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

[Technical Field]

[0001] This invention relates to a composition. [Background technology]

[0002] In recent years, advances in lithography technology have led to rapid miniaturization of semiconductors (patterns) and pixels in the manufacturing of semiconductor devices and liquid crystal display elements. Generally, the miniaturization of pixels is achieved by shortening the wavelength of the exposure light source. Specifically, while ultraviolet light, such as the g-line and i-line, was traditionally used, far-ultraviolet exposure using KrF excimer lasers (248nm) and ArF excimer lasers (193nm) is now becoming the focus of mass production, and the introduction of extreme ultraviolet (EUV) lithography (13.5nm) is also progressing. Electron beams (EB) are also used to form fine patterns.

[0003] Conventional lithography resist materials are polymer-based materials capable of forming amorphous films. Examples include polymer-based materials such as polymethyl methacrylate and polyhydroxystyrene or polyalkyl methacrylate having acid-dissociable groups (see, for example, Non-Patent Document 1 below). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Shinji Okazaki, et al., "40 Years of Lithography Technology," S&T Publishing, December 9, 2016. [Overview of the project] [Problems that the invention aims to solve]

[0005] However, for resins and other materials using polymer-based materials, there is still a need to improve sensitivity to EUV and EB, as well as exposure defects that occur when forming lithography films such as resist films.

[0006] The present invention has been made in view of these problems, and aims to provide a composition capable of forming a lithography film with excellent EUV and EB sensitivity. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have discovered 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 with excellent EUV and EB sensitivity, thus 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] [ka]

[0010] (In formula (A1), each R independently represents a non-functional organic group, R 1 Each of the following independently represents a monovalent functional group having 0 to 30 carbon atoms, excluding iodine atoms and hydroxyl groups, which may be identical or different, and which does not contain polymerizable unsaturated bonds; each of the following independently represents a group having a protecting group; each of the following independently represents an iodine atom or a hydroxyl group; each of the following independently represents an integer from 0 to 3; and each of the following independently represents an integer from 1 to 4. However, the sum of r1 to r4 represents an integer from 1 to 4.

[0011] [ka]

[0012] (In formula (B1), each R' independently represents an organic group that is not a functional group, and R 1 ' each independently represents a monovalent functional group having 0 to 30 carbon atoms, which may be the same or different and does not contain a polymerizable unsaturated bond, excluding an iodine atom and 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 from 1 to 4, and r 1’ ~r 3’ each independently represents an integer from 0 to 3, and r 4’ each independently represents an integer from 1 to 4. However, formula (B1) has at least one formyl group. The sum of r 1’ ~r 4’ represents an integer from 1 to 4.).

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

[0014] [Chemical formula]

[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 from 0 to 2, and r4 each independently represents an integer from 1 to 3. However, the sum of r1, r2, and r4 represents an integer from 1 to 3.).

[0016] [Chemical formula]

[0017] (In formula (B2), R', R 1 ', Z', and n1 are defined the same as in formula (B1). r1’ and r 2’ Each of these independently represents an integer between 0 and 2, and r 4’ Each of these independently represents an integer from 1 to 3. However, r 1’ , r 2’ , and r 4’ The sum of these values ​​represents an integer between 1 and 3.

[0018] [ka]

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

[0020] [ka]

[0021] (In formula (B4), R', R 1 ', Z', and n1 are defined in the same way as in formula (B1) above. 1’ and r 2’ Each of these independently represents an integer between 0 and 2, and r 4’ Each of these independently represents an integer from 1 to 3. However, r 1’ , r 2’ , and r 4’ The sum of these values ​​represents an integer between 1 and 3.

[0022] [3] The composition according to [2], wherein the compound represented by formula (A2) is selected from the group consisting of the compound represented by the following formula (A3), the compound represented by the following formula (A4), and the compound represented by the following formula (A5).

[0023] [ka]

[0024] (In equation (A3), p represents an integer between 1 and 3.)

[0025] [ka]

[0026] (In equation (A4), p represents an integer between 1 and 3.)

[0027] [ka]

[0028] (In equation (A5), p represents an integer between 1 and 4.)

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

[0030] [ka]

[0031] [5] The composition according to [4], wherein the compound represented by formula (A2) is selected from the group consisting of the compound represented by formula (A6) and the compound 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) is 1 ppm by mass or more and 10,000 ppm by mass or less in the composition.

[0033] [7] A composition according to any one of [1] to [6] that 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] A composition according to any one of [1] to [8], for use in lithography. [Effects of the Invention]

[0036] According to the present invention, it is possible to provide a composition capable of forming lithography films with excellent EUV and EB sensitivity. [Modes for carrying out the invention]

[0037] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). Note that the following embodiment is illustrative for explaining the present invention, and the present invention is not limited to this embodiment. In this specification, "X~Y" includes the endpoints X and Y.

[0038] [Composition] The composition of this embodiment includes 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] [ka]

[0040] In formula (A1), each R independently represents a non-functional organic group, and R 1Each of the following independently represents a monovalent functional group having 0 to 30 carbon atoms, excluding iodine atoms and hydroxyl groups, which may be the same or different, and which does not contain polymerizable unsaturated bonds; each of the following independently represents a group having a protecting group; each of the following independently represents an iodine atom or a hydroxyl group; each of the following independently represents an integer from 0 to 3; and each of the following independently represents an integer from 1 to 4. However, the sum of r1 to r4 represents an integer from 1 to 4.

[0041] [ka]

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

[0043] The composition, having such a configuration, can form lithography films with excellent EUV and EB sensitivity. The reason for this is not clear, but the inventors deduce it as follows. However, the reason is not limited to this.

[0044] In the composition, since compounds (A1) and (B1) contain iodine atoms, the composition has a very high absorption rate for radiation such as EUV and can exhibit a sensitizing effect during radiation irradiation. Furthermore, compounds (A1) and (B1) also contain formyl groups. When a compound contains a formyl group, the compound becomes more stable in the composition due to the reaction between the formyl group and the substrate (resin), and the condensation of the formyl groups themselves. Compositions containing these compounds can be formed more stably for lithography films such as resist films, thus facilitating film formation. In addition, compounds (A1) and (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 thermal damage even in semiconductor manufacturing processes that involve a relatively large number of heating steps. Furthermore, compounds (A1) and (B1) have very similar structures, while compound (B1) is bulkier than compound (A1). Therefore, by using compounds (A1) and (B1), the crystallinity of compound (A1) and compound (B1) can be appropriately inhibited in the composition. As a result, the solubility stability in organic solvents is increased, making film formation even easier. Therefore, it is presumed that, according to the composition of this embodiment, it is possible to suitably form a lithography film that has reduced defects in the film and excellent sensitivity to radiation such as EUV.

[0045] Furthermore, if compound (A1) and / or compound (B1) further contain hydroxyl groups, the composition containing such compounds exhibits greater solubility. This composition is thought to effectively suppress the generation of fine particles, thus reducing film defects and tending to more effectively form lithography films with superior EUV and EB sensitivity.

[0046] [Compound represented by formula (A1)] The composition contains the compound represented by the above formula (A1). In formula (A1), R represents a non-functional organic group. Examples of organic groups include alkyl groups having 1 to 30 carbon atoms.

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

[0048] Preferably, the alkyl group is a methyl group, an ethyl group, or a propyl group (including isomers; the same applies hereinafter). When compound (A1) contains such alkyl groups, it tends to form a lithography film that is more suitable, with fewer film defects and better EUV and EB sensitivity.

[0049] In formula (A1), R 1 This represents a monovalent functional group with 0 to 30 carbon atoms, excluding iodine atoms and hydroxyl groups, which may be the same or different, and which does not contain polymerizable unsaturated bonds. Examples of polymerizable unsaturated bonds include ethylenic double bonds and triple bonds. Compound (A1) is R 1 Including this element tends to result in fewer defects in the film and the formation of more suitable lithography films with superior EUV and EB sensitivity.

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

[0051] Of these groups, those that can have substituents may have substituents. Unless otherwise defined, "substitution" means that one or more hydrogen atoms in a functional group are replaced by substituents. Examples of "substituents" include halogen atoms, hydroxyl 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 are either substituted or have substituents, or other R 1 They may form a ring structure. Preferred examples of groups that may form a ring structure include glycidyl groups, cyclic acetal groups, and groups in which two adjacent hydroxyl groups form an acetal protecting group structure.

[0052] R 1 Preferably, these are alkoxy groups having 1 to 30 carbon atoms, aldehyde groups having 1 to 30 carbon atoms, carboxyl groups having 1 to 30 carbon atoms, carboxylic acid ester groups having 2 to 10 carbon atoms, alkoxyalkyl groups having 2 to 30 carbon atoms, hydroxyalkyl groups having 1 to 30 carbon atoms, halogen atoms other than iodine, nitro groups, amino groups, and cyano groups. More preferably, these are alkoxy groups having 1 to 30 carbon atoms, aldehyde groups having 1 to 30 carbon atoms, carboxyl groups having 1 to 30 carbon atoms, carboxylic acid ester groups having 2 to 10 carbon atoms, alkoxyalkyl groups having 2 to 30 carbon atoms, and hydroxyalkyl groups having 1 to 30 carbon atoms. More preferably, the group is an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, and an alkoxyalkyl group having 2 to 30 carbon atoms; even more preferably, the group is an alkoxy group having 1 to 30 carbon atoms and an aldehyde group having 1 to 30 carbon atoms; and even more preferably, the group is an alkoxy group having 1 to 30 carbon atoms. 1When such groups are included, the film defects are further reduced, and lithography films with superior EUV and EB sensitivity tend to be formed more favorably.

[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 groups. The alkoxy group may be linear, branched, or cyclic. Among these, methoxy and ethoxy groups are preferred as alkoxy groups. 1 When such groups are included, the film defects are further reduced, and lithography films with superior EUV and EB sensitivity tend to be formed more favorably.

[0054] Examples of aldehyde groups with 1 to 30 carbon atoms include the formyl group (*-CHO) and *-R 2 Groups represented by -CHO are examples. In this specification, the asterisk "*" in a group indicates a bonding site. 2 Examples include linear or branched alkyl groups having a total of 1 to 20 carbon atoms. The alkyl group may refer to the above. The alkyl group may have substituents. The substituent may refer to the above. Among these, the aldehyde group is preferably a formyl group. 1 When such groups are included, the film defects are further reduced, and lithography films with superior EUV and EB sensitivity tend to be formed more favorably.

[0055] Examples of carboxyl groups having 1 to 30 carbon atoms include the acetate group, the propionic acid group, and the butyric acid group.

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

[0057] A carbon-2 to carbon-30 alkoxyalkyl group or a carbon-1 to carbon-30 hydroxyalkyl group is more preferably -CH2-OR 2 This is shown by R 2 This is a hydrogen atom, a C1-C29 alkyl group, or a C1-C29 aryl group. Examples of alkyl groups may be found above. Examples of aryl groups include phenyl, toluyl, benzyl, methylbenzyl, xylyl, mesityl, naphthyl, and anthryl groups. The alkyl group or aryl group may have substituents. Examples of substituents include alkoxy groups. Therefore, the aforementioned -OR 2 R 2 For example, in one embodiment, this could be -CH2-OC2H5.

[0058] Examples of halogen atoms other than iodine include fluorine, chlorine, and bromine. 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 called a dissociable group. Preferably, the protecting group is an acid-dissociable group that dissociates in the presence of an acid. Preferred such groups include 1-substituted ethyl groups, 1-substituted n-propyl groups, 1-branched alkyl groups, silyl groups, acyl groups, 1-substituted alkoxymethyl groups, cyclic ether groups, alkoxycarbonyl groups, and alkoxycarbonylalkyl groups. Since A becomes a functional group when the protecting group is removed, R 1 It is a type of [unclear].

[0060] The protecting group is preferably a hydroxyl group or a carboxyl group protected by an acid-dissociable group. Examples of such groups include *-OR a -OR b The group shown is R. a This refers to linear or branched alkylene groups having 1 to 3 carbon atoms. b Examples of alkyl groups include monovalent linear or branched alkyl groups having 1 to 3 carbon atoms, cyclic alkyl groups, or divalent cyclic alkyl groups that form a ring with adjacent oxygen atoms. Examples of alkylene groups include methylene, ethylene, and propylene groups. Examples of alkyl groups may be found by referring to the above. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, and cyclopentyl groups.

[0061] In formula (A1), Z represents either an iodine atom or a hydroxyl group. Formula (A1) preferably contains both an iodine atom and a hydroxyl group as Z, as this tends to lead to the formation of lithography films with fewer defects and superior EUV and EB sensitivity.

[0062] In formula (A1), R, R 1 A and Z are bonded at any possible positions. In formula (A1), the iodine atom, formyl group, R, R 1Groups other than A and Z are hydrogen atoms. Each r1 independently represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0. Each r2 independently represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 1 or 2, and even more preferably 1. Each r3 independently represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0. Each r4 independently represents an integer from 1 to 4, preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 2. The sum of r1 to r4 is an integer from 1 to 4 and is less than or equal to "benzene valency - 2". When the numbers of r1 to r4 are within the above range, there is a tendency to be able to form lithography films that have fewer defects in the film and are more suitable for EUV and EB sensitivity.

[0063] [Compound represented by formula (A2)] The compound represented by formula (A1) preferably contains the compound represented by formula (A2) below (hereinafter also simply referred to as "compound (A2)"). When the composition contains compound (A2) as compound (A1), it tends to be possible to more suitably form a lithography film with fewer defects and superior EUV and EB sensitivity.

[0064] [ka]

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

[0066] In formula (A2), R, R 1 , and Z are bonded at any possible position. Note that in formula (A2), at least one hydrogen atom is bonded, but iodine, formyl group, R, R 1Groups other than Z are hydrogen atoms. Each r1 independently represents an integer from 0 to 2, preferably 0 or 1, more preferably 0. Each r2 independently represents an integer from 0 to 3, preferably 0 to 2, more preferably 1 or 2, even more preferably 1. Each r4 independently represents an integer from 1 to 3, preferably 1 or 2, more preferably 2. The sum of r1, r2, and r4 is an integer from 1 to 3, and is less than or equal to "benzene valency -3". When the numbers of r1, r2, and r4 are within the above range, there is a tendency to be able to more suitably form lithography films with fewer defects and better EUV and EB sensitivity.

[0067] [Compounds represented by formula (A3) to compounds represented by formula (A5)] It is more preferable that the compound represented by formula (A2) contains one or more compounds selected from the group consisting of the compound represented by formula (A3) below (hereinafter also simply referred to as "compound (A3)"), the compound represented by formula (A4) below (hereinafter also simply referred to as "compound (A4)"), and the compound represented by formula (A5) below (hereinafter also simply referred to as "compound (A5)"). When the composition contains one or more compounds selected from the group consisting of compounds (A3), compounds (A4), and compounds (A5) as compound (A1) or (A2), the number of defects in the film is further reduced, and a lithography film with even better EUV and EB sensitivity tends to be formed more favorably. In formulas (A3) to (A5), groups other than the iodine atom, formyl group, methoxy group, and hydroxyl group are hydrogen atoms. In formulas (A3) to (A5), the iodine atom is bonded at any position where it can be bonded.

[0068] [ka]

[0069] In formula (A3), p represents an integer from 1 to 3. Since it tends to be possible to form lithography films that have even fewer defects and even better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.

[0070] [ka]

[0071] In formula (A4), p represents an integer from 1 to 3. Since it tends to be possible to form lithography films that have even fewer defects and even better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.

[0072] [ka]

[0073] In formula (A5), p represents an integer from 1 to 4. Since it tends to be possible to form lithography films that have even fewer defects and even better EUV and EB sensitivity, p is preferably an integer from 1 to 3, and more preferably 1 or 2.

[0074] [Compounds represented by formula (A3') and compounds represented by formula (A4')] It is even more preferable that the compound represented by formula (A2) contains one or more compounds selected from the group consisting of the compound represented by formula (A3') below (hereinafter also simply referred to as "compound (A3')") and the compound represented by formula (A4') below (hereinafter also simply referred to as "compound (A4')". When the composition contains one or more compounds selected from the group consisting of compound (A3') and compound (A4') as compound (A1) or (A2), it tends to be possible to form a lithography film that has even more defects in the film and even better EUV and EB sensitivity. In formulas (A3') and (4'), groups other than the iodine atom, formyl group, methoxy group, and hydroxyl group are hydrogen atoms. In formulas (A3') and (4'), the iodine atom is bonded at any possible position.

[0075] [ka]

[0076] In formula (A3'), p represents an integer from 1 to 3. Since it tends to be possible to form a lithography film that is more suitable, with further reductions in film defects and even better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.

[0077] [ka]

[0078] In formula (A4'), p represents an integer from 1 to 3. Since it tends to be possible to form a lithography film that is more suitable, with further reductions in film defects and even better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.

[0079] [Compounds represented by formula (A6) to compounds represented by formula (A10)] It is even more preferable that the compound represented by formula (A2) contains one or more compounds selected from the group consisting of the compound represented by formula (A6) below (hereinafter also simply referred to as "compound (A6)"), the compound represented by formula (A7) below (hereinafter also simply referred to as "compound (A7)"), the compound represented by formula (A8) below (hereinafter also simply referred to as "compound (A8)"), the compound represented by formula (A9) below (hereinafter also simply referred to as "compound (A9)"), and the compound represented by formula (A10) below (hereinafter also simply referred to as "compound (A10)"), and it is even more preferable that it contains one or more compounds selected from the group consisting of compound (A6) and compound (A7). If the composition contains one or more compounds selected from the group consisting of compounds (A6), (A7), (A8), (A9), and (A10) as compound (A1) or (A2), there is a tendency for the film defects to be further reduced and for a lithography film with even better EUV and EB sensitivity to be formed even more favorably. If the composition contains one or more compounds selected from the group consisting of compounds (A6) and (A7) as compound (A1) or (A2), there is a tendency for the film defects to be further reduced and for a lithography film with even better EUV and EB sensitivity to be formed even more favorably.

[0080] [ka]

[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, there is a tendency to be able to form a lithography film that is more suitable, with fewer film defects and better EUV and EB sensitivity.

[0082] [Compound represented by formula (B1)] The composition contains the compound represented by the above formula (B1). In formula (B1), R' represents a non-functional organic group. R' may refer 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 alkyl groups as organic groups, it tends to form lithography films with fewer defects and superior EUV and EB sensitivity.

[0083] In formula (B1), R 1 ' represents a monovalent functional group with 0 to 30 carbon atoms, excluding iodine atoms and hydroxyl groups, which may be the same or different, and which does not contain polymerizable unsaturated bonds. 1 'As for R in the above formula (A1), 1 You may also refer to the following. Compound (B1) is R 1 The inclusion of ' tends to result in fewer film defects and the formation of lithography films with superior EUV and EB sensitivity, making them more suitable for lithography.

[0084] R 1 Preferably, the ' is a C1-C30 alkoxy group, a C1-C30 aldehyde group, a C1-C30 carboxyl group, a C2-C10 carboxylic acid ester group, a C2-C30 alkoxyalkyl group, a C1-C30 hydroxyalkyl group, a halogen atom other than iodine, a nitro group, an amino group, and a cyano group. More preferably, the ' is a C1-C30 alkoxy group, a C1-C30 aldehyde group, a C1-C30 carboxyl group, a C2-C10 carboxylic acid ester group, a C2-C30 alkoxyalkyl group, and a C1-C30 hydroxyalkyl group. Even more preferably, the ' is a C1-C30 alkoxy group, a C1-C30 aldehyde group, a C1-C30 carboxyl group, a C2-C10 carboxylic acid ester group, and a C2-C30 alkoxyalkyl group, and even more preferably, the ' is a C1-C30 alkoxy group and a C1-C30 aldehyde group. R 1 When such groups are included, film defects are reduced, and films with superior EUV and EB sensitivity tend to be more suitable for lithography.

[0085] Preferably, the alkoxy groups having 1 to 30 carbon atoms are methoxy groups and ethoxy groups. 1 When such groups are included, film defects are reduced, and films with superior EUV and EB sensitivity tend to be more suitable for lithography.

[0086] The aldehyde group having 1 to 30 carbon atoms is preferably a formyl group. 1 When such groups are included, film defects are reduced, and films with superior EUV and EB sensitivity tend to be more suitable for lithography.

[0087] In formula (B1), A' represents a group having a protecting group. A' may refer to A in formula (A1) above.

[0088] Preferably, the protecting group is a hydroxyl group or a carboxyl group protected by an acid-dissociable group. Such a group may refer to the protecting group in formula (A1) above.

[0089] In formula (B1), Z' represents either an iodine atom or a hydroxyl group. Formula (B1) preferably contains both an iodine atom and a hydroxyl group as Z', as this tends to lead to a more suitable formation of lithography films with reduced defects and superior EUV and EB sensitivity.

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

[0091] In formula (B1), R', R 1 ', A', Z', and X are bonded at any possible positions. Note that in formula (B1), the iodine atom, formyl group, R', R1 Groups other than ', A', Z', and X become hydrogen atoms.

[0092] n1 represents an integer from 1 to 4. Preferably, n1 is an integer from 1 to 3, and more preferably 1 or 2. When n1, which is the number of repeats of compound (B1), is within the above range, there is a tendency to be able to form a lithography film that is more suitable, with fewer defects in the film and better EUV and EB sensitivity.

[0093] r 1’ Each of these independently represents an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and even more preferably 0. 2’ Each of these independently represents an integer between 0 and 3, preferably between 0 and 2, more preferably 1 or 2, and even more preferably 1. 3’ Each of these independently represents an integer between 0 and 3, preferably between 0 and 2, more preferably 0 or 1, and even more preferably 0. 4’ Each of these independently represents an integer from 1 to 4, preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 2. 1’ ~r 4’ The sum is an integer between 1 and 4, and is less than or equal to "benzene's valency - 2". 1’ ~r 4’ When the number of defects falls within the above range, it tends to result in a reduction in film defects and the formation of lithography films with superior EUV and EB sensitivity.

[0094] Formula (B1) has at least one formyl group. At least one formyl group is bonded to any bondable position in formula (B1). The number of formyl groups is preferably an integer from 1 to 5, more preferably an integer from 1 to 4, and even more preferably an integer from 1 to 3. When the number of formyl groups in compound (B1) is within the above range, there is a tendency to form a lithography film that is more suitable, with fewer film defects and better EUV and EB sensitivity.

[0095] [Compound represented by formula (B2) - Compound represented by formula (B4)] The compound represented by formula (B1) preferably contains one or more 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 selected from the group consisting of compound (B2), compound (B3), and compound (B4), the defects of the film are further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity tends to be more preferably formed. In formulas (B2) to (B4), groups other than the iodine atom, formyl group, R', R 1 ', and Z' are hydrogen atoms. In formulas (B2) to (B4), the formyl group is bonded at any position where bonding is possible.

[0096]

Chemical formula

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

[0098] In formula (B2), R', R 1 ', and Z' are bonded at any position where bonding is possible. In formula (B2), one hydrogen atom is bonded, but groups other than the iodine atom, formyl group, R', R 1 ', and Z' are hydrogen atoms. n1 represents an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 1 or 2. r 1’Each independently represents an integer from 0 to 2, preferably 0 or 1, more preferably 0. r 2’ Each independently represents an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 1 or 2, still more preferably 1. r 4’ Each independently represents an integer from 1 to 3, preferably 1 or 2, more preferably 2. r 1’ , r 2’ , and r 4’ The sum of and is an integer from 1 to 3 and is not more than "the valence of benzene - 3". n1, r 1’ , r 2’ , and r 4’ When the numbers of and are within the above ranges, defects in the film are further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity tends to be more suitably formed.

[0099]

Chemical formula

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

[0101] In formula (B3), R’, R 1 ’, and Z’ are bonded at any position where bonding is possible. In formula (B3), groups other than iodine atoms, carbonyl groups, formyl groups, R’, R 1 ’, and Z’ are hydrogen atoms. n1 represents an integer from 1 to 4, preferably an integer from 1 to 3, more preferably 1 or 2. r 1’ Each independently represents an integer from 0 to 3, preferably an integer from 1 to 3, more preferably 0 or 1, still more preferably 0. r 2’Each of these independently represents an integer between 0 and 3, preferably between 0 and 2, more preferably 1 or 2, and even more preferably 1. 4’ Each of these independently represents an integer from 1 to 4, preferably an integer from 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 less than or equal to "benzene valency -2". 1’ , r 2’ , and r 4’ When the number of defects falls within the above range, it tends to result in a reduction in film defects and the formation of lithography films with superior EUV and EB sensitivity.

[0102] [ka]

[0103] In formula (B4), R', R 1 ', Z', and n1 are defined in the same way as in formula (B1) above. 1’ and r 2’ Each of these independently represents an integer between 0 and 2, and r 4’ Each of these independently represents an integer from 1 to 3. However, r 1’ , r 2’ , and r 4’ The sum of these values ​​represents an integer between 1 and 3.

[0104] In formula (B4), R', R 1 ', and Z' are bonded at any possible positions. Note that in formula (B4), iodine atom, ether bond, formyl group, R', R 1 Groups other than ', and Z' are hydrogen atoms. n1 represents an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 1 or 2. 1’ Each of these independently represents an integer between 0 and 2, preferably 0 or 1, and more preferably 0. 2’ Each of these independently represents an integer between 0 and 3, preferably between 0 and 2, more preferably 1 or 2, and even more preferably 1.4’ Each of these independently represents an integer from 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 between 1 and 3, and is less than or equal to "benzene's valency -3". 1’ , r 2’ , and r 4’ When the number of defects falls within the above range, it tends to result in a reduction in film defects and the formation of lithography films with superior EUV and EB sensitivity.

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

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[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, and 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, there is a tendency to be able to form a lithography film that is more suitable, with fewer film defects and better EUV and EB sensitivity.

[0112] Furthermore, in order to further improve etching defects, the content of the compound represented by formula (B1) in the composition is preferably 4000 ppm by mass or more and 8000 ppm by mass or less. In order to have better long-term stability, the content of the compound represented by formula (B1) in the composition is preferably 1 ppm by mass or more and 3000 ppm by mass or less, and more preferably 2 ppm by mass or more and 30 ppm by mass or less.

[0113] [Method for producing the compound represented by formula (A1) and the compound represented by formula (B1)] Compounds (A1) and (B1) can be produced by any method that does not impair their effects. However, a production method including the step of introducing an iodine atom and a formyl group into a compound having a benzene ring is preferred. As the compound having a formyl group into a benzene ring, such as benzaldehyde, commercially available products may be used. Such compounds can also be obtained, for example, by oxidizing a compound having a hydroxyl group into a benzene ring, such as phenol, or by 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 I2 under acidic or alkaline conditions. Compounds (A1) and / or (B1) can be produced by this reaction. 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 a compound having a benzene ring, a functional group in which an iodine atom can be replaced by a substitution reaction, and further optionally R 1 The method includes an iodization step in which an iodine atom is introduced as a substitution reaction to a raw material containing the above. Another method for producing compound (A1) and / or (B1) is to use a compound having a benzene ring and, if necessary, R 1 The raw materials containing the above may include an iodization step in which iodine is introduced radically or as a cation or anion. Similarly, a method can be carried out in which an iodine atom is introduced as Z or Z' into compound (A1) or (B1), respectively.

[0114] (Iodination process) As an iodination step, methods such as introducing a halogen from an amino group by a Sandmeyer reaction or the like; reacting iodine chloride in an organic solvent (for example, Japanese Patent Publication No. 2012-180326, Japanese Patent Publication No. 2000-256231, Japanese Patent Publication No. 2010-159233, J. Chem. Soc. 636, 1943); or adding iodine dropwise to an alkaline aqueous solution of phenol under alkaline conditions in the presence of β-cyclodextrin (Japanese Patent Publication No. 63-101342, Japanese Patent Publication No. 2003-64012) can be appropriately selected.

[0115] The iodinating agent is not particularly limited, but examples 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 molars or more, more preferably 1.5 molars or more, and even more preferably 2.0 molars or more.

[0116] The iodization reaction can proceed by reacting at least an iodizing agent with the substrate, and the target compound can be obtained by using known iodization reaction conditions using methods described in non-patent literature such as Adv.Synth.Catal.2007,349,1159-1172, Organic Letters;Vol.6;(2004);p.2785-2788, "Organic Synthesis of Bromine and Iodine Compounds: Reagents and Synthesis Methods" (supervised by Hitomi Suzuki, authored by Manac Co., Ltd. Research Institute, Maruzen Publishing), and patents such as US5300506, US5434154, US2009 / 281114, EP1439164, and WO2006 / 101318. Examples of iodinating agents that can be used include, but are not limited to, iodine compounds, monoliths of iodide, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetran-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodide fluoride, tert-butyl hypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complexes, trifluoroacetyl hypoiodide, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenylphosphate-methyliodide, iodine-thallium(I) acetate, 1-chloro-2-iodoethane, and iodine-copper(II) acetate.

[0117] In the iodination reaction, one or more additives may be added to promote the reaction or suppress 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 materials such as zeolites. In the iodination process, the ratio of additives to iodinating agent is preferably 0.5 molar times, more preferably 0.5 molar times or more and 2.0 molar times or less, and even more preferably 0.5 molar times or more and 1.5 molar times or less.

[0118] In the iodination process, 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 preferable in terms of improving reaction efficiency and purity. Examples of iodination sources include the iodinating agents mentioned above. Examples of oxidizing agents include iodic acid, periodic acid, hydrogen peroxide, and other additives (such as hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, silver trifluoroacetate, and cerium(IV)ammonium nitrate (CAN)). Furthermore, for phenols having carboxylic acid groups or nitro groups, the iodination reaction can also be carried out using iodocation species formed by combining an iodine source such as iodine with a silver salt or fuming sulfuric acid. Furthermore, for other relatively inert aromatic compounds, the iodination reaction can be carried out by forming hypoiodic acid or iodocation species by combining an iodine source with an inorganic salt. Examples of inorganic salts include potassium peroxodisulfate, which can be used as appropriate. A method of introducing iodine to an aliphatic alcohol group by substitution reaction can also be used as appropriate. Suitable iodizing agents include, for example, hydrogen halides, phosphorus halides, sulfonyl halides (NaI / acetone combination), thionyl halides, trimethylsilane halides, Vilsmeyer's reagent, and the Abel reaction (triphenylphosphine combined with an iodine source).

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

[0120] The reaction temperature in the iodination step is not particularly limited and may be any temperature from the freezing point to 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 in 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 allow iodination to proceed more efficiently. In addition, the concentration of the iodinating agent in the reaction system can be controlled by using a reflux condenser equipped with a Dean-Stark or the like to control the concentration of the iodinating agent in the reaction solution.

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

[0122] (Protecting group introduction step) The introduction of the protecting group represented by A or A' in the preferred method for producing compound (A1) and / or (B1) can be introduced into a compound having a benzene ring by known methods. For example, methods can be appropriately selected from those described in Green's Protective Groups in Organic Synthesis (by Peter GM Wuts, WILEY), pp. 17-553.

[0123] In the protecting group introduction step, the ratio of the protecting group introducer to the substrate is not particularly limited, but is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and even more preferably 1.5 molar times or more. The reaction temperature in the protecting group introduction step is not particularly limited, but is generally suitable in the range of 0°C to 200°C, and from the viewpoint of yield, is preferably 10°C to 190°C, more preferably 25°C to 150°C, and even more preferably 50°C to 100°C. 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 process) In compounds (A1) and (B1), the formyl group and the hydroxyl group at Z can be obtained, for example, by introducing a carboxyl group or an ester group and then reducing it.

[0125] As a reduction method, known methods can be used, for example, a method using metal hydride complex compounds of sodium borohydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (SBMEA), and diisobutylaluminum hydride (DIBAL); a method using metal hydrides such as aluminum hydride; or a method using these reducing agents together with reducing aids such as aluminum chloride or ethanedithiol. The reducing ability of the reducing agent may be adjusted by modifying part of its structure with alkoxy groups or hydrocarbon groups, or by using it in combination with Lewis acids. 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 carried out at room temperature or under heated conditions, but it may also be carried out under cooling to adjust the reactivity, and is not particularly limited, but -20°C to 150°C is preferred, 0°C to 150°C is more preferred, and 20°C to 120°C is even more preferred. In the reduction step, the ratio of reducing agent to substrate is not particularly limited, but is preferably 0.5 molar times or more, more preferably 1.0 molar time or more, and even more preferably 1.5 molar times 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 ester groups to convert them to hydroxyl groups is not particularly limited, but examples 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 the reducing agent in combination with calcium chloride or lithium chloride. The solvent is not particularly limited, but examples include THF (tetrahydrofuran), DMSO, chloroform, and toluene, with toluene being preferred, and it is more preferable to use methanol in combination.

[0127] It is preferable to remove residual metal impurities from compounds (A1) and (B1) by further purification after obtaining them as crude products through the above reaction. In other words, it is preferable to avoid residual metal impurities from the viewpoint of preventing deterioration of the resin over time and storage stability, as well as from the viewpoint of process suitability and manufacturing yield due to defects when the resin is applied to semiconductor manufacturing processes. Metal impurities may originate from reaction aids in the manufacturing process of compounds (A1) and / or (B1), or from the reaction vessel or other manufacturing equipment used for manufacturing.

[0128] The residual amount (content) of the aforementioned metal impurities is preferably less than 1 ppm relative to the compound, 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 amount of metal is 1 ppm or more, there is a concern that it may cause material modification or deterioration over time due to interaction with other compounds. Furthermore, regarding alkali metals and alkalinity-type 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 resins for semiconductor processes using compounds (A1) and (B1). This raises concerns about defects and performance degradation due to residual metals in the semiconductor manufacturing process, as well as a decrease in properties due to the doping effect of metal elements on the substrate.

[0129] The purification method is not particularly limited, but methods such as those described in International Publication 2015 / 080240 or International Publication 2018 / 159707 can be used. Specifically, the purification method includes the steps of dissolving compound (A1) and / or (B1) in an organic solvent that is not arbitrarily miscible with water to obtain an organic phase, and then transferring the metal components contained in the organic phase, which contains compound (A1) and / or (B1) and the organic solvent, to the aqueous phase by contacting the organic phase with an acidic aqueous solution and performing an extraction treatment, and then separating the organic phase and the aqueous phase. The organic solvent that is not arbitrarily miscible with water is usually an organic solvent classified as a water-insoluble solvent. The organic solvent is not particularly limited, but an organic solvent that can be safely applied to semiconductor manufacturing processes is preferred. The amount of organic solvent used is usually 10% by mass relative to the compound used.

[0130] Specific examples of organic solvents used include those described in International Publication 2015 / 080240, for example. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), and ethyl acetate are preferred, with cyclohexanone and propylene glycol monomethyl ether acetate being more preferred.

[0131] The aforementioned acidic aqueous solution is appropriately selected from aqueous solutions of generally known organic and inorganic compounds dissolved in water. For example, those described in International Publication 2015 / 080240 can be cited. These acidic aqueous solutions can be used individually or in combination of two or more. Examples of acidic aqueous solutions include mineral acid aqueous solutions and organic acid aqueous solutions. Examples of mineral acid aqueous solutions include aqueous solutions containing one or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of organic acid aqueous solutions include aqueous solutions containing one or more 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 range of the acidic aqueous solution is approximately 0 to 5, and more preferably approximately 0 to 3.

[0132] Other purification methods include the method using filters described later; a method of dispersing and suspending an ion exchange resin in a container using an adsorbent ion exchange resin in a column system; and a method of distillation, which can be used as appropriate.

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

[0134] (purification method) • Filter purification process (liquid passage process) In the method for producing compound (A1) and / or (B1), purification may be performed, for example, by a filter purification step or a treatment step using an ion exchange resin. As the filter purification step, known methods such as those described in WO2022 / 009966 and WO2017 / 038968 can be used. As the ion exchange resin, known methods such as those described in WO2017 / 038964 can be used.

[0135] [Distillation Process] Another purification method involves distilling the compound itself. The distillation method is not particularly limited, but known methods such as atmospheric distillation, reduced-pressure distillation, molecular distillation, and steam distillation can be used.

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

[0137] Compounds (A1) and (B1) exhibit a sensitizing effect on lithography compositions containing them upon irradiation with radiation. Therefore, one embodiment of this invention may be a method for exhibiting a sensitizing effect on lithography compositions upon irradiation with radiation using compounds (A1) and (B1), and it is preferable to use two or more types of compounds (A1) and (B1). The reason for this is not limited, but it is thought that compounds (A1) and (B1) promote the absorption of radiation. This effect is particularly pronounced under extreme ultraviolet (EUV) irradiation. The sensitizing effect can take several forms, and when a photosensitive layer fabricated using a lithography composition is used as a resist film for lithography, it can be confirmed, for example, as follows: 1) Using a surface exposure method without a pattern, measure the film thickness obtained after exposure, optionally through a PEB process (a process of heat treatment after exposure) and optionally through a development process (a process of dissolving and removing the exposed or unexposed areas with a developer). 2) The exposure amount is changed, and the film thickness of the resulting film is measured. The exposure amount at which the film thickness changes rapidly is defined as the sensitivity in the surface exposure method. 3) If sensitivity is confirmed on the lower exposure side, it can be determined that there was a sensitizing effect. In addition, in a method of pattern formation by exposure, 1) the exposure amount is changed to form a pattern, and the exposure amount at which the specified line width is achieved after exposure is defined as the sensitivity. 2) If sensitivity is confirmed on the lower exposure side, it can be determined that there was a sensitizing effect. Furthermore, lithography compositions containing compounds (A1) and (B1) are useful for suppressing defects in resist patterns. In particular, in pattern evaluation under extreme ultraviolet (EUV) light, this can also be confirmed by the reduction of defects such as pitting and bridging. These defects are caused by fluctuations in optical exposure or exposure conditions that are substantially similar to defects due to low exposure. However, if the resist film has a sensitizing effect, the fluctuations and defects are avoided by enhanced absorption, and the defects are reduced. When using the composition of this embodiment in a lithography composition, the composition of this embodiment can be used directly as a component of the lithography composition.Alternatively, the compounds (A1) and (B1) can be processed into resins (substrate (A)) and additives (acid generator (C), crosslinking agent (G), acid diffusion inhibitor (E), other components (F), etc.) containing them as partial structures, and these resins and additives can be used as lithography compositions.

[0138] The lithography composition comprises compounds (A1) and (B1), and may optionally contain other components such as a substrate (A), solvent (S), acid generator (C), crosslinking agent (G), and acid diffusion control agent (E). Each component is described below.

[0139] [Compounds (A1) and (B1)] The lithography composition comprises compounds (A1) and (B1). Preferably, composition (A) contains two or more compounds (B1). The inclusion of two or more compounds (B1) tends to reduce etching defects, as shown in the examples described later. The reason for this reduction in etching defects is unclear, but for example, it is possible that the compatibility between compounds (A1) and (B1) in composition (A) improves, reducing fine defects in the resulting film. When two or more compounds (B1) are included, the structures of the repeating units may be identical or different.

[0140] [Base material (A)] In this embodiment, substrate (A) refers to a compound other than compounds (A1) and (B1) that can be used as a resist. Substrate (A) may be a resin. For example, substrate (A) refers to a substrate 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), and electron beam (EB) lithography (e.g., a substrate for lithography or a substrate for resists). Examples of 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 having metallic elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof. Among these, phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials having metallic elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof, are preferred from the viewpoint of the shape of the resist pattern obtained.

[0141] 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, from the viewpoint of reducing defects in the film formed using composition (A) and achieving a good pattern shape. The weight-average molecular weight can be the 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 in which compounds (A1) and (B1) are dissolved, and known solvents can be used as appropriate. Specific examples of 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; lactic acid esters; aliphatic carboxylic acid esters; other esters; aromatic hydrocarbons; ketones; amide 3:9; lactones, etc. Specific examples of these are disclosed in International Publication No. 2020 / 040161.

[0143] The solvent (S) used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), CHN (cyclohexanone), CPN (cyclopentanone), 2-heptanone, anisole, butyl acetate, 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 solid components and solvent (S) are not particularly limited, but it is preferable that the solid components make up 1 to 80% by mass and the solvent 20 to 99% by mass, more preferably 1 to 50% by mass and the solvent 50 to 99% by mass, even more preferably 2 to 40% by mass and the solvent 60 to 98% by mass, and particularly preferably 2 to 10% by mass and the solvent 90 to 98% by mass. The amount of solid components is defined as the total mass of the solid components (the sum of the solid components including the base material (A), compound (A1), compound (B1), acid generator (C), crosslinking agent (G), acid diffusion control agent (E), and other components (F) that are used as optional components, the same applies hereinafter).

[0145] [Acid Generator (C)] The composition (A) of this embodiment preferably contains one or more acid generators (C). An acid generator (C) is a material that generates acid directly or indirectly upon irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-rays, and ion beams. As an acid generator (C), for example, one described in International Publication No. 2013 / 024778 can be used. Two or more acid generators (C) can also be used in combination.

[0146] The amount of acid generator (C) used is preferably 0.001 to 49% by mass of the total mass of the solid components, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 5 to 25% by mass. 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), compound (A1), and compound (B1). The crosslinking agent (G) crosslinks the substrate (A) intramolecularly or intermolecularly in the presence of 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") that can crosslink the substrate (A). As a crosslinking agent (G) having such crosslinkable groups, for example, one described in International Publication No. 2013 / 024778 can be used. 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 of the total mass of the solid components, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass. 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 alkaline developer is improved, and it is possible to suppress a decrease in the residual film rate and the occurrence of swelling or meandering of the pattern. On the other hand, when the blending ratio is 50% by mass or less, it is possible to suppress a decrease in the heat resistance of the resist.

[0149] [Acid diffusion control agent (E)] The composition (A) of this embodiment may contain an acid diffusion control agent (E). The acid diffusion control agent (E) controls the diffusion of acid generated from the acid generator by radiation irradiation within the resist film, thereby preventing undesirable chemical reactions in unexposed areas. Using the acid diffusion control agent (E) tends to improve the storage stability of the composition (A) of this embodiment. Furthermore, using the acid diffusion control agent (E) can improve the resolution of the film formed using the composition (A) of this embodiment. In addition, using the acid diffusion control agent (E) tends to improve process stability by suppressing linewidth changes in the resist pattern due to variations in the pre-irradiation and post-irradiation storage times. Examples of acid diffusion control agents (E) include radiodegradable basic compounds as described in International Publication No. 2013 / 024778. Two or more acid diffusion control agents (E) can also be used in combination.

[0150] The amount of acid diffusion control agent (E) is preferably 0.001 to 49% by mass of the total mass of solid components, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass. When the amount of acid diffusion control agent (E) is within the above range, it tends to prevent deterioration of resolution, pattern shape, dimensional fidelity, etc. Furthermore, even if the settling time from electron beam irradiation to heating after radiation irradiation is long, it is possible to suppress deterioration of the shape of the upper layer of the pattern. Also, when the amount is 10% by mass or less, it tends to prevent deterioration of sensitivity, developability of unexposed areas, etc. Furthermore, by using such an acid diffusion control agent (E), the storage stability of the resist composition is improved, the resolution is improved, and changes in the line width of the resist pattern due to variations in the settling time before and after radiation irradiation can be suppressed, which tends to improve process stability.

[0151] [Other ingredients (F)] The composition (A) of this embodiment may contain one or more of the following additives as other components (F). (Dissolution accelerator) A dissolution accelerator increases the solubility of a solid component in the developer when its solubility is too low, thereby moderately increasing the dissolution rate of the compound during development. The dissolution accelerator is preferably one with a low molecular weight; for example, a low molecular weight phenolic compound can be used. Examples of low molecular weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. Two or more dissolution accelerators can also be used in combination.

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

[0153] (Soluble control agent) A dissolution control agent controls the solubility of solid components in the developer when their solubility is too high, thereby moderately reducing the dissolution rate during development. Preferably, such a dissolution control agent does not undergo chemical changes during processes such as resist film firing, radiation irradiation, and development.

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

[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 used is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass of the total mass of the solid component, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0156] (Surfactants) The surfactant improves the coatability, striation, and resist developability of composition (A) of this embodiment. The surfactant may be anionic, cationic, nonionic, or amphoteric. Nonionic surfactants are preferred. Nonionic surfactants have good affinity with the solvent used in the manufacture of 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 alkylphenyl 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 is adjusted as appropriate depending on the type of solid component used, but is preferably 0 to 49% by mass of the total mass of the solid component, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0157] (Organic carboxylic acids, or phosphorus oxoacids, or derivatives of said oxoacids) Organic carboxylic acids, or phosphorus oxoacids, or derivatives thereof (hereinafter also referred to as "acids or derivatives") have effects such as preventing sensitivity degradation, improving resist pattern shape, or improving storage stability. Examples of organic carboxylic acids include malonic acid, as described in Patent Document 1. Examples of phosphorus oxoacids or derivatives thereof include phosphonic acid or its ester derivatives, as described in Patent Document 1, with phosphonic acid being particularly preferred among these.

[0158] The aforementioned acid or derivative can be used alone or in combination of two or more. The amount of the acid or derivative is adjusted as appropriate depending on the type of compound used, but is preferably 0 to 49% by mass of the total mass of the solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass.

[0159] (Other additives) Furthermore, composition (A) of this embodiment may optionally contain additives other than those described above. Examples of such additives include dyes, pigments, and adhesive aids. For example, incorporating dyes or pigments is preferable because it makes the latent image of the exposed area visible and mitigates the effects of halation during exposure. Also, incorporating adhesive aids is preferable because it can improve adhesion to the substrate. Further examples of other additives include anti-halation agents, preservative stabilizers, defoamers, shape modifiers, and specifically 4-hydroxy-4'-methyl chalcone.

[0160] [Proportion of each component in the composition] In 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 the solid components is the sum of the solid components including the base material (A), compound (A1), compound (B1), acid generator (C), crosslinking agent (G), acid diffusion control agent (E), and other components (F) that are used as optional. The mass ratio of 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. When the mass ratio is within this range, high sensitivity and exposure variation in the depth direction tend to be suppressed. 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, and 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, there is a tendency to be able to form lithography films that have fewer defects in the film and are more suitable for EUV and EB sensitivity.

[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, and 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, there is a tendency to be able to form a lithography film that is more suitable, with fewer film defects and better EUV and EB sensitivity.

[0163] The content of the compound represented by formula (B1) in composition (A) is preferably 0.001 ppm by mass or more and 5000 ppm by mass or less, and more preferably 0.01 ppm by mass or more and 3000 ppm by mass or less. When the content of compound (B1) is within the above range, there is a tendency to be able to form a lithography film that is more suitable, with fewer film defects and better EUV and EB sensitivity.

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

[0165] In 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 control agent (E) / other components (F) is as follows, relative to the total solid content of composition (A) of this embodiment: Preferably, the values ​​are 1.5~99.0 / 0.2~96.4 / 0.001~49 / 0~49 / 0.001~49 / 0~49, More preferably, 5~98.5 / 0.5~89 / 1~40 / 0~40 / 0.01~10 / 0~5, More preferably, the values ​​are 15-97.5 / 1-69 / 3-30 / 0-30 / 0.01-5 / 0-1. Particularly preferred are 25-96.5 / 1.5-50 / 3-30 / 0-30 / 0.01-3 / 0.

[0166] The proportion of each component is selected from the range such that its total proportion equals 100% by mass. This particular composition tends to result in superior performance in terms of sensitivity, resolution, and developability. "Solid content" refers to the components excluding the solvent, and "total solid content" refers to the sum of the components constituting the composition, excluding the solvent, equaling 100% by mass.

[0167] The composition (A) of this embodiment is typically prepared by dissolving each component in a solvent to form a homogeneous solution, and then filtering it as needed, for example, through a filter with a pore size of about 0.2 μm.

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

[0169] Composition (A) exhibits a sensitizing effect under radiation irradiation. Furthermore, composition (A) exhibits an excellent sensitizing effect under EUV exposure. Therefore, the present invention also provides a method for increasing the sensitivity of a lithography composition under radiation irradiation or EUV exposure. As described above, it is preferable to use two or more compounds (B1) in this sensitizing method.

[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 metal species classified as transition metals such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, if the residual amount of metal is 1 ppm or more, there is a concern that it may cause material modification and degradation over time due to interaction with other compounds. Furthermore, if the residual amount of alkali metals and alkalinity-type metals such as Na, K, Ca, and Mg is 1 ppm or more, it may not be possible to sufficiently reduce the metal residue when producing resins for semiconductor processes using the compound, and there is a concern that it may cause defects or a decrease in yield due to performance degradation caused by residual metals in the semiconductor manufacturing process. In composition (A), it is preferable that the total content of Na, K, and Fe is within the above range. [Examples]

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

[0172] [Measurement method] [Nuclear magnetic resonance (NMR)] The structure of the compound was confirmed by NMR measurement using the "Avance500III spectrometer" (trade name, manufactured by Bruker) under the following conditions. [ 1 H-NMR measurement] Frequency: 500MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measurement temperature: 23℃ [ 13 C-NMR measurement] Frequency: 125MHz Solvent: CDCl3 or d6-DMSO Internal standard: Use the solvent used. Measurement temperature: 23℃

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

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

[0175] [ka]

[0176] In a 30L glass reaction vessel, 1300g (8.55mol) of vanillin (4-hydroxy-3-methoxybenzaldehyde) and 5.6L of methanol were charged, and nitrogen was blown into the reaction vessel at a flow rate of 200mL / min to start stirring. After confirming the dissolution of vanillin, 2.6L of deionized water and 635g (6mol) of sodium carbonate were charged, and the mixture was stirred at room temperature (22°C) for 3 hours. 2600g (10.3mol) of iodine was added in installments, and the mixture was stirred at room temperature (22°C) for 20 hours. Subsequently, 16.6% aqueous sodium sulfite solution was added until both the solution decolorized and the system became basic, and then 4.3L of water was added and the mixture was stirred for 1 hour. The precipitated solid was filtered using a suction filter, rinsed, slurry washed, and dried to obtain 1900g of a white solid.

[0177] The white solid was purified by column chromatography to obtain compound (5IV). Using a liquid chromatograph (Shimadzu Corporation Nexera®-i LC-2020C 3D), the purity of compound (5IV) was measured at a detection wavelength of 254 nm, confirming a purity of over 99.9%. Liquid chromatography-mass spectrometry (LC-MS) analysis revealed a molecular weight of 278. Furthermore, regarding the white solid... 1When H-NMR measurement was carried out, it was confirmed that it had the chemical structure of 4-hydroxy-5-iodo-3-methoxybenzaldehyde (Compound (5IV)). 1 The assignment of H-NMR is shown below. δ(ppm)(d6-DMSO): 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.9 (1H, Ph), 7.5 (1H, Ph), 3.8 (3H, -CH3)

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

[0179] [Chemical Formula]

[0180] A white solid was obtained in the same manner as in Synthesis Example 1, except that 1420 g of ethyl vanillin was used instead of 1300 g of vanillin.

[0181] The white solid was purified by column chromatography to obtain Compound (5IEV). As a result of measurement using a liquid chromatograph in the same manner as in Synthesis Example 1 above, it was confirmed that the purity of Compound (5IEV) was 99.9% or more. As a result of analysis by liquid chromatography-mass spectrometry (LC-MS), the molecular weight was 292. Also, regarding the white solid 1 When H-NMR measurement was carried out, it was confirmed that it had the chemical structure of 4-hydroxy-5-iodo-3-ethoxybenzaldehyde (Compound (5IEV)). 1 The assignment of H-NMR is shown below. δ(ppm)(d6-DMSO): 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.9 (1H, Ph), 7.5 (1H, Ph), 4.1 (2H, -CH2-), 1.4 (3H, -CH3)

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

[0183] [ka]

[0184] 150 g (1.2 mol) of 4-hydroxybenzaldehyde and 1 L of methanol (Kanto Chemical) were weighed into a 3 L three-necked flask equipped with a stirrer and a nitrogen flow valve. The flask was immersed in a water bath, the water bath temperature was set to 40°C, and the flask was heated while stirring under a nitrogen flow valve, and 200 mL of water was added. When the internal temperature reached 34°C, 309.4 g (3.7 mol) of sodium bicarbonate (NaHCO3) was added all at once.

[0185] When the internal temperature reached 38°C, 654.5 g (2.6 mol) of iodine (I2) was added in portions, taking care to avoid effervescence, and the mixture was stirred at 40°C for 3 hours. After that, the flask was cooled with water, and sodium sulfite aqueous solution (Na2SO3) was added dropwise until the solution turned yellowish-white to obtain the reaction mixture.

[0186] 3 L of water was placed in a container equipped with a stirrer, the reaction solution was poured in and stirred for 15 minutes to obtain precipitate 1. Precipitate 1 was filtered and washed with 500 mL of water to obtain filter product 1. Filter product 1 was placed in a container equipped with a stirrer, 1 L of water was added and stirred for 15 minutes to obtain precipitate 2. Precipitate 2 was filtered and washed with 300 mL of water to obtain filter 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 precipitate 3. Precipitate 3 was filtered and washed with 150 mL of methanol to obtain precipitate 4. Precipitate 4 was separated using column chromatography (packing material: spherical and neutral silica gel 60N (product name) manufactured by Kanto Chemical Co., Ltd.) by applying a gradient so that the ratio of ethyl acetate to hexane (ethyl acetate:hexane) as the developing solvent was 1:9 to 9:1, thereby obtaining compound (35DI4HBA), compound (3I4HBA), and compound (DM-3I4HBA) in a ratio of 1:0.9:0.5.

[0188] Analysis of each component by liquid chromatography-mass spectrometry (LC-MS) revealed that the molecular weights were 374 for compound (35DI4HBA), 248 for compound (3I4HBA), and 494 for compound (DM-3I4HBA). Furthermore, measurements of each component using liquid chromatography, in the same manner as in Synthesis Example 1 above, confirmed that the LC purity at 254 nm was 99.9% or higher for each component. Also, regarding each ingredient 1 ¹H-NMR measurements confirmed that the compounds (35DI4HBA), (3I4HBA), and (DM-3I4HBA) each possessed their respective chemical structures. 1 The assignment of the H-NMR spectrum is shown below.

[0189] ·Compound (35DI4HBA) δ(ppm)(d6-DMSO): 10.8(1H, -CHO), 9.8(1H, -OH), 8.0(2H, Ph) ·Compound (3I4HBA) δ(ppm)(d6-DMSO): 11.6(1H, -OH), 10.8(1H, -CHO), 6.7~8.0(3H, Ph) ·Compound (DM-3I4HBA) δ(ppm)(d6-DMSO): 11.0(2H, -CHO), 9.8(2H, -OH), 8.2~8.3(4H, Ph)

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

[0191] [Chemical Formula]

[0192] Compound (35DI2HBA) and 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] As a result of analyzing each component by liquid chromatography-mass spectrometry (LC-MS), the molecular weights were 374 for Compound (35DI2HBA) and 494 for Compound (DM-3I2HBA), respectively. Also, 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. Also, for each component 1 When 1H-NMR measurement was performed, it was confirmed that each had the chemical structure of Compound (35DI2HBA) and Compound (DM-3I2HBA). For each component 1 The assignment of 1H-NMR is shown below.

[0194] ·Compound (35DI2HBA) δ (ppm) (d6-DMSO): 21.4 (1H, -OH), 10.8 (1H, -CHO), 8.0 - 8.2 (2H, Ph) ·Compound (DM-3I2HBA) δ (ppm) (d6-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) Compounds (DM-5IV), (DM2-5IV), (DM3-5IV), (DM4-5IV), and (DM5-5IV) were synthesized according to the following procedure.

[0196] [ka]

[0197] In a 100L stainless steel reaction vessel connected to a reflux tubing, 871g of vanillin and 4900ml of methanol were charged, and the mixture was stirred at 220rpm for 1 hour under a nitrogen flow to dissolve the vanillin in methanol. While cooling the reaction vessel with ice, an aqueous sodium hydroxide solution, prepared by dissolving 757g of sodium hydroxide in 1260mL of pure water, was gradually added to the reaction vessel. Next, 3200g of iodine was divided into 10 parts and gradually added to the reaction vessel over 60 minutes. After that, the mixture was stirred for 8 hours while maintaining the internal temperature at 60°C using a water bath. Then, while stirring at 120rpm under ice cooling, 21L of 6mol / L hydrochloric acid solution was added dropwise over 1 hour, followed by a further 30 minutes of stirring. Subsequently, 2.3L of 20% by mass sodium sulfite solution was added while stirring, and then 3.5L of pure water was added to obtain a precipitate. The obtained precipitate was collected by filtration. The resulting solid filtrate was separated using column chromatography (packing material: 60N silica gel for column chromatography (spherical, neutral), particle size 100-200 μm (product name)) manufactured by Kanto Chemical Co., Ltd., by applying a gradient so that the ratio of ethyl acetate to hexane (ethyl acetate:hexane) was 1:9 to 9:1. This yielded 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] Analysis of each component by liquid chromatography-mass spectrometry (LC-MS) revealed that 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, measurements of each component using liquid chromatography, in the same manner as in Synthesis Example 1 above, confirmed that the LC purity at 254 nm was 99.9% or higher for each component. Also, regarding each ingredient 1 ¹H-NMR measurements confirmed that each compound possessed the chemical structures of compounds (DM-5IV), (DM2-5IV), (DM3-5IV), (DM4-5IV), and (DM5-5IV). 1 The assignment of the H-NMR spectrum is shown below.

[0199] ·Compound (DM-5IV) δ(ppm)(d6-DMSO): 11.0(2H, -CHO), 9.8(2H, -OH), 7.5(2H, Ph), 3.8(6H, -CH3) ·Compound (DM2-5IV) δ(ppm)(d6-DMSO): 20.0(1H, -OH), 10.8(1H, -CHO), 9.8(1H, -OH), 7.0~7.6(4H, Ph), 3.8(6H, -CH3) ·Compound (DM3-5IV δ(ppm)(d6-DMSO): 20.0(2H, -OH), 10.8(1H, -CHO), 9.8(1H, -OH), 7.0~7.6(6H, Ph), 3.8(9H, -CH3) ·Compound (DM4-5IV) δ(ppm)(d6-DMSO): 10.8(2H, -CHO), 8.7(1H, -OH), 6.9~7.8(4H, Ph), 3.8(6H, -CH3) ·Compound (DM5-5IV) δ(ppm)(d6-DMSO): 10.8(3H, -CHO), 8.7(1H, -OH), 6.9~7.8(6H, Ph), 3.8(9H, -CH3)

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

[0201] [ka]

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

[0203] Analysis of each component by liquid chromatography-mass spectrometry (LC-MS) revealed that 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, measurements of each component using liquid chromatography, in the same manner as in Synthesis Example 1 above, confirmed that the LC purity at 254 nm was 99.9% or higher for each component. Also, regarding each ingredient 1 ¹H-NMR measurements confirmed that each compound possessed the chemical structures of (DM-5IEV), (DM2-5IEV), (DM3-5IEV), (DM4-5IEV), and (DM5-5IEV). 1 The assignment of the H-NMR spectrum is shown below.

[0204] • Compound (DM-5IEV) δ (ppm) (d6-DMSO): 10.8 (2H, -CHO), 9.8 (2H, -OH), 7.9 (2H, Ph), 4.1 (4H, -CH2-), 1.4 (6H, -CH3) Compound (DM2-5IEV) δ (ppm) (d6-DMSO): 20.0 (1H, -OH), 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.1~7.4 (4H, Ph), 4.1 (4H, -CH2-), 1.4 (6H, -CH3) ·Compound (DM3-5IEV) δ (ppm) (d6-DMSO): 20.0 (2H, -OH), 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.0~7.6 (6H, Ph), 4.1 (6H, -CH2-), 1.4 (9H, -CH3) Compound (DM4-5IEV) δ (ppm) (d6-DMSO): 10.8 (2H, -CHO), 8.7 (1H, -OH), 6.9~7.8 (4H, Ph), 4.1 (4H, -CH2-), 1.4 (6H, -CH3) Compound (DM5-5IEV) δ (ppm) (d6-DMSO): 10.8 (3H, -CHO), 8.7 (1H, -OH), 6.9~7.8 (6H, Ph), 4.1 (6H, -CH2-), 1.4 (9H, -CH3)

[0205] [Synthesis of Compound B] [Synthetic Example 7] Compound (DM-3I4HBA), compound (DM2-3I4HBA), compound (DM3-3I4HBA), compound (DM4-3I4HBA), and compound (DM5-3I4HBA). The following compounds were synthesized: compound (DM-3I4HBA), compound (DM2-3I4HBA), compound (DM3-3I4HBA), compound (DM4-3I4HBA), and compound (DM5-3I4HBA).

[0206]

change

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

[0208] Analysis of each component by liquid chromatography-mass spectrometry (LC-MS) revealed that the molecular weights were 494 for compound (DM-3I4HBA), 494 for compound (DM2-3I4HBA), 740 for compound (DM3-3I4HBA), 494 for compound (DM4-3I4HBA), and 740 for compound (DM5-3I4HBA). Furthermore, measurements of each component using liquid chromatography, in the same manner as in Synthesis Example 1 above, confirmed that the LC purity at 254 nm was 99.9% or higher for each component. Also, regarding each ingredient 1 ¹H-NMR measurements confirmed that the compounds (DM-3I4HBA), (DM2-3I4HBA), (DM3-3I4HBA), (DM4-3I4HBA), and (DM5-3I4HBA) each possessed the following chemical structures. 1 The assignment of the H-NMR spectrum is shown below.

[0209] ·Compound (DM-3I4HBA) δ(ppm)(d6-DMSO): 11.0(2H, -CHO), 9.8(2H, -OH), 8.2~8.3(4H, Ph) ·Compound (DM2-3I4HBA) δ(ppm)(d6-DMSO): 21.4(1H, -OH), 11.6(1H, -OH), 11.0(1H, -CHO), 6.7~8.2(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)(d6-DMSO): 11.0(2H, -CHO), 9.8(1H, -OH), 7.0~8.2(5H, Ph) ·Compound (DM5-3I4HBA) δ (ppm) (d6-DMSO): 11.0 (3H, -CHO), 9.8 (1H, -OH), 7.0~8.2 (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) Compounds (DM-3I2HBA), (DM2-3I2HBA), (DM3-3I2HBA), (DM4-3I2HBA), and (DM5-3I2HBA) were synthesized according to the following procedure.

[0211] [ka]

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

[0213] Analysis of each component by liquid chromatography-mass spectrometry (LC-MS) revealed that the molecular weights were 494 for compound (DM-3I2HBA), 494 for compound (DM2-3I2HBA), 740 for compound (DM3-3I2HBA), 494 for compound (DM4-3I2HBA), and 740 for compound (DM5-3I2HBA). Furthermore, measurements of each component using liquid chromatography, in the same manner as in Synthesis Example 1 above, confirmed that the LC purity at 254 nm was 99.9% or higher for each component. Also, regarding each ingredient 1¹H-NMR measurements confirmed that each compound possessed the chemical structures of (DM-3I2HBA), (DM2-3I2HBA), (DM3-3I2HBA), (DM4-3I2HBA), and (DM5-3I2HBA). 1 The assignment of the H-NMR spectrum is shown below.

[0214] ·Compound (DM-3I2HBA) δ(ppm)(d6-DMSO): 18.1(2H, -OH), 11.0(2H, -CHO), 8.1(4H, Ph) ·Compound (DM2-3I2HBA) δ(ppm)(d6-DMSO): 12~17(2H, -OH), 11.0(1H, -CHO), 6.7~8.2(5H, Ph) ·Compound (DM3-3I2HBA) δ(ppm)(d6-DMSO): 12~17(3H, -OH), 11.0(1H, -CHO), 6.7~8.2(7H, Ph) ·Compound (DM4-3I2HBA) δ(ppm)(d6-DMSO): 16~17(1H, -OH), 11.0(2H, -CHO), 7.1~7.7(5H, Ph) ·Compound (DM5-3I2HBA) δ(ppm)(d6-DMSO): 16~17(1H, -OH), 11.0(3H, -CHO), 7.1~7.7(7H, Ph)

[0215] [Preparation of composition] [Examples 1-29 and Comparative Examples 1-5] The compounds obtained in Synthesis Examples 1 to 8 were mixed to obtain the compositions for Examples 1 to 29 and Comparative Examples 1 to 5, respectively, so as shown in Table 1. In Table 1, compound A1 is the compound represented by formula (A1), and compounds B1 to B3 are compounds represented by formula (B1). In Table 1, the values ​​for each component represent parts by mass. Components that are not included are indicated as "none" for the compound name and "-" for the parts by mass.

[0216] [Table 1]

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

[0218] [ka]

[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 off and dried under reduced pressure to obtain a white powdery polymer MAR represented by the above formula (MAR). The weight-average molecular weight (Mw) of this polymer was 11,500, and the dispersion (Mw / Mn) was 1.90. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) were determined using standard polystyrene as the standard substance by GPC (gel permeation chromatography). 13 ¹³C-NMR measurements revealed that the composition ratio (molar ratio) in the above formula (MAR) was a:b:c:d = 60:10:15:15. Note that the above formula (MAR) is a simplified representation to show the ratio of each constituent unit; however, the order of the constituent units is random, and it is not a block copolymer where each constituent unit forms an independent block. For units containing benzene, the molar ratio was determined based on the integral ratio of the carbon in the main chain directly bonded to the benzene ring. For methacrylate units (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate), the molar ratio was determined based on the integral ratio of the carbonyl carbon in the ester bond.

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

[0221] (base material) • MAR…The 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] [Table 2]

[0223] [evaluation] [Pattern evaluation (pattern formation) of electron beam (EB) resist patterns] Each of the lithography compositions obtained in Examples 30-60 and Comparative Examples 6-11 was rotationally 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 obtained resist film was irradiated with an electron beam using an EB lithography system (ELS-7500 (product name), manufactured by Elionix Co., Ltd.) with a 1:1 line-and-space setting at 50 nm intervals. After irradiation, each 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. Subsequently, the resist film was washed with ultrapure water for 30 seconds and dried to form a resist pattern.

[0224] (Evaluation of resist pattern shape) 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. For the resist pattern shape after development, patterns where the pattern width at a position 10% above the pattern height from the surface of the silicon wafer was less than +10% of the full width at half maximum (FWHM) were evaluated as "A", and patterns where the FWHM was +10% or more were evaluated as "C". (Resist pattern defect) Furthermore, regarding resist pattern defects after development, the number of spherical foreign objects was used as an indicator for a resist pattern with a length of 1 μm. (Evaluation Criteria) S: Number of spherical foreign objects = 0 A: 0 pieces < Number of spherical foreign objects ≤ 5 pieces C: 5 pieces < Number of spherical foreign objects (Electron beam lithography sensitivity) The minimum electron beam energy required to draw a shape without pattern distortion was defined as "electron beam lithography sensitivity." A value equal to or better than Comparative Example 11 was assigned an "A," while a value inferior to Comparative Example 11 was assigned a "C."

[0225] Table 3 shows the evaluation results for resist pattern shape, resist pattern defects, and electron beam lithography sensitivity.

[0226] [Table 3]

[0227] [EUV exposure sensitivity and etching defects] (EUV exposure sensitivity) Each of the lithography compositions obtained in Examples 30-60 and Comparative Examples 6-11 was rotationally coated onto a silicon wafer, and then baked at 110°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. Next, an extreme ultraviolet (EUV) exposure system (EUVES-7000 (product name), manufactured by Lithotech Japan Co., Ltd.) was used to measure 1 mJ / cm². 2 From 1 mJ / cm 2 80 mJ / cm² each 2 After increasing the exposure dose to a certain level using maskless shot exposure, the wafer was baked (PEB) at 110°C for 90 seconds, developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and obtained a wafer with 80 shot exposures on the wafer. For each shot exposure area obtained, the film thickness was measured using an optical interferometer (VM3200, (product name), manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and profile data of film thickness against exposure dose was obtained. The exposure value at which the slope of the film thickness variation with respect to exposure dose was largest was set to the sensitivity value (mJ / cm²). 2 This was calculated as an indicator of the EUV sensitivity of the resist.

[0228] (etching defect) Each of the lithography compositions obtained in Examples 30-60 and Comparative Examples 6-11 was coated onto an 8-inch silicon wafer with a 100 nm thick oxide film formed on the outermost layer, and baked at 110°C for 60 seconds to form a 100 nm thick photoresist layer. Next, using an extreme ultraviolet (EUV) lithography system (EUVES-7000 (product name), manufactured by Lithotech Japan Co., Ltd.), the entire wafer was shot-exposed with an exposure dose 10% less than the EUV sensitivity value obtained in the EUV sensitivity evaluation described above. The wafer was then baked (PEB) at 110°C for 90 seconds and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a wafer with 80 shots of exposure across the entire wafer surface.

[0229] The fabricated exposed wafers were etched using an etching system (Telius SCCM, (product name), manufactured by Tokyo Electron Ltd.) with CF4 / Ar gas until the oxide film was etched to a thickness of 50 nm. The wafers fabricated by etching were evaluated for defects using a defect inspection system (Surfscan SP5, (product name), manufactured by KLA), and the number of cone defects larger than 19 nm was used as an indicator 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 for EUV exposure sensitivity and etching defects.

[0231] [Table 4]

[0232] [Preparation of purified product of the composition according to Example 15] [Process 1: Purification with acid] 150 g of a 10% by mass solution (10%) of the composition according to Example 15 dissolved in propylene glycol monomethyl ether acetate (PGMEA) was placed in a 1000 mL four-necked flask (bottomless type), and heated to 80°C while stirring. Next, 37.5 g of aqueous oxalic acid solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This separated the oil phase and the aqueous phase, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes, and the aqueous phase was removed. After repeating this operation three times, residual water and PGMEA were concentrated and removed by reducing the pressure inside the flask to 200 hPa or less while heating to 80°C. Subsequently, an electronic material (EL) grade PGMEA (reagent manufactured by Kanto Chemical Co., Ltd.) was diluted and the concentration was adjusted to 10% by mass to obtain a PGMEA solution of the composition according to Example 15 with reduced metal content.

[0233] [Process 2: Acid-free processing] A PGMEA solution of the composition according to Example 15 was obtained by adjusting the concentration to 10% by mass using the same method as in Treatment 1, except that ultrapure water was used instead of an aqueous oxalic acid solution.

[0234] [evaluation] [Metal content] The sodium (Na), potassium (K), and iron (Fe) metal content (ppb) of 10% by mass PGMEA solutions of the composition according to Example 15 after Treatment 1 (hereinafter simply referred to as "the composition according to Example 15 after Treatment 1"), the composition according to Example 15 after Treatment 2 (hereinafter simply referred to as "the composition according to Example 15 after Treatment 2"), and the composition according to Example 15 without treatment (hereinafter simply referred to as "the composition according to the untreated Example 15") was measured by inductively coupled plasma mass spectrometry (ICP-MS). The measurement results for each are shown in Table 5.

[0235] [Table 5]

[0236] [Preparation of Lithography Compositions] [Examples 61 and 62, and Reference Example 1] The 10% by mass PGMEA solution of the composition according to Example 15 in Treatment 1, the 10% by mass PGMEA solution of the composition according to Example 15 in Treatment 2, and the 10% by mass PGMEA solution of the untreated composition according to Example 15 were each condensed and the PGMEA was removed by distillation to obtain the composition according to Example 15 in Treatment 1, the composition according to Example 15 in Treatment 2, and the untreated composition according to Example 15, respectively. Subsequently, the compositions from Example 15 of Treatment 1, Example 15 of Treatment 2, and the untreated Example 15 were mixed with a substrate, an acid generator, an acid diffusion inhibitor, and an organic solvent to obtain the lithography compositions for Examples 61 and 62 and Reference Example 1, respectively, so as shown in Table 6. In Table 6, the substrate, acid generator, acid diffusion inhibitor, and organic solvent are as described above.

[0237] [Table 6]

[0238] [evaluation] [EUV exposure sensitivity and etching defects] (EUV exposure sensitivity) In the same manner as the EUV exposure sensitivity evaluation method described above, the lithography compositions for Examples 61 and 62, and Reference Example 1, were evaluated for their respective sensitivity values ​​(mJ / cm²). 2 The following was calculated and used as an indicator of the EUV sensitivity of the resist:

[0239] (etching defect) In the same manner as the etching defect evaluation method described above, the lithography compositions according to Examples 61 and 62, and Reference Example 1, were evaluated for defects, and the number of cone defects of 19 nm or larger was determined as an indicator of etching defects.

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

[0241] [Table 7]

[0242] [Preparation of composition] [Examples 63-87 and Comparative Example 12] The compounds obtained in Synthesis Examples 1 and 5 were mixed to obtain the compositions for Examples 63 to 87 and Comparative Example 12, respectively, so as shown in Table 8. In Table 8, Compound A1 refers to the compound represented by formula (A1), and Compound B1 refers to the compound represented by formula (B1). In Table 8, the values ​​for each component represent parts by mass. Components that are not included are indicated as "none" for the compound name and "-" for the parts by mass. The organic solvents are as follows.

[0243] (organic solvent) • THF…Tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.)

[0244] [Table 8]

[0245] [evaluation] [Stability over time] (Condition 1) The time-dependent stability of the compositions obtained in Examples 63-87 and Comparative Example 12 was evaluated using a UV-Vis spectrophotometer. Specifically, the absorbance of the compositions at 450 nm, 550 nm, and 650 nm was measured using a UV-Vis spectrophotometer (Shimadzu Corporation UV-3600plus and MPC-603A (product name)), and their average value A0 was determined. Subsequently, the compositions were stored in a nitrogen-filled desiccator, and the desiccator was placed in a 40°C constant temperature bath and left for one month. After the period of storage, the absorbance of the compositions at 450 nm, 550 nm, and 650 nm was measured in the same manner as above, and their average value A1 was determined. The difference between the average value A0 and the average value A1, ΔA (ΔA = A), was calculated. 01-A1) was calculated, and the difference was used to evaluate the stability over time.

[0246] (Condition 2) Except for using a desiccator filled with air instead of a desiccator filled with nitrogen, the difference ΔA for each of the compositions obtained in Examples 63-87 and Comparative Example 12 was calculated in the same manner as in Condition 1 above, and the time-dependent stability was evaluated using this difference.

[0247] Table 9 shows the evaluation results for the long-term stability under conditions 1 and 2.

[0248] [Table 9]

[0249] [Preparation of composition] [Examples 88-105] The compounds obtained in Synthesis Examples 1 to 8 were mixed to obtain the compositions for Examples 88 to 105, respectively, so as shown in Table 10. In Table 10, Examples 1, 2, 4, 10, 11, 13, 15, 16, 18, 20, 21, 23, 25, 26, 28, and Comparative Examples 1 to 5 are compositions obtained in the above examples or comparative examples, respectively. For these compositions, please refer to Table 1. In Table 10, compound A1 is the compound represented by formula (A1), and compound B1 is the compound represented by formula (B1). In Table 10, the values ​​for each component represent parts by mass. For components that are not included, the compound name is indicated as "none" and the parts by mass is indicated as "-".

[0250] [Table 10]

[0251] [Preparation of Lithography Compositions] [Examples 106-123] Lithography compositions for Examples 106-123 were obtained by mixing the base material, the compositions obtained in Examples 88-105, the acid generator, the acid diffusion inhibitor, and the organic solvent 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, 57, and Comparative Examples 6-11 are lithography compositions obtained in the above examples or comparative examples, respectively. Table 2 may also be referred to for these lithography compositions. In Table 11, the values ​​for each component represent parts by mass. Components that are not included are indicated as "none" in the composition name and as "-" in the parts by mass. In Table 11, the base material, acid generator, acid diffusion inhibitor, and organic solvent are as follows.

[0252] (base material) • MAR…The 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] [Table 11]

[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, 106-123, and Comparative Examples 6-11 was rotationally 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 obtained resist film was irradiated with an electron beam using an EB lithography system (ELS-7500 (product name), manufactured by Elionix Co., Ltd.) with a 1:1 line-and-space setting at 50 nm intervals. After irradiation, each 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. Subsequently, the resist film was washed with ultrapure water for 30 seconds and dried to form a resist pattern.

[0255] (Evaluation of resist pattern shape) 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. For the resist pattern shape after development, patterns where the pattern width at a position 10% above the pattern height from the surface of the silicon wafer was less than +10% of the full width at half maximum (FWHM) were evaluated as "A", and patterns where the FWHM was +10% or more were evaluated as "C". (Resist pattern defect) Furthermore, regarding resist pattern defects after development, the number of spherical foreign objects was used as an indicator for a resist pattern with a length of 1 μm. (Evaluation Criteria) S: Number of spherical foreign objects = 0 A: 0 pieces < Number of spherical foreign objects ≤ 5 pieces C: 5 pieces < Number of spherical foreign objects (Electron beam lithography sensitivity) The minimum electron beam energy required to draw a shape without pattern distortion was defined as "electron beam lithography sensitivity" and evaluated according to the following criteria. (Evaluation Criteria) SS: Equivalent to or better than Example 30. S: Inferior to Example 30, but equal to or better than Example 44. A': It is inferior to Example 44, but is equal to or better than Comparative Example 7. B: It is inferior to Comparative Example 7, but is equal to or better than Comparative Example 11. C: Inferior to Comparative Example 11

[0256] Table 12 shows the evaluation results for resist pattern shape, resist pattern defects, and electron beam lithography sensitivity.

[0257] [Table 12]

[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, 106-123, and Comparative Examples 6-11 were 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 / cm²) is determined in the same manner as the EUV exposure sensitivity evaluation method described above. 2 The following was calculated and used as an indicator of the EUV sensitivity of the resist:

[0259] (etching defect) For each lithography composition after storage, defect evaluation was performed in the same manner as the etching defect evaluation method described above, and the number of cone defects of 19 nm or larger was determined as an indicator of etching defects.

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

[0261] [Table 13]

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

[0263] According to the present invention, it is possible to provide a composition capable of forming lithography films with excellent EUV and EB sensitivity. For this reason, the composition of the present invention can be suitably used in lithography technology.

Claims

1. One or more compounds selected from the group consisting of compounds represented by the following formula (A6) and compounds represented by the following formula (A7), A composition comprising a compound represented by the following formula (B1). 【Chemistry 1】 【Chemistry 2】 (In formula (B1), R' independently represents a non-functional organic group, R 1 Each of the following independently represents a monovalent functional group having 0 to 30 carbon atoms, which may be the same or different, excluding an iodine atom or a hydroxyl group, and which does not contain polymerizable unsaturated bonds; each of the following independently represents a group having a protecting group; each of the following independently represents an iodine atom or a hydroxyl group; each of the following independently represents a single bond, a carbonyl group, or a divalent oxygen atom; n 1 represents an integer from 1 to 4, and r 1’ ~r 3’ Each of these independently represents an integer from 0 to 3, and r 4’ Each of these independently represents an integer from 1 to 4. However, formula (B1) has at least one formyl group. 1’ ~r 4’ The sum of these values ​​represents an integer between 1 and 4.

2. The compound represented by formula (B1) includes one or more compounds selected from the group consisting of the compound represented by the following formula (B2), the compound represented by the following formula (B3), and the compound represented by the following formula (B4). The composition according to claim 1. 【Transformation 3】 (In formula (B2), R', R 1 ', Z', and n 1 are defined the same as in the above formula (B1). r 1’ and r 2’ each independently represent an integer from 0 to 2, and r 4’ each independently represent an integer from 1 to 3. However, the sum of r 1’ , r 2’ , and r 4’ represents an integer from 1 to 3.). 【Chemistry 4】 (In formula (B3), R', R 1 ', Z', and n 1 r is defined in the same way as in formula (B1) above. 1’ and r 2’ Each of these independently represents an integer from 0 to 3, and r 4’ Each of these independently represents an integer from 1 to 4. However, r 1’ ,r 2’ , and r 4’ The sum of these values ​​represents an integer between 1 and 4. 【Transformation 5】 (In formula (B4), R', R 1 ', Z', and n 1 r is defined in the same way as in formula (B1) above. 1’ and r 2’ Each of these independently represents an integer between 0 and 2, and r 4’ Each of these independently represents an integer from 1 to 3. However, r 1’ ,r 2’ , and r 4’ The sum of these values ​​represents an integer between 1 and 3.

3. 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. The composition according to claim 1.

4. The composition according to claim 1, which exhibits a sensitizing effect upon radiation irradiation.

5. The composition according to claim 1, wherein the content of metal impurities is less than 1 ppm.

6. The composition according to claim 1, for use in lithography.

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