any temperature between the freezing point and the boiling point of the solvent used in the reaction, but is preferably 0°C to 150°C, more preferably 20°C to 150°C, and even more preferably 50°C to 120°C. The reaction time of the iodination step is also not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours. The reaction system may be refluxed to more efficiently proceed with iodination. Furthermore, in order to control the concentration of the iodinating agent in the reaction system, a reflux tube equipped with a Dean-Stark or the like may be used to control the concentration of the iodinating agent in the reaction solution.

[0121] The iodine substitution reaction in the iodination step can be caused to proceed by reacting at least an iodinating agent with a substrate. For example, the target compound can be obtained under known iodine substitution reaction conditions such as a Sandmeyer reaction using the methods described in Chemistry-A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84, etc.

[0122] (Protective Group Introduction Step) In the preferred production method of compound (A1) and / or (B1), the protective group represented by A or A' can be introduced into a compound having a benzene ring by a known method, for example, a method appropriately selected from the methods described in Green's Protective Groups in Organic Synthesis (Peter G.M. Wuts, WILEY), pp. 17 to 553.

[0123] The ratio of the protecting group introducing agent to the substrate in the protecting group introduction step is not particularly limited, but is preferably 0.5 molar equivalents or more, more preferably 1.0 molar equivalents or more, and even more preferably 1.5 molar equivalents or more. The reaction temperature in the protecting group introduction step is not particularly limited, but is generally suitable at a temperature of 0°C to 200°C. From the viewpoint of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is even more preferred. The preferred temperature range is 0°C to 100°C. The reaction time in the protecting group introduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.

[0124] (Reduction Step) In the compounds (A1) and (B1), the formyl group and the hydroxy group in Z can be obtained, for example, by introducing a carboxyl group or an ester group and then reducing it.

[0125] Known methods can be used for the reduction, including, for example, methods using metal hydride complexes such as sodium borohydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (SBMEA), and diisobutylaluminum hydride (DIBAL); methods using metal hydrides such as aluminum hydride; and methods using these reducing agents together with reduction promoters such as aluminum chloride and ethanedithiol. The reducing agent's reducing ability may be adjusted by modifying a portion of its structure with an alkoxy group or a hydrocarbon group, or by using it in combination with a Lewis acid. Known solvents such as methanol, ethanol, 2-propanol, DMF (dimethylformamide), and DMSO (dimethyl sulfoxide) can be used as the solvent for the reduction reaction. The reaction temperature can be performed at room temperature or under heated conditions, or can be cooled to adjust the reactivity. The reaction temperature is not particularly limited, but is preferably −20° C. to 150° C., more preferably 0° C. to 150° C., and even more preferably 20° C. to 120° C. The ratio of the reducing agent to the substrate in the reduction step is not particularly limited, but is preferably 0.5 molar equivalent or more, more preferably 1.0 molar equivalent or more, and even more preferably 1.5 molar equivalent or more. The reaction time in the reduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.

[0126] The reducing agent used in the step of reducing the ester group to convert it to a hydroxy group is not particularly limited, but examples thereof include boron-based reducing agents and lithium-based reducing agents. As the reducing agent, it is preferable to use a boron-based reducing agent such as sodium borohydride or borane, and it is more preferable to use a reducing agent in combination with calcium chloride or lithium chloride. The solvent is not particularly limited, but examples thereof include THF (tetrahydrofuran), DMSO, chloroform, toluene, etc., and it is preferable to use toluene, and it is more preferable to use it in combination with methanol.

[0127] After the compounds (A1) and (B1) are obtained as crude products by the above reaction, it is preferable to further purify them to remove residual metal impurities. That is, it is preferable to avoid residual metal impurities from the viewpoints of preventing deterioration of the resin over time and storage stability, as well as from the viewpoints of process suitability and production yield due to defects when the resin is applied to a semiconductor manufacturing process. Metal impurities may originate from reaction aids in the manufacturing process of compounds (A1) and / or (B1), or from the reaction kettle and other manufacturing equipment used in the manufacturing process.

[0128] The residual amount (content) of the above-mentioned metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb. In particular, for metal species classified as transition metals, such as Fe (iron), Ni (nickel), Sn (tin), Zn (zinc), Cu (copper), Sb (antimony), W (tungsten), and Al (aluminum), if the residual metal amount is 1 ppm or more, there is a concern that interaction with other compounds may cause denaturation or deterioration of the material over time. Furthermore, with regard to alkali metals and alkalinity metals such as Na (sodium), K (potassium), Ca (calcium), and Mg (magnesium), if the residual metal content in the resin is 1 ppm or more, it is not possible to sufficiently reduce the residual metal content when producing a resin for semiconductor manufacturing processes using compounds (A1) and (B1), which may result in defects or performance degradation due to the residual metal in the semiconductor manufacturing process, resulting in a decrease in yield, and there is a concern that the doping effect of the metal element on the substrate may result in a decrease in characteristics.

[0129] The purification method is not particularly limited, and the methods described in International Publication No. 2015 / 080240 and International Publication No. 2018 / 159707 can be used. Specifically, the purification method includes dissolving compound (A1) and / or (B1) in an organic solvent that is immiscible with water to obtain an organic phase, contacting the organic phase with an acidic aqueous solution to perform an extraction treatment, thereby transferring metal components contained in the organic phase containing compound (A1) and / or (B1) and the organic solvent to the aqueous phase, and then separating the organic phase from the aqueous phase. The organic solvent that is immiscible with water is typically an organic solvent classified as a water-insoluble solvent. The organic solvent is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes. The amount of organic solvent used is typically about 10% by mass based on the compound used.

[0130] Specific examples of the organic solvent to be used include those described in International Publication No. 2015 / 080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, and the like are preferred, with cyclohexanone and propylene glycol monomethyl ether acetate being more preferred.

[0131] The acidic aqueous solution can be appropriately selected from aqueous solutions prepared by dissolving commonly known organic or inorganic compounds in water. Examples include those described in International Publication No. 2015 / 080240. These acidic aqueous solutions can be used alone or in combination of two or more. Examples of the acidic aqueous solution include mineral acid aqueous solutions and organic acid aqueous solutions. Examples of the mineral acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the organic acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. The pH of the acidic aqueous solution is in the range of about 0 to 5, and more preferably about 0 to 3.

[0132] Other purification methods that can be used include a method using a filter, which will be described later; a method using an adsorbent ion exchange resin, in which a liquid is passed through a column, a dispersion / suspension treatment of the ion exchange resin in a container; and a method using distillation.

[0133] In the method for producing compound (A1) and / or (B1), the order and number of the iodination step, the protecting group introduction step, and the reduction step are not particularly limited and can be appropriately selected depending on the structure of the target compound.

[0134] (Purification Method) - Filter Purification Step (Liquid Passage Step) In the method for producing compound (A1) and / or (B1), purification may be performed using, for example, a filter purification step or a treatment step using an ion exchange resin. As the filter purification step, known methods such as the steps described in WO2022 / 009966 and WO2017 / 038968 can be used. As the ion exchange resin, known methods such as the step described in WO2017 / 038964 can be used.

[0135] [Distillation Step] Another purification method is to distill the compound itself. The distillation method is not particularly limited, and known methods such as atmospheric distillation, reduced pressure distillation, molecular distillation, and steam distillation can be used.

[0136] [Composition for lithography] The composition of the present embodiment is useful as a composition for lithography. The composition may be a composition for use in lithography. Hereinafter, the composition of the present embodiment will be described as a composition for lithography (hereinafter also simply referred to as "composition (A)").

[0137] The compounds (A1) and (B1) exhibit a sensitizing effect on the lithography composition containing them upon irradiation with radiation. Therefore, one aspect of this embodiment may be a method for exhibiting a sensitizing effect on the lithography composition upon irradiation with radiation using the compounds (A1) and (B1), and it is preferable to use two or more compounds (A1) and (B1). The reason for this is thought to be, but is not limited to, that the compounds (A1) and (B1) promote absorption of radiation. This effect is particularly pronounced when irradiated with extreme ultraviolet (EUV) radiation. The sensitizing effect can take multiple forms, and when a photosensitive layer formed using the lithography composition is used as a resist film for lithography, it can be confirmed, for example, as follows: 1) Using a patternless surface exposure method, the film thickness of the film obtained is measured after exposure, if necessary, followed by a PEB process (a process of performing a heat treatment after exposure) and, if necessary, a development process (a process of dissolving and removing exposed or unexposed areas with a developer). 2) The exposure dose is changed, the thickness of the resulting film is measured, and the exposure dose at which the film thickness changes drastically is defined as the sensitivity in the surface exposure method. 3) If sensitivity is confirmed on the low exposure dose side, a sensitizing effect can be confirmed. Furthermore, in a method of forming a pattern by exposure, 1) a pattern is formed by changing the exposure dose, and the sensitivity is defined as the exposure dose at which a specified line width is achieved after exposure. 2) If sensitivity is confirmed on the lower exposure dose side, a sensitizing effect can be confirmed. Furthermore, lithography compositions containing compounds (A1) and (B1) are useful for suppressing defects in resist patterns. In particular, in pattern evaluation using extreme ultraviolet (EUV) light, defects such as pitting and bridging can be confirmed by reducing defects. These defects are caused by fluctuations in the optical exposure dose or exposure conditions where the exposure dose is low and the exposure state is essentially similar to defects. However, if the resist film has a sensitizing effect, these fluctuations and defects are avoided by promoting absorption, and the defects are reduced. When the composition of this embodiment is used in a lithography composition, the composition of this embodiment can be used directly as a component of the lithography composition.Alternatively, as another method, the compounds (A1) and (B1) may be processed into a resin (substrate (A)) containing the compounds (A1) and (B1) as a partial structure, and additives (such as an acid generator (C), a crosslinking agent (G), an acid diffusion inhibitor (E), or other component (F)), and the resin and additives may be used as constituent components in a composition for lithography.

[0138] The composition for lithography contains the compounds (A1) and (B1), and may contain other components, such as a base material (A), a solvent (S), an acid generator (C), a crosslinking agent (G), and an acid diffusion controller (E), as necessary. Each component will be described below.

[0139] [Compounds (A1) and (B1)] The lithography composition contains compounds (A1) and (B1). It is preferable that composition (A) contains two or more types of compound (B1). When two or more types of compound (B1) are contained, etching defects shown in the examples below tend to be reduced. The reason for the reduction in etching defects is unclear, but it is thought that, for example, the compatibility between compounds (A1) and (B1) in composition (A) is improved, which may reduce fine defects when a film is formed. When two or more types of compound (B1) are contained, the structures of the repeating units may be the same or different.

[0140] [Substrate (A)] In this embodiment, the substrate (A) refers to a compound other than compounds (A1) and (B1) that can be used as a resist. The substrate (A) may be a resin. For example, the substrate (A) refers to a substrate (e.g., a substrate for lithography or a substrate for resist) that can be used as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB). Examples of the substrate (A) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof. Among these, from the viewpoint of the shape of the resist pattern that can be obtained, preferred are phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives of these.

[0141] From the viewpoints of reducing defects in a film formed using the composition (A) and achieving a good pattern shape, the weight average molecular weight of the substrate (A) is preferably 2000 to 49900, more preferably 2000 to 29900, and even more preferably 2000 to 14900. The weight average molecular weight can be a value obtained by measuring the weight average molecular weight in terms of polystyrene using GPC.

[0142] [Solvent (S)] The solvent (S) in this embodiment may be any solvent capable of dissolving the compounds (A1) and (B1), and known solvents may be used as appropriate. Specific examples of the solvent (S) include ethylene glycol monoalkyl ether acetates; ethylene glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates (e.g., propylene glycol monomethyl ether acetate); propylene glycol monoalkyl ethers; lactate esters; aliphatic carboxylic acid esters; other esters; aromatic hydrocarbons; ketones; 3:9 amides; lactones, etc. Specific examples of these solvents include those disclosed in International Publication No. WO 2020 / 040161.

[0143] The solvent (S) used in the present 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, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0144] In this embodiment, the amounts of the solid components and the solvent (S) are not particularly limited, but are preferably 1 to 80% by mass of the solid components and 20 to 99% by mass of the solvent, more preferably 1 to 50% by mass of the solid components and 50 to 99% by mass of the solvent, even more preferably 2 to 40% by mass of the solid components and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid components and 90 to 98% by mass of the solvent. The total mass of the solid components (the sum of the solid components including optional components such as the base material (A), compound (A1), compound (B1), acid generator (C), crosslinking agent (G), acid diffusion controller (E), and other components (F) (hereinafter the same)) is defined as the amount of the solid components.

[0145] [Acid Generator (C)] The composition (A) of the present embodiment preferably contains one or more acid generators (C). The acid generator (C) is a material that generates an acid directly or indirectly when irradiated with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays, and ion beam. As the acid generator (C), for example, those described in WO 2013 / 024778 can be used. Two or more types of acid generators (C) can also be used in combination.

[0146] The amount of the acid generator (C) used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, still more preferably 3 to 30% by mass, and particularly preferably 5 to 25% by mass, of the total mass of the solid components. By using the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained.

[0147] [Crosslinking Agent (G)] The composition (A) of this embodiment preferably contains one or more crosslinking agents (G). The crosslinking agent (G) can crosslink at least one of the substrate (A), the compound (A1), and the compound (B1). The crosslinking agent (G) intramolecularly or intermolecularly crosslinks the substrate (A) in the presence of the acid generated from the acid generator (C). Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the substrate (A). Examples of the crosslinking agent (G) having a crosslinkable group include those described in WO 2013 / 024778. Two or more crosslinking agents (G) can also be used in combination.

[0148] In this embodiment, the amount of crosslinking agent (G) used is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass, of the total mass of the solid components. When the blending ratio of the crosslinking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the resist film in an alkaline developer tends to be improved, and a decrease in the residual film rate and the occurrence of swelling or meandering of the pattern tend to be suppressed. On the other hand, when the blending ratio is 50% by mass or less, a decrease in the heat resistance of the resist tend to be suppressed.

[0149] [Acid Diffusion Controller (E)] The composition (A) of this embodiment may contain an acid diffusion controller (E). The acid diffusion controller (E) has the effect of controlling the diffusion of acid generated from the acid generator upon irradiation in the resist film, thereby preventing undesirable chemical reactions in unexposed areas. The use of the acid diffusion controller (E) tends to improve the storage stability of the composition (A) of this embodiment. Furthermore, the use of the acid diffusion controller (E) can improve the resolution of a film formed using the composition (A) of this embodiment. In addition, the use of the acid diffusion controller (E) can suppress changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, tending to improve process stability. Examples of the acid diffusion controller (E) include radiation-decomposable basic compounds such as those described in WO 2013 / 024778. Two or more types of acid diffusion controllers (E) can also be used in combination.

[0150] The amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, 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, based on the total mass of the solid components. When the amount of the acid diffusion controller (E) is within the above range, degradation of resolution, pattern shape, dimensional fidelity, and the like tends to be prevented. Furthermore, even if the exposure time between electron beam irradiation and post-exposure heating is long, degradation of the shape of the upper layer of the pattern can be suppressed. Furthermore, when the amount is 10% by mass or less, degradation of sensitivity, developability of unexposed areas, and the like tends to be prevented. Furthermore, the use of such an acid diffusion controller (E) improves the storage stability and resolution of the resist composition, and also suppresses changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, tending to improve process stability.

[0151] [Other Components (F)] The composition (A) of this embodiment may contain one or more of the following additives as the other component (F). (Dissolution Promoter) When the solubility of a solid component in a developer is too low, the dissolution promoter increases the solubility and appropriately increases the dissolution rate of the compound during development. The dissolution promoter is preferably a low-molecular-weight compound, and examples of such a compound include low-molecular-weight phenolic compounds. Examples of low-molecular-weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. Two or more dissolution promoters may also be used in combination.

[0152] The amount of the dissolution promoter to be added is adjusted appropriately depending on the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0153] (Dissolution Controller) When the solubility of a solid component in a developer is too high, the dissolution controller controls the solubility and appropriately reduces the dissolution rate during development. Such a dissolution controller is preferably one that does not undergo chemical changes during processes such as baking, irradiation, and development of the resist film.

[0154] The dissolution controller is not particularly limited, but examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. Two or more dissolution controllers can also be used in combination. The amount of the dissolution controller is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0155] (Sensitizer) The sensitizer absorbs the energy of the irradiated radiation and transfers that energy to the acid generator (C), thereby increasing the amount of acid produced and improving the apparent sensitivity of the resist. Examples of such sensitizers include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. Two or more sensitizers can also be used in combination. The amount of sensitizer added is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0156] (Surfactant) The surfactant improves the coatability, striation, resist developability, etc. of the composition (A) of this embodiment. The surfactant may be an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant. Preferred surfactants include nonionic surfactants. Nonionic surfactants have good affinity with the solvent used in producing the composition (A) of this embodiment, and can further enhance the effects of the composition of this embodiment. Examples of nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol. Commercially available surfactants described in Patent Document 1 can also be used. The amount of surfactant added is adjusted appropriately depending on the type of solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0157] (Organic Carboxylic Acid, or Phosphorus Oxo Acid, or Derivative of the Oxo Acid) Organic carboxylic acids, phosphorus oxo acids, or derivatives of the oxo acids (hereinafter also referred to as "acids or derivatives") have effects such as preventing sensitivity degradation, improving resist pattern shape, or improving post-deposition stability. Examples of organic carboxylic acids include malonic acid as described in Patent Document 1. Examples of phosphorus oxo acids or derivatives thereof include phosphonic acid or derivatives thereof such as esters as described in Patent Document 1, and among these, phosphonic acid is particularly preferred.

[0158] The amount of the acid or derivative may be adjusted appropriately depending on the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.

[0159] (Other Additives) Furthermore, the composition (A) of this embodiment may contain additives other than the components described above, as necessary. Examples of such additives include dyes, pigments, and adhesion promoters. For example, the incorporation of a dye or pigment is preferable because it can visualize the latent image in the exposed area and mitigate the effects of halation during exposure. Furthermore, the incorporation of an adhesion promoter is preferable because it can improve adhesion to the substrate. Further examples of other additives include antihalation agents, storage stabilizers, antifoaming agents, shape modifiers, and the like, specifically 4-hydroxy-4'-methylchalcone.

[0160] [Ratio of Components in the Composition] In the composition (A) of this embodiment, the total amount of compounds (A1) and (B1) is preferably 10 ppm to 10% by mass of the total mass of the solid components of the composition. In this disclosure, the total mass of solid components refers to the sum of solid components including optional components such as the base material (A), compound (A1), compound (B1), acid generator (C), crosslinking agent (G), acid diffusion controller (E), and other components (F). The mass ratio of the base material (A) to the total amount of compounds (A1) and (B1) is preferably 3:97 to 99.5:0.5, and more preferably 10:90 to 99:1. A mass ratio within this range tends to provide high sensitivity and minimize variation in exposure depth. The mass ratio is more preferably 30:70 to 98:2, and even more preferably 50:50 to 97:3.

[0161] The content of the compound represented by formula (A1) in composition (A) is preferably 1 ppm by mass or more and 10,000 ppm by mass or less, more preferably 10 ppm by mass or more and 5,000 ppm by mass or less. When the content of compound (A1) is within the above range, defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity tends to be more suitably formed.

[0162] The content of the compound represented by formula (B1) in composition (A) is preferably 1 ppm by mass or more and 10,000 ppm by mass or less, more preferably 1 ppm by mass or more and 8,000 ppm by mass or less. When the content of compound (B1) is within the above range, defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity tends to be more suitably formed.

[0163] The content of the compound represented by formula (B1) in composition (A) is preferably 0.001 mass ppm or more and 5000 mass ppm or less, more preferably 0.01 mass ppm or more and 3000 mass ppm or less. When the content of compound (B1) is within the above range, defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity tends to be more suitably formed.

[0164] In the composition (A) of this embodiment, the total amount of the base material (A), the compound (A1), and the compound (B1) is preferably 50 to 99.4 mass %, more preferably 55 to 95 mass %, even more preferably 60 to 95 mass %, and particularly preferably 70 to 95 mass %, of the total mass of the solid components. When the total amount is within the above range, the resolution tends to be further improved and the line edge roughness (LER) tends to be further reduced.

[0165] In the composition (A) of this embodiment, the mass ratio (mass %) of the base material (A) / compounds (A1) and (B1) / acid generator (C) / crosslinking agent (G) / acid diffusion controller (E) / other component (F) relative to the total mass of the solid content of the composition (A) of this embodiment is preferably 1.5 to 99.0 / 0.2 to 96.4 / 0.001 to 49 / 0 to 49 / 0.001 to 49 / 0 to 49, more preferably 5 to 98.5 / 0.5 to 89 / 1 to 40 / 0 to 40 / 0.01 to 10 / 0 to 5, even more preferably 15 to 97.5 / 1 to 69 / 3 to 30 / 0 to 30 / 0.01 to 5 / 0 to 1, and particularly preferably 25 to 96.5 / 1.5 to 50 / 3 to 30 / 0 to 30 / 0.01 to 3 / 0.

[0166] The blending ratio of each component is selected from each range so that the total sum adds up to 100% by mass. This blending ratio tends to result in excellent performance in terms of sensitivity, resolution, developability, etc. "Solid content" refers to the components excluding the solvent, and "total mass of solid content" refers to the sum of the components constituting the composition excluding the solvent, which is 100% by mass.

[0167] Composition (A) of the present embodiment is usually prepared at the time of use by dissolving each component in a solvent to form a homogeneous solution, and then, if necessary, filtering the solution through a filter having a pore size of about 0.2 μm, for example.

[0168] [Physical Properties of Composition (A)] The composition (A) of this embodiment can form an amorphous film by spin coating. Furthermore, the composition (A) of this embodiment can be applied to general semiconductor manufacturing processes. Furthermore, the composition (A) of this embodiment can produce either a positive resist pattern or a negative resist pattern, depending on the type of developer used.

[0169] Composition (A) exhibits a sensitizing effect upon irradiation with radiation. Composition (A) also exhibits an excellent sensitizing effect upon EUV exposure. Therefore, the present invention also provides a method for increasing the sensitivity of a composition for lithography upon irradiation with radiation or EUV exposure. As described above, the sensitizing method preferably uses two or more types of compound (B1).

[0170] The content of metal impurities in composition (A) (also referred to as "residual amount") is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb. In particular, for transition metals such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, if the residual metal amount is 1 ppm or more, there is a concern that interactions with other compounds may cause denaturation or deterioration of the material over time. Furthermore, if the residual amount of alkali metals or alkalinity metals such as Na, K, Ca, and Mg is 1 ppm or more, the residual metal amount cannot be sufficiently reduced when using the compound to produce a resin for semiconductor manufacturing, which may lead to defects and performance degradation caused by residual metals in the semiconductor manufacturing process, resulting in a decrease in yield. It is preferable that the total content of Na, K, and Fe in composition (A) is within the above range.

[0171] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0172] [Measurement Method] [Nuclear Magnetic Resonance (NMR)] The structure of the compound was confirmed by NMR measurement using a nuclear magnetic resonance spectrometer "Avance 500III spectrometer" (trade name, manufactured by Bruker) under the following conditions. １ H-NMR measurement] Frequency: 500 MHz Solvent: CDCl ３ , or d ６ -DMSO Internal standard: TMS Measurement temperature: 23℃ [ １３ C-NMR measurement] Frequency: 125 MHz Solvent: CDCl ３ , or d ６ -DMSO Internal standard: Use the solvent used Measurement temperature: 23°C

[0173] [Molecular Weight] The molecular weight of the compound was measured by liquid chromatography-mass spectrometry (LC-MS) using Acquity UPLC / MALDI-Synapt HDMS manufactured by Waters.

[0174] [Synthesis of Compound A] [Synthesis Example 1] Compound (5IV) Compound (5IV) was synthesized according to the following procedure.

[0175]

[0176] A 30 L glass reaction vessel was charged with 1,300 g (8.55 mol) of vanillin (4-hydroxy-3-methoxybenzaldehyde) and 5.6 L of methanol, and nitrogen was blown into the reaction vessel at a flow rate of 200 mL / min, followed by stirring. After confirming dissolution of the vanillin, 2.6 L of ion-exchanged water and 635 g (6 mol) of sodium carbonate were charged, and the mixture was stirred at room temperature (22 ° C) for 3 hours. 2,600 g (10.3 mol) of iodine was added in portions, and the mixture was stirred at room temperature (22 ° C) for 20 hours. Subsequently, a 16.6% aqueous solution of sodium sulfite was added until both the solution was decolorized and the system reached basicity, after which 4.3 L of water was added and the mixture was stirred for 1 hour. The precipitated solid was filtered using a suction filter, rinsed, reslurried, and dried, yielding 1,900 g of a white solid.

[0177] The white solid was purified by column chromatography to obtain compound (5IV). Measurement using a liquid chromatograph (Nexera (registered trademark)-i LC-2020C 3D (product name) manufactured by Shimadzu Corporation) at a detection wavelength of 254 nm confirmed that the purity of compound (5IV) was 99.9% or higher. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed that the molecular weight was 278. Regarding the white solid, １ H-NMR measurement confirmed that the compound had the chemical structure of 4-hydroxy-5-iodo-3-methoxybenzaldehyde (compound (5IV)). １ The H-NMR assignments are shown below: δ (ppm) (d ６ -DMSO): 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.9 (1H, Ph), 7.5 (1H, Ph), 3.8 (3H, -CH ３ )

[0178] [Synthesis of Compound A] [Synthesis Example 2] Compound (5IEV) Compound (5IEV) was synthesized according to the following procedure.

[0179]

[0180] A white solid was obtained in the same manner as in Synthesis Example 1, except that 1,420 g of ethyl vanillin was used instead of 1,300 g of vanillin.

[0181] The white solid was purified by column chromatography to obtain compound (5IEV). As in Synthesis Example 1, the purity of compound (5IEV) was confirmed to be 99.9% or higher by liquid chromatography-mass spectrometry (LC-MS). The molecular weight of the white solid was found to be 292. １ H-NMR measurement confirmed that the compound had the chemical structure of 4-hydroxy-5-iodo-3-ethoxybenzaldehyde (compound (5IEV)). １ The H-NMR assignments are shown below: δ (ppm) (d ６ -DMSO): 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.9 (1H, Ph), 7.5 (1H, Ph), 4.1 (2H, -CH２ -), 1.4 (3H, -CH ３ )

[0182] [Synthesis of Compounds A and B] [Synthesis Example 3] Compound (35DI4HBA), Compound (3I4HBA), and Compound (DM-3I4HBA) Compound (35DI4HBA), Compound (3I4HBA), and Compound (DM-3I4HBA) were synthesized according to the following procedure.

[0183]

[0184] 150 g (1.2 mol) of 4-hydroxybenzaldehyde and 1 L of methanol (Kanto Chemical) were weighed into a 3 L three-neck flask equipped with a stirrer and a nitrogen flow. The flask was immersed in a water bath, the temperature of the water bath was set to 40°C, and the mixture was heated with stirring under a nitrogen stream, and 200 mL of water was added. When the internal temperature reached 34°C, 309.4 g (3.7 mol) of sodium bicarbonate (NaHCO ３ ) was added all at once.

[0185] When the internal temperature reached 38°C, 654.5 g (2.6 mol) of iodine (I ２ ) was added in portions while being careful not to foam, and the mixture was stirred at 40°C for 3 hours. After that, the flask was cooled with water, and an aqueous sodium sulfite solution (Na ２ SO ３ ) was added dropwise until the solution turned yellowish white to obtain a reaction solution.

[0186] 3 L of water was placed in a container equipped with a stirrer, and the reaction solution was poured therein and stirred for 15 minutes to obtain precipitate 1. Precipitate 1 was filtered and washed with 500 mL of water to obtain filtered product 1. Filtered product 1 was placed in a container equipped with a stirrer, and 1 L of water was added thereto and stirred for 15 minutes to obtain precipitate 2. Precipitate 2 was filtered and washed with 300 mL of water to obtain filtered product 2.

[0187] The filtered product 2 was placed in a container equipped with a stirrer, 500 mL of methanol was added, and the mixture was stirred for 15 minutes to obtain a precipitate 3. The precipitate 3 was filtered and washed with 150 mL of methanol to obtain a precipitate 4. The precipitate 4 was separated using column chromatography (packing material: spherical and neutral silica gel 60N (trade name) manufactured by Kanto Chemical Co., Inc.) with a gradient of ethyl acetate and hexane as a developing solvent in a ratio of 1:9 to 9:1 (ethyl acetate:hexane), thereby obtaining compound (35DI4HBA), compound (3I4HBA), and compound (DM-3I4HBA) in a ratio of 1:0.9:0.5.

[0188] Each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weights were 374 for compound (35DI4HBA), 248 for compound (3I4HBA), and 494 for compound (DM-3I4HBA). Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1 above, and the LC purity at 254 nm was confirmed to be 99.9% or higher for each component. １ H-NMR measurements confirmed that the compounds had the chemical structures of compound (35DI4HBA), compound (3I4HBA), and compound (DM-3I4HBA), respectively. １ The H-NMR assignments are shown below.

[0189] ・Compound (35DI4HBA) δ (ppm) (d ６ -DMSO): 10.8 (1H, -CHO), 9.8 (1H, -OH), 8.0 (2H, Ph) Compound (3I4HBA) δ (ppm) (d ６ -DMSO): 11.6 (1H, -OH), 10.8 (1H, -CHO), 6.7-8.0 (3H, Ph) Compound (DM-3I4HBA) δ (ppm) (d ６ -DMSO): 11.0 (2H, -CHO), 9.8 (2H, -OH), 8.2 to 8.3 (4H, Ph)

[0190] [Synthesis of Compounds A and B] [Synthesis Example 4] Compound (35DI2HBA) and Compound (DM-3I2HBA) Compound (35DI2HBA) and Compound (DM-3I2HBA) were synthesized according to the following procedure.

[0191]

[0192] The compound (35DI2HBA) and the compound (DM-3I2HBA) were obtained in a ratio of 1:0.5 (compound (35DI2HBA):compound (DM-3I2HBA)) in the same manner as in Synthesis example 3, except that 2-hydroxybenzaldehyde was used instead of 4-hydroxybenzaldehyde.

[0193] Each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weights of the compound (35DI2HBA) and the compound (DM-3I2HBA) were found to be 374 and 494, respectively. Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1, and the LC purity at 254 nm was confirmed to be 99.9% or higher. １ H-NMR measurements confirmed that the compounds had the chemical structures of compound (35DI2HBA) and compound (DM-3I2HBA). １ The H-NMR assignments are shown below.

[0194] ・Compound (35DI2HBA) δ (ppm) (d ６ -DMSO): 21.4 (1H, -OH), 10.8 (1H, -CHO), 8.0 to 8.2 (2H, Ph) Compound (DM-3I2HBA) δ (ppm) (d ６ -DMSO): 18.1 (2H, -OH), 11.0 (2H, -CHO), 8.1 (4H, Ph)

[0195] [Synthesis of Compound B] [Synthesis Example 5] Compound (DM-5IV), Compound (DM2-5IV), Compound (DM3-5IV), Compound (DM4-5IV), and Compound (DM5-5IV) Compound (DM-5IV), compound (DM2-5IV), compound (DM3-5IV), compound (DM4-5IV), and compound (DM5-5IV) were synthesized according to the following procedure.

[0196]

[0197] A 100 L stainless steel reaction vessel connected to a reflux condenser was charged with 871 g of vanillin and 4900 ml of methanol, and the vanillin was dissolved in methanol by stirring at 220 rpm for 1 hour under a nitrogen flow. While the reaction vessel was ice-cooled, an aqueous sodium hydroxide solution prepared by dissolving 757 g of sodium hydroxide in 1260 mL of pure water was gradually added to the reaction vessel. Subsequently, 3200 g of iodine was divided into 10 portions, and the entire amount of iodine was gradually added to the reaction vessel over 60 minutes. The mixture was then stirred for 8 hours while maintaining the internal temperature at 60 ° C. in a water bath. Subsequently, while stirring at 120 rpm under ice cooling, 21 L of a 6 mol / L aqueous hydrochloric acid solution was added dropwise over 1 hour, followed by further stirring for 30 minutes. Subsequently, 2.3 L of a 20% by weight aqueous sodium sulfite solution was added with stirring, and then 3.5 L of pure water was further added to obtain a precipitate. The resulting precipitate was collected by filtration. The resulting solid filtrate was separated using column chromatography (packing material: silica gel 60N (spherical, neutral) particle size 100 to 200 μm (trade name) for column chromatography manufactured by Kanto Chemical Co., Inc.) with a gradient of ethyl acetate and hexane as a developing solvent in a ratio of 1:9 to 9:1 (ethyl acetate:hexane), to obtain 380 g of compound (DM-5IV), 5 g of compound (DM2-5IV), 0.5 g of compound (DM3-5IV), 9 g of compound (DM4-5IV), and 1.5 g of compound (DM5-5IV).

[0198] Each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weights were 554 for compound (DM-5IV), 428 for compound (DM2-5IV), 578 for compound (DM3-5IV), 428 for compound (DM4-5IV), and 578 for compound (DM5-5IV). Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1, and it was confirmed that the LC purity at 254 nm was 99.9% or higher for each component. １H-NMR measurement confirmed that the compounds had the chemical structures of compound (DM-5IV), compound (DM2-5IV), compound (DM3-5IV), compound (DM4-5IV), and compound (DM5-5IV). １ The H-NMR assignments are shown below.

[0199] ・Compound (DM-5IV) δ (ppm) (d ６ -DMSO): 11.0 (2H, -CHO), 9.8 (2H, -OH), 7.5 (2H, Ph), 3.8 (6H, -CH ３ ) ・Compound (DM2-5IV) δ (ppm) (d ６ -DMSO): 20.0 (1H, -OH), 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.0 to 7.6 (4H, Ph), 3.8 (6H, -CH3) Compound (DM3-5IV δ (ppm) (d ６ -DMSO): 20.0 (2H, -OH), 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.0 to 7.6 (6H, Ph), 3.8 (9H, -CH ３ ) ・Compound (DM4-5IV) δ (ppm) (d ６ -DMSO): 10.8 (2H, -CHO), 8.7 (1H, -OH), 6.9 to 7.8 (4H, Ph), 3.8 (6H, -CH ３ ) ・Compound (DM5-5IV) δ (ppm) (d ６ -DMSO): 10.8 (3H, -CHO), 8.7 (1H, -OH), 6.9-7.8 (6H, Ph), 3.8 (9H, -CH ３ )

[0200] [Synthesis of Compound B] [Synthesis Example 6] Compound (DM-5IEV), Compound (DM2-5IEV), Compound (DM3-5IEV), Compound (DM4-5IEV), and Compound (DM5-5IEV) Compound (DM-5IEV), compound (DM2-5IEV), compound (DM3-5IEV), compound (DM4-5IEV), and compound (DM5-5IEV) were synthesized according to the following procedure.

[0201]

[0202] Compound (DM-5IEV), compound (DM2-5IEV), compound (DM3-5IEV), compound (DM4-5IEV), and compound (DM5-5IEV) were obtained in the same manner as in Synthesis example 5, except that ethyl vanillin was used instead of vanillin.

[0203] Each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weights were 582 for compound (DM-5IEV), 456 for compound (DM2-5IEV), 620 for compound (DM3-5IEV), 456 for compound (DM4-5IEV), and 620 for compound (DM5-5IEV). Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1, and the LC purity at 254 nm was confirmed to be 99.9% or higher for each component. １ H-NMR measurements confirmed that the compounds had the chemical structures of compound (DM-5IEV), compound (DM2-5IEV), compound (DM3-5IEV), compound (DM4-5IEV), and compound (DM5-5IEV). １ The H-NMR assignments are shown below.

[0204] ・Compound (DM-5IEV) δ (ppm) (d ６ -DMSO): 10.8 (2H, -CHO), 9.8 (2H, -OH), 7.9 (2H, Ph), 4.1 (4H, -CH ２ -), 1.4 (6H, -CH ３ ) ・Compound (DM2-5IEV) δ (ppm) (d ６ -DMSO): 20.0 (1H, -OH), 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.1 to 7.4 (4H, Ph), 4.1 (4H, -CH ２ -), 1.4 (6H, -CH ３ ) ・Compound (DM3-5IEV) δ (ppm) (d ６ -DMSO): 20.0 (2H, -OH), 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.0 to 7.6 (6H, Ph), 4.1 (6H, -CH ２ -), 1.4 (9H, -CH ３) ・Compound (DM4-5IEV) δ (ppm) (d ６ -DMSO): 10.8 (2H, -CHO), 8.7 (1H, -OH), 6.9 to 7.8 (4H, Ph), 4.1 (4H, -CH ２ -), 1.4 (6H, -CH ３ ) ・Compound (DM5-5IEV) δ (ppm) (d ６ -DMSO): 10.8 (3H, -CHO), 8.7 (1H, -OH), 6.9 to 7.8 (6H, Ph), 4.1 (6H, -CH ２ -), 1.4 (9H, -CH ３ )

[0205] [Synthesis of Compound B] [Synthesis Example 7] Compound (DM-3I4HBA), Compound (DM2-3I4HBA), Compound (DM3-3I4HBA), Compound (DM4-3I4HBA), and Compound (DM5-3I4HBA) Compound (DM-3I4HBA), Compound (DM2-3I4HBA), Compound (DM3-3I4HBA), Compound (DM4-3I4HBA), and Compound (DM5-3I4HBA) were synthesized according to the following procedure.

[0206]

[0207] Compound (DM-3I4HBA), compound (DM2-3I4HBA), compound (DM3-3I4HBA), compound (DM4-3I4HBA), and compound (DM5-3I4HBA) were obtained in the same manner as in Synthesis example 5, except that 4-hydroxybenzaldehyde was used instead of vanillin.

[0208] As a result of analyzing each component by liquid chromatography-mass spectrometry (LC-MS), the molecular weights of compound (DM-3I4HBA) were 494, compound (DM2-3I4HBA) 494, compound (DM3-3I4HBA) 740, compound (DM4-3I4HBA) 494, and compound (DM5-3I4HBA) 740. Furthermore, as a result of measuring each component using a liquid chromatograph in the same manner as in Synthesis Example 1 above, it was confirmed that the LC purity at 254 nm was 99.9% or higher for each component. １H-NMR measurement confirmed that the compounds had the chemical structures of compound (DM-3I4HBA), compound (DM2-3I4HBA), compound (DM3-3I4HBA), compound (DM4-3I4HBA), and compound (DM5-3I4HBA). １ The H-NMR assignments are shown below.

[0209] ・Compound (DM-3I4HBA) δ (ppm) (d ６ -DMSO): 11.0 (2H, -CHO), 9.8 (2H, -OH), 8.2-8.3 (4H, Ph) Compound (DM2-3I4HBA) δ (ppm) (d ６ -DMSO): 21.4 (1H, -OH), 11.6 (1H, -OH), 11.0 (1H, -CHO), 6.7 to 8.2 (5H, Ph) Compound (DM3-3I4HBA) δ (ppm) (d6-DMSO): 21.4 (2H, -OH), 11.6 (1H, -OH), 11.0 (1H, -CHO), 6.7-8.2 (7H, Ph) Compound (DM4-3I4HBA) δ (ppm) (d ６ -DMSO): 11.0 (2H, -CHO), 9.8 (1H, -OH), 7.0 to 8.2 (5H, Ph) Compound (DM5-3I4HBA) δ (ppm) (d ６ -DMSO): 11.0 (3H, -CHO), 9.8 (1H, -OH), 7.0 to 8.2 (7H, Ph)

[0210] [Synthesis of Compound B] [Synthesis Example 8] Compound (DM-3I2HBA), Compound (DM2-3I2HBA), Compound (DM3-3I2HBA), Compound (DM4-3I2HBA), and Compound (DM5-3I2HBA) Compound (DM-3I2HBA), Compound (DM2-3I2HBA), Compound (DM3-3I2HBA), Compound (DM4-3I2HBA), and Compound (DM5-3I2HBA) were synthesized according to the following procedure.

[0211]

[0212] Compound (DM-3I2HBA), compound (DM2-3I2HBA), compound (DM3-3I2HBA), compound (DM4-3I2HBA), and compound (DM5-3I2HBA) were obtained in the same manner as in Synthesis example 5, except that 2-hydroxybenzaldehyde was used instead of vanillin.

[0213] As a result of analyzing each component by liquid chromatography-mass spectrometry (LC-MS), the molecular weights of compound (DM-3I2HBA) were 494, compound (DM2-3I2HBA) 494, compound (DM3-3I2HBA) 740, compound (DM4-3I2HBA) 494, and compound (DM5-3I2HBA) 740, respectively. Furthermore, as a result of measuring each component using a liquid chromatograph in the same manner as in Synthesis Example 1 above, it was confirmed that the LC purity at 254 nm was 99.9% or more for each component. １ H-NMR measurements confirmed that the compounds had the chemical structures of compound (DM-3I2HBA), compound (DM2-3I2HBA), compound (DM3-3I2HBA), compound (DM4-3I2HBA), and compound (DM5-3I2HBA). １ The H-NMR assignments are shown below.

[0214] ・Compound (DM-3I2HBA) δ (ppm) (d ６ -DMSO): 18.1 (2H, -OH), 11.0 (2H, -CHO), 8.1 (4H, Ph) Compound (DM2-3I2HBA) δ (ppm) (d ６ -DMSO): 12-17 (2H, -OH), 11.0 (1H, -CHO), 6.7-8.2 (5H, Ph) Compound (DM3-3I2HBA) δ (ppm) (d ６ -DMSO): 12-17 (3H, -OH), 11.0 (1H, -CHO), 6.7-8.2 (7H, Ph) Compound (DM4-3I2HBA) δ (ppm) (d ６ -DMSO): 16-17 (1H, -OH), 11.0 (2H, -CHO), 7.1-7.7 (5H, Ph) Compound (DM5-3I2HBA) δ (ppm) (d ６-DMSO): 16-17 (1H, -OH), 11.0 (3H, -CHO), 7.1-7.7 (7H, Ph)

[0215] [Preparation of Compositions] [Examples 1 to 29 and Comparative Examples 1 to 5] The compounds obtained in Synthesis Examples 1 to 8 were mixed to obtain the compositions shown in Table 1, to obtain compositions according to Examples 1 to 29 and Comparative Examples 1 to 5. In Table 1, Compound A1 is a compound represented by Formula (A1), and Compounds B1 to B3 are each compounds represented by Formula (B1). In Table 1, the numerical values ​​for each component indicate parts by mass. For components that were not included, the compound name is indicated as "none" and the parts by mass are indicated as "-".

[0216]

[0217] [Preparation of Composition for Lithography] [Preparation of Base Material] Polymer MAR A polymer MAR represented by the following formula (MAR) was synthesized as a base material for a composition for lithography according to the following procedure.

[0218]

[0219] 0.5 g of 4-hydroxystyrene, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was filtered and dried under reduced pressure to obtain a polymer MAR represented by the above formula (MAR) in the form of a white powder. The weight-average molecular weight (Mw) of this polymer was 11,500, and the dispersity (Mw / Mn) was 1.90. The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC (gel permeation chromatography) using standard polystyrene as a standard substance. １３As a result of C-NMR measurement, the composition ratio (molar ratio) in the above formula (MAR) was found to be a:b:c:d = 60:10:15:15. Note that, although the above formula (MAR) is written in a simplified form to indicate the ratio of each structural unit, the order of the structural units is random, and it is not a block copolymer in which each structural unit forms an independent block. The molar ratio was determined based on the integral ratio of the main chain carbon directly bonded to benzene for units having benzene, and the carbonyl carbon of the ester bond for methacrylate-based units (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate).

[0220] Examples 30 to 60 and Comparative Examples 6 to 11 Lithography compositions according to Examples 30 to 60 and Comparative Examples 6 to 10 were obtained by mixing a base material, each of the compositions obtained in Examples 1 to 29 and Comparative Examples 1 to 5, an acid generator, an acid diffusion inhibitor, and an organic solvent so as to obtain the compositions shown in Table 2. A lithography composition according to Comparative Example 11 was obtained by mixing a base material, an acid generator, an acid diffusion inhibitor, and an organic solvent. In Table 2, the numerical values ​​for each component indicate parts by mass. Components that were not included are indicated as "none" in the composition name and "-" in the parts by mass. In Table 2, the base material, acid generator, acid diffusion inhibitor, and organic solvent are as follows:

[0221] (Base material) MAR...polymer MAR represented by the above formula (MAR) (Acid generator) TPS-109...triphenylsulfonium nonafluorobutanesulfonate (manufactured by Midori Chemical Co., Ltd.) (Acid diffusion inhibitor) TOA...tri-n-octylamine (manufactured by Kanto Chemical Co., Ltd.) (Organic solvent) PGMEA...propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.)

[0222]

[0223] [Evaluation] [Pattern Evaluation (Pattern Formation) of Electron Beam (EB) Resist Pattern] Each of the lithography compositions obtained in Examples 30 to 60 and Comparative Examples 6 to 11 was spin-coated onto a clean silicon wafer and then pre-exposure baked (PB) on a hot plate at 110°C to form a 50 nm thick resist film. The resulting resist film was irradiated with an electron beam using an EB lithography system (ELS-7500 (trade name), manufactured by Elionix Co., Ltd.) in a 1:1 line-and-space setting with 50 nm spacing. After irradiation, the resist film was heated at 110°C for 90 seconds and developed by immersion in an alkaline developer of 2.38% by mass of tetramethylammonium hydroxide (TMAH) for 60 seconds. The resist film was then washed with ultrapure water for 30 seconds and dried to form a resist pattern.

[0224] (Resist Pattern Shape Evaluation) The cross-sectional shape of the obtained 50 nm L / S (1:1) resist pattern was observed using an electron microscope (S-4800, product name) manufactured by Hitachi, Ltd. Regarding the resist pattern shape after development, a pattern width at a position 10% above the pattern height from the surface of the silicon wafer relative to the half-width of the pattern cross section was evaluated as "A" if it was less than +10% of the half-width, and as "C" if it was +10% or more of the half-width. (Resist Pattern Defects) Furthermore, regarding the resist pattern defects after development, the number of spherical foreign particles in a 1 μm long resist pattern was determined as an index. (Evaluation Criteria) S: Number of spherical foreign matter = 0 A: 0 < number of spherical foreign matter ≦ 5 C: 5 < number of spherical foreign matter (Electron Beam Litigation Sensitivity) The minimum amount of electron beam energy capable of lithographing a shape without pattern collapse was defined as "electron beam lithography sensitivity." Electron beam lithography sensitivity equivalent to or better than that of Comparative Example 11 was rated as "A," and sensitivity inferior to that of Comparative Example 11 was rated as "C."

[0225] The evaluation results of the resist pattern shape, resist pattern defects, and electron beam writing sensitivity are shown in Table 3.

[0226]

[0227] [EUV Exposure Sensitivity and Etching Defects] (EUV Exposure Sensitivity) Each of the lithography compositions obtained in Examples 30 to 60 and Comparative Examples 6 to 11 was spin-coated on a silicon wafer and baked at 110°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. The photoresist layer was then irradiated with an extreme ultraviolet (EUV) exposure device (EUVES-7000 (trade name), manufactured by LithoTech Japan Co., Ltd.) at 1 mJ / cm. ２ to 1 mJ / cm ２ 80 mJ / cm ２ After maskless shot exposure with the exposure dose increased to 1000 ppm, the wafer was baked (PEB) at 110°C for 90 seconds and developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, yielding a wafer with 80 shots of exposure on the wafer. For each of the resulting shot exposure areas, the film thickness was measured using an optical interference film thickness meter (VM3200, (trade name), manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness versus the exposure dose was obtained, and the exposure dose at which the slope of the film thickness variation versus the exposure dose was greatest was determined as the sensitivity value (mJ / cm). ２ ) and used as an index of the EUV sensitivity of the resist.

[0228] (Etching Defects) Each of the lithography compositions obtained in Examples 30 to 60 and Comparative Examples 6 to 11 was applied to an 8-inch silicon wafer having a 100 nm-thick oxide film formed on the outermost surface, and baked at 110°C for 60 seconds to form a 100 nm-thick photoresist layer. Next, using an extreme ultraviolet (EUV) exposure device (EUVES-7000 (trade name), manufactured by Litho Tech Japan Co., Ltd.), the entire wafer was subjected to shot exposure at an exposure dose 10% less than the EUV sensitivity value obtained in the above-mentioned EUV sensitivity evaluation, and further baked at 110°C for 90 seconds (PEB), and developed for 60 seconds with a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution to obtain a wafer that had been shot-exposed for 80 shots across the entire wafer.

[0229] The exposed wafer was then subjected to an etching process using a Telius SCCM (trade name, manufactured by Tokyo Electron Ltd.). ４Etching was performed using Ar / Ar gas until the oxide film was etched by 50 nm. The wafers produced by etching were subjected to defect evaluation using a defect inspection device (Surfscan SP5 (trade name), manufactured by KLA Corporation), and the number of cone defects of 19 nm or more was determined as an index of etching defects. (Evaluation criteria) S: Number of cone defects ≦ 6 A: 6 < Number of cone defects ≦ 10 B: 10 < Number of cone defects ≦ 80 C: 80 < Number of cone defects ≦ 400 D: 400 < Number of cone defects

[0230] Table 4 shows the evaluation results of EUV exposure sensitivity and etching defects.

[0231]

[0232] [Preparation of Purified Product of the Composition of Example 15] [Process 1: Acid Purification] 150 g of a solution (10% by mass) of the composition of Example 15 dissolved in propylene glycol monomethyl ether acetate (PGMEA) was charged into a 1000 mL four-neck flask (bottomless) and heated to 80 ° C. with stirring. Next, 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This resulted in separation 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, and the aqueous phase was removed. After repeating this operation three times, the flask was heated to 80 ° C. while reducing the pressure in the flask to 200 hPa or less, and the residual water and PGMEA were concentrated and distilled off. Thereafter, electronic material (EL) grade PGMEA (a reagent manufactured by Kanto Chemical Co., Ltd.) was diluted to adjust the concentration to 10 mass %, thereby obtaining a PGMEA solution of the composition according to Example 15 having a reduced metal content.

[0233] [Treatment 2: Treatment without Using Acid] A PGMEA solution of the composition of Example 15, adjusted to a concentration of 10 mass %, was obtained in the same manner as in Treatment 1, except that ultrapure water was used instead of the aqueous oxalic acid solution.

[0234] [Evaluation] [Metal Content] The metal contents (ppb) of sodium (Na), potassium (K), and iron (Fe) were measured by inductively coupled plasma mass spectrometry (ICP-MS) for a 10 mass% PGMEA solution of the composition of Example 15 that underwent treatment 1 (hereinafter simply referred to as "the composition of Example 15 of Treatment 1"), a 10 mass% PGMEA solution of the composition of Example 15 that underwent treatment 2 (hereinafter simply referred to as "the composition of Example 15 of Treatment 2"), and a 10 mass% PGMEA solution of the composition of Example 15 that did not undergo any treatment (hereinafter simply referred to as "the untreated composition of Example 15"). The respective measurement results are shown in Table 5.

[0235]

[0236] [Preparation of Lithography Compositions] [Examples 61 and 62, and Reference Example 1] A 10 mass% PGMEA solution of the composition according to Example 15 (Process 1), a 10 mass% PGMEA solution of the composition according to Example 15 (Process 2), and a 10 mass% PGMEA solution of the composition according to untreated Example 15 were each condensed, and the PGMEA was distilled off to obtain a composition according to Example 15 (Process 1), a composition according to Example 15 (Process 2), and a composition according to untreated Example 15, respectively. Then, each of the composition according to Example 15 (Process 1), the composition according to Example 15 (Process 2), and the composition according to untreated Example 15 was mixed with a base material, an acid generator, an acid diffusion inhibitor, and an organic solvent to obtain the compositions according to Examples 61 and 62, and Reference Example 1, respectively. In Table 6, the base material, acid generator, acid diffusion inhibitor, and organic solvent are as described above.

[0237]

[0238] [Evaluation] [EUV Exposure Sensitivity and Etching Defects] (EUV Exposure Sensitivity) The compositions for lithography according to Examples 61 and 62 and Reference Example 1 were evaluated for their sensitivity values ​​(mJ / cm 2 ) in the same manner as in the evaluation method for EUV exposure sensitivity described above. ２ ) was calculated and used as an index of the EUV sensitivity of the resist.

[0239] (Etching Defects) In the same manner as in the evaluation method for etching defects described above, the lithography compositions of Examples 61 and 62 and Reference Example 1 were each evaluated for defects, and the number of cone defects of 19 nm or more was determined as an index of etching defects.

[0240] Table 7 shows the evaluation results of EUV exposure sensitivity and etching defects.

[0241]

[0242] [Preparation of Compositions] [Examples 63 to 87 and Comparative Example 12] The compounds obtained in Synthesis Examples 1 and 5 were mixed to obtain the compositions shown in Table 8, thereby obtaining compositions according to Examples 63 to 87 and Comparative Example 12. In Table 8, Compound A1 represents the compound represented by Formula (A1), and Compound B1 represents the compound represented by Formula (B1). In Table 8, the numerical values ​​for each component represent parts by mass. For components that were not included, the compound name is indicated as "none" and the parts by mass are indicated as "-". The organic solvents used were as follows:

[0243] (Organic solvent) THF...tetrahydrofuran (Kanto Chemical Co., Ltd.)

[0244]

[0245] [Evaluation] [Stability over time] (Condition 1) Using an ultraviolet-visible spectrophotometer, the stability over time of each of the compositions obtained in Examples 63 to 87 and Comparative Example 12 was evaluated. Specifically, using an ultraviolet-visible spectrophotometer (UV-3600plus and MPC-603A (trade name) manufactured by Shimadzu Corporation), the absorbance of each composition was measured at 450 nm, 550 nm, and 650 nm, and the average value A ０ The composition was then stored in a desiccator filled with nitrogen, and the desiccator was placed in a thermostatic chamber at 40°C and left for one month. After leaving the composition, the absorbances at 450 nm, 550 nm, and 650 nm were measured in the same manner as above, and the average value A １ The average value A ０ and average value A １ The difference ΔA (ΔA = A ０１ -A１ ) was calculated, and the difference was used to evaluate the stability over time.

[0246] (Condition 2) The difference ΔA was calculated for each of the compositions obtained in Examples 63 to 87 and Comparative Example 12 in the same manner as in Condition 1 above, except that a desiccator filled with air was used instead of a desiccator filled with nitrogen, and the difference was used to evaluate the stability over time.

[0247] The evaluation results of the stability over time under conditions 1 and 2 are shown in Table 9.

[0248]

[0249] [Preparation of Compositions] [Examples 88 to 105] The compounds obtained in Synthesis Examples 1 to 8 were mixed to obtain the compositions shown in Table 10, thereby obtaining compositions according to Examples 88 to 105. In Table 10, Examples 1, 2, 4, 10, 11, 13, 15, 16, 18, 20, 21, 23, 25, 26, and 28, and Comparative Examples 1 to 5, respectively, are compositions obtained in the above Examples or Comparative Examples. For these compositions, reference may be made to Table 1. In Table 10, Compound A1 is a compound represented by Formula (A1), and Compound B1 is a compound represented by Formula (B1). In Table 10, the numerical values ​​for each component indicate parts by mass. For components that were not included, the compound name is indicated as "none" and the parts by mass are indicated as "-."

[0250]

[0251] [Preparation of Lithography Compositions] [Examples 106 to 123] Lithography compositions according to Examples 106 to 123 were obtained by mixing a base material, each of the compositions obtained in Examples 88 to 105, an acid generator, an acid diffusion inhibitor, and an organic solvent so as to obtain the compositions shown in Table 11. In Table 11, Examples 30, 31, 33, 39, 40, 42, 44, 45, 47, 49, 50, 52, 54, 55, and 57, and Comparative Examples 6 to 11, respectively, are lithography compositions obtained in the above examples or comparative examples. For these lithography compositions, see Table 2. In Table 11, the numerical values ​​for each component are in parts by mass. For components that were not included, the composition name is marked "None" and the parts by mass are marked "-". In Table 11, the base material, acid generator, acid diffusion inhibitor, and organic solvent are as follows:

[0252] (Base material) MAR...polymer MAR represented by the above formula (MAR) (Acid generator) TPS-109...triphenylsulfonium nonafluorobutanesulfonate (manufactured by Midori Chemical Co., Ltd.) (Acid diffusion inhibitor) TOA...tri-n-octylamine (manufactured by Kanto Chemical Co., Ltd.) (Organic solvent) PGMEA...propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.)

[0253]

[0254] [Evaluation] [Pattern Evaluation (Pattern Formation) of Electron Beam (EB) Resist Patterns] Each of the lithography compositions obtained in Examples 30, 31, 33, 39, 40, 42, 44, 45, 47, 49, 50, 52, 54, 55, 57, 106 to 123 and Comparative Examples 6 to 11 was spin-coated onto a clean silicon wafer and then pre-exposure baked (PB) on a hot plate at 110°C to form a 50 nm thick resist film. The resulting resist film was irradiated with an electron beam using an EB lithography system (ELS-7500 (trade name), manufactured by Elionix Co., Ltd.) with a 1:1 line-and-space setting and 50 nm spacing. After irradiation, the resist film was heated at 110°C for 90 seconds and developed by immersion in an alkaline developer containing 2.38% by weight of tetramethylammonium hydroxide (TMAH) for 60 seconds. Thereafter, the resist film was washed with ultrapure water for 30 seconds and dried to form a resist pattern.

[0255] (Resist Pattern Shape Evaluation) The cross-sectional shape of the resulting 50 nm L / S (1:1) resist pattern was observed using an electron microscope (S-4800, product name) manufactured by Hitachi, Ltd. Regarding the resist pattern shape after development, a pattern width at a position 10% above the pattern height from the surface of the silicon wafer relative to the half-width of the pattern cross section was evaluated as "A" if it was less than +10% of the half-width, and a pattern width at least +10% of the half-width was evaluated as "C." (Resist Pattern Defects) Furthermore, regarding resist pattern defects after development, the number of spherical foreign particles in a 1 μm long resist pattern was determined as an index. (Evaluation Criteria) S: Number of spherical foreign particles = 0 A: 0 < Number of spherical foreign particles ≦ 5 C: 5 < Number of spherical foreign particles (Electron Beam Litigation Sensitivity) The minimum electron beam energy amount capable of lithographing a shape without pattern collapse was defined as "electron beam lithography sensitivity," and was evaluated according to the following criteria. (Evaluation criteria) SS: Equal to or better than Example 30. S: Inferior to Example 30, but equal to or better than Example 44. A': Inferior to Example 44, but equal to or better than Comparative Example 7. B: Inferior to Comparative Example 7, but equal to or better than Comparative Example 11. C: Inferior to Comparative Example 11.

[0256] The evaluation results of the resist pattern shape, resist pattern defects, and electron beam writing sensitivity are shown in Table 12.

[0257]

[0258] [EUV Exposure Sensitivity and Etching Defects] First, each of the lithography compositions obtained in Examples 30, 31, 33, 39, 40, 42, 44, 45, 47, 49, 50, 52, 54, 55, 57, 106 to 123 and Comparative Examples 6 to 11 was placed in a sealed container filled with nitrogen and stored at 25°C for 3 months. (EUV Exposure Sensitivity) For each of the lithography compositions after storage, the sensitivity value (mJ / cm) was measured in the same manner as in the above-mentioned method for evaluating EUV exposure sensitivity. ２ ) was calculated and used as an index of the EUV sensitivity of the resist.

[0259] (Etching Defects) After storage, each of the compositions for lithography was evaluated for defects in the same manner as in the above-described method for evaluating etching defects, and the number of cone defects of 19 nm or more was determined as an index of etching defects.

[0260] Table 13 shows the evaluation results of EUV exposure sensitivity and etching defects.

[0261]

[0262] This application is based on a Japanese patent application (Patent Application No. 2024-029540) filed on February 29, 2024, the contents of which are incorporated herein by reference.

[0263] According to the present invention, a composition capable of forming a lithography film having excellent EUV and EB sensitivity can be provided, and therefore the composition of the present invention can be suitably used particularly in lithography techniques.

Claims

1. A composition comprising a compound represented by the following formula (A1) and a compound represented by the following formula (B1): (In formula (A1), each R independently represents an organic group that is not a functional group, and R 1 each independently represent a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups; each A independently represents a group having a protecting group; each Z independently represents an iodine atom or a hydroxy group; each r1 to r3 independently represent an integer of 0 to 3; and each r4 independently represent an integer of 1 to 4, provided that the sum of r1 to r4 represents an integer of 1 to 4. (In formula (B1), each R′ independently represents an organic group that is not a functional group, and R 1 Each A' independently represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding an iodine atom or a hydroxy group; each A' independently represents a group having a protecting group; each Z' independently represents an iodine atom or a hydroxy group; each X independently represents a single bond, a carbonyl group, or a divalent oxygen atom; n1 represents an integer of 1 to 4; r 1’ ~r 3’ each independently represents an integer of 0 to 3; 4’ Each independently represents an integer of 1 to 4, provided that formula (B1) has at least one formyl group. 1’ ~r 4’ The sum of these represents an integer of 1 to 4.

2. The composition according to claim 1, wherein the compound represented by formula (A1) includes a compound represented by the following formula (A2): and the compound represented by formula (B1) includes one or more compounds selected from the group consisting of a compound represented by the following formula (B2), a compound represented by the following formula (B3), and a compound represented by the following formula (B4): (In formula (A2), R, R 1 and Z are defined the same as in formula (A1). r1 and r2 each independently represent an integer of 0 to 2, and r4 each independently represent an integer of 1 to 3, provided that the sum of r1, r2, and r4 represents an integer of 1 to 3. (In formula (B2), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 2; 4’ are each independently an integer of 1 to 3. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 3. (In formula (B3), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 3; 4’ are each independently an integer of 1 to 4. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 4. (In formula (B4), R', R 1 ', Z', and n1 are defined the same as in formula (B1). 1’ and r 2’ each independently represents an integer of 0 to 2; 4’ are each independently an integer of 1 to 3. 1’ , r 2’ , and r 4’ The sum of these represents an integer of 1 to 3.

3. The composition according to claim 2, wherein the compound represented by formula (A2) comprises at least one compound selected from the group consisting of a compound represented by formula (A3), a compound represented by formula (A4), and a compound represented by formula (A5): (In formula (A3), p represents an integer of 1 to 3.) (In formula (A4), p represents an integer of 1 to 3.) (In formula (A5), p represents an integer of 1 to 4.) 4. The composition according to claim 2, wherein the compound represented by formula (A2) comprises at least one compound selected from the group consisting of a compound represented by formula (A6), a compound represented by formula (A7), a compound represented by formula (A8), a compound represented by formula (A9), and a compound represented by formula (A10):

5. The composition according to claim 4, wherein the compound represented by formula (A2) comprises at least one compound selected from the group consisting of the compound represented by formula (A6) and the compound represented by formula (A7).

6. The composition according to claim 1, wherein the content of the compound represented by formula (B1) in the composition is 1 ppm by mass or more and 10,000 ppm by mass or less.

7. The composition according to claim 1, which exhibits a sensitizing effect when exposed to radiation.

8. The composition of claim 1, wherein the metal impurity content is less than 1 ppm.

9. The composition of claim 1, which is used in lithography.

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