Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
  • C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
  • C07C47/565—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups all hydroxy groups bound to the ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
  • C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
  • C07C47/57—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups polycyclic
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
  • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/86—Ketones containing a keto group bound to a six-membered aromatic ring containing —CHO groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

• miniaturizing pixels are to shorten the wavelength of the exposure light source.
• ultraviolet light such as g-line and i-line
• far-ultraviolet exposure using KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) is now becoming the norm in mass production, and extreme ultraviolet (EUV) lithography (13.5 nm) is also being introduced.
• Electron beams (EB) are also used to form fine patterns.
• lithography resist materials have been polymeric materials capable of forming amorphous films.
• examples include polymeric materials such as polymethyl methacrylate, and polyhydroxystyrene or polyalkyl methacrylate with acid-dissociable groups (see, for example, Non-Patent Document 1 below).
• the present invention was made in consideration of these issues, and aims to provide a composition that can form a lithography film with excellent EUV and EB sensitivity.
• composition containing a specific compound represented by formula (1) and a specific compound represented by formula (2) can form a lithography film with excellent EUV and EB sensitivity, leading to the completion of the present invention.
• a composition comprising a compound represented by the following formula (A1) and a compound represented by the following formula (B1):
• each R independently represents an organic group that is not a functional group; each R independently represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups; each A independently represents a group having a protecting group; each Z independently represents an iodine atom or a hydroxy group; each r to r independently represents an integer of 0 to 3; and each r independently represents an integer of 1 to 4, with the proviso that the sum of r to r represents an integer of 1 to 4.
• each R' independently represents an organic group that is not a functional group; each R1 ' independently represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups; each A' independently represents a group having a protecting group; each Z' independently represents an iodine atom or a hydroxy group; each X independently represents a single bond, a carbonyl group, or a divalent oxygen atom; n1 represents an integer of 1 to 4; each r1 ' to r3 ' independently represent an integer of 0 to 3; and each r4 ' independently represent an integer of 1 to 4, provided that formula (B1) has at least one formyl group; the sum of r1' to r4 ' represents an integer of 1 to 4.
• R, R 1 and Z are defined the same as in formula (A1).
• r 1 and r 2 each independently represent an integer of 0 to 2
• r 4 each independently represent an integer of 1 to 3, provided that the sum of r 1 , r 2 and r 4 represents an integer of 1 to 3.
• R', R 1 ', Z', and n 1 are defined the same as in formula (B1).
• r 1 ' and r 2 ' each independently represent an integer of 0 to 2
• r 4 ' each independently represent an integer of 1 to 3, with the proviso that the sum of r 1 ' , r 2 ' , and r 4 ' represents an integer of 1 to 3.
• R', R 1 ', Z', and n 1 are defined the same as in formula (B1).
• r 1' and r 2' each independently represent an integer of 0 to 3
• r 4' each independently represent an integer of 1 to 4, provided that the sum of r 1' , r 2' , and r 4' represents an integer of 1 to 4.
• R', R 1 ', Z', and n 1 are defined the same as in formula (B1).
• r 1' and r 2' each independently represent an integer of 0 to 2
• r 4' each independently represent an integer of 1 to 3, with the proviso that the sum of r 1' , r 2' , and r 4' represents an integer of 1 to 3.
• composition according to [2], wherein the compound represented by formula (A2) includes one or more compounds selected from the group consisting of compounds represented by the following formula (A3), compounds represented by the following formula (A4), and compounds represented by the following formula (A5).
• composition according to [2] or [3], wherein the compound represented by formula (A2) includes one or more compounds selected from the group consisting of compounds represented by formula (A6), compounds represented by formula (A7), compounds represented by formula (A8), compounds represented by formula (A9), and compounds represented by formula (A10).
• composition according to [4], wherein the compound represented by formula (A2) includes one or more compounds selected from the group consisting of compounds represented by formula (A6) and compounds represented by formula (A7).
• the present invention provides a composition capable of forming a lithography film with excellent EUV and EB sensitivity.
• the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment.
• "X to Y" includes the extreme values X and Y.
• composition contains a compound represented by the following formula (A1) (hereinafter also simply referred to as “compound (A1)”) and a compound represented by the following formula (B1) (hereinafter also simply referred to as “compound (B1)”).
• each R independently represents an organic group that is not a functional group, each R independently represents a monovalent functional group that may be the same or different and has 0 to 30 carbon atoms and does not contain a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups, each A independently represents a group having a protecting group, each Z independently represents an iodine atom or a hydroxy group, each r to r independently represents an integer of 0 to 3, and each r independently represents an integer of 1 to 4 , provided that the sum of r to r represents an integer of 1 to 4.
• each R' independently represents an organic group that is not a functional group
• each R 1 ' independently represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups
• each A' independently represents a group having a protecting group
• each Z' independently represents an iodine atom or a hydroxy group
• each X independently represents a single bond, a carbonyl group, or a divalent oxygen atom
• n 1 independently represents an integer of 1 to 4
• r 1' to r 3' independently represent an integer of 0 to 3
• each r 4' independently represent an integer of 1 to 4.
• formula (B1) has at least one formyl group. The sum of r 1' to r 4' is an integer of 1 to 4.
• the composition When the composition has such a structure, it becomes possible for the composition to form a lithography film with excellent EUV and EB sensitivity. While the reason for this is unclear, the inventors speculate as follows. However, the reason is not limited to this.
• the compound (A1) and the compound (B1) contain an iodine atom, and therefore the composition has a very high absorption rate of radiation such as EUV, and can exhibit a sensitizing effect when irradiated with radiation. Furthermore, compound (A1) and compound (B1) also contain a formyl group. When a compound contains a formyl group, the compound is stabilized in the composition due to reaction between the formyl group and the substrate (resin) or condensation between formyl groups. A composition containing such a compound can more stably form a film for lithography, such as a resist film, and therefore facilitates film formation.
• compound (A1) and compound (B1) contain a benzene ring and have a high content of aromatic rings.
• the heat resistance of the composition is relatively high, and the composition is less susceptible to heat damage even in semiconductor manufacturing processes that include a relatively large number of heating steps.
• the compounds (A1) and (B1) have very similar structures, while the compound (B1) is bulkier than the compound (A1). Therefore, by using the compounds (A1) and (B1), the crystallinity of the compound (A1) and the crystallinity of the compound (B1) can be appropriately inhibited in the composition. Therefore, the dissolution stability in organic solvents is increased, making film formation easier. For this reason, it is presumed that the composition of this embodiment can reduce defects in the film and suitably form a film for lithography that has excellent sensitivity to radiation such as EUV.
• the composition containing such a compound has higher dissolution stability. It is believed that such a composition can effectively suppress the generation of fine particles, which tends to further reduce film defects and more favorably form a film for lithography that has excellent EUV and EB sensitivity.
• composition contains a compound represented by the above formula (A1).
• R represents an organic group that is not a functional group, such as an alkyl group having 1 to 30 carbon atoms.
• alkyl groups having 1 to 30 carbon atoms include linear and branched alkyl groups.
• alkyl groups include methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, sec-hexyl, tert-hexyl, n-heptyl, n-octyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpentan-3-yl, and n-nonyl.
• the alkyl group is a methyl group, an ethyl group, or a propyl group (including isomers; the same applies hereinafter).
• compound (A1) contains such an alkyl group, film defects tend to be reduced, and a film for lithography with superior EUV and EB sensitivity tends to be more suitable.
• R1 represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups. Examples of polymerizable unsaturated bonds include ethylenic double bonds and triple bonds.
• compound (A1) contains R1 , film defects tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity tends to be more suitably formed.
• R1 is a functional group, not an alkyl group.
• R1 include an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a halogen atom other than an iodine atom, a nitro group, an amino group, a thiol group, and a cyano group.
• substituted means that one or more hydrogen atoms in the functional group are substituted with a substituent.
• substituted include a halogen atom, a hydroxy group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an acyl group having 1 to 30 carbon atoms (preferably
• These groups may form a ring structure within a substituent, a group having a substituent, or together with another R 1.
• Preferred examples of the group that may form a ring structure include a glycidyl group, a cyclic acetal group, and a group in which two adjacent hydroxyl groups have an acetal protecting group structure.
• R1 is preferably an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group.
• R1 is an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or a hydroxyalkyl group having 1 to 30 carbon atoms.
• alkoxy groups having 1 to 30 carbon atoms More preferred are alkoxy groups having 1 to 30 carbon atoms, aldehyde groups having 1 to 30 carbon atoms, carboxy groups having 1 to 30 carbon atoms, carboxylic acid ester groups having 2 to 10 carbon atoms, and alkoxyalkyl groups having 2 to 30 carbon atoms, and even more preferred are alkoxy groups having 1 to 30 carbon atoms and aldehyde groups having 1 to 30 carbon atoms, and even more preferred are alkoxy groups having 1 to 30 carbon atoms.
• R 1 contains such a group, there is a tendency that defects in the film are further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.
• alkoxy groups having 1 to 30 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-hexanoxy, and 2-methylpropoxy.
• the alkoxy group may be linear, branched, or cyclic. Of these, preferred alkoxy groups are methoxy and ethoxy.
• Examples of the aldehyde group having 1 to 30 carbon atoms include a formyl group (*-CHO) and a group represented by *-R 2 -CHO. In this specification, the "*" in the group indicates the bonding site.
• R 2 include linear or branched alkyl groups having a total of 1 to 20 carbon atoms. For the alkyl group, see above. The alkyl group may have a substituent. For the substituent, see above. Of these, the aldehyde group is preferably a formyl group. When R 1 contains such a group, there is a tendency that defects in the film are further reduced and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.
• carboxyl groups having 1 to 30 carbon atoms examples include acetate groups, propionate groups, and butyrate groups.
• Examples of carboxylic acid ester groups having 2 to 10 carbon atoms include methyl ester groups, ethyl ester groups, n-propyl ester groups, isopropyl ester groups, n-butyl ester groups, tert-butyl ester groups, octyl ester groups, 2-ethylhexyl ester groups, dodecyl ester groups, octadecyl ester groups, and docosyl ester groups.
• R 2 is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms.
• the alkyl group may refer to the above.
• Examples of the aryl group include a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthryl group.
• the alkyl group or the aryl group may have a substituent. Examples of the substituent include an alkoxy group. Therefore, in one embodiment, R 2 of the -OR 2 can be -CH 2 -OC 2 H 5 , for example.
• Halogen atoms other than iodine atoms include, for example, fluorine atoms, chlorine atoms, and bromine atoms.
• I represents an iodine atom.
• A represents a group having a protecting group.
• a protecting group refers to a group that dissociates under specific conditions, and is also referred to as a dissociable group.
• the protecting group is preferably an acid-dissociable group that dissociates in the presence of an acid.
• Preferred examples of such groups include a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group.
• A becomes a functional group by removing the protecting group, and is therefore a type of R1 .
• the group having a protecting group is preferably a group in which a hydroxyl group or a carboxyl group is protected with an acid-dissociable group.
• groups include groups represented by *-O-R a -O-R b .
• R a is a linear or branched alkylene group having 1 to 3 carbon atoms.
• R b is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group that forms a ring together with the adjacent oxygen atom.
• alkylene groups include a methylene group, an ethylene group, and a propylene group.
• alkyl groups include those described above.
• Examples of cyclic alkyl groups include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.
• Z represents an iodine atom or a hydroxy group. It is preferable that formula (A1) contains both an iodine atom and a hydroxy group as Z, as this tends to reduce film defects, improve EUV and EB sensitivity, and more suitably form a film for lithography.
• R, R 1 , A, and Z are bonded at any bondable position.
• groups other than the iodine atom, formyl group, R, R 1 , A, and Z are hydrogen atoms.
• Each r 1 independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• Each r 2 independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1.
• Each r 3 independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• Each r 4 independently represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2.
• the sum of r 1 to r 4 is an integer of 1 to 4 and is equal to or less than "the valence of benzene minus 2".
• the compound represented by formula (A1) preferably contains a compound represented by the following formula (A2) (hereinafter also simply referred to as "compound (A2)").
• A2) a compound represented by the following formula (A2)
• the composition contains compound (A2) as compound (A1), there is a tendency that defects in the film are further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.
• R, R 1 , and Z are defined as in formula (A1).
• r 1 and r 2 each independently represent an integer of 0 to 2
• r 4 each independently represent an integer of 1 to 3, provided that the sum of r 1 , r 2 , and r 4 represents an integer of 1 to 3.
• R, R 1 , and Z are bonded at any bondable position.
• at least one hydrogen atom is bonded, but groups other than the iodine atom, formyl group, R, R 1 , and Z are hydrogen atoms.
• Each r 1 independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
• Each r 2 independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1.
• Each r 4 independently represents an integer of 1 to 3, preferably 1 or 2, and more preferably 2.
• r 1 , r 2 , and r 4 is an integer of 1 to 3 and is equal to or less than "the valence of benzene minus 3."
• r 1 , r 2 , and r 4 are within the above ranges, there is a tendency that defects in the film are further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity can be more suitably formed.
• the compound represented by formula (A2) contains one or more compounds selected from the group consisting of a compound represented by formula (A3) below (hereinafter also referred to simply as “compound (A3)”), a compound represented by formula (A4) below (hereinafter also referred to simply as “compound (A4)”), and a compound represented by formula (A5) below (hereinafter also referred to simply as “compound (A5)”).
• composition contains one or more compounds selected from the group consisting of compound (A3), compound (A4), and compound (A5) as compound (A1) or (A2), film defects are further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be more suitably formed.
• groups other than iodine atoms, formyl groups, methoxy groups, and hydroxy groups are hydrogen atoms.
• the iodine atom is bonded to any available position.
• p represents an integer of 1 to 3. Because this tends to further reduce film defects and more favorably form a film for lithography that has even better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.
• p represents an integer of 1 to 3. Because this tends to further reduce film defects and more favorably form a film for lithography that has even better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.
• p represents an integer of 1 to 4. Because this tends to further reduce film defects and more favorably form a film for lithography that has even better EUV and EB sensitivity, p is preferably an integer of 1 to 3, and more preferably 1 or 2.
• the compound represented by formula (A2) includes one or more compounds selected from the group consisting of a compound represented by the following formula (A3') (hereinafter also simply referred to as “compound (A3')”) and a compound represented by the following formula (A4') (hereinafter also simply referred to as "compound (A4')").
• the composition includes one or more compounds selected from the group consisting of compound (A3') and compound (A4') as compound (A1) or (A2), film defects are further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be further preferably formed.
• groups other than iodine atoms, formyl groups, methoxy groups, and hydroxy groups are hydrogen atoms.
• the iodine atom is bonded to any available position.
• p represents an integer of 1 to 3. Because this tends to further reduce film defects and more favorably form a film for lithography that has better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.
• p represents an integer of 1 to 3. Because this tends to further reduce film defects and more favorably form a film for lithography that has better EUV and EB sensitivity, p is preferably 1 or 2, and more preferably 1.
• the compound represented by formula (A2) includes one or more compounds selected from the group consisting of a compound represented by formula (A6) below (hereinafter also simply referred to as “compound (A6)”), a compound represented by formula (A7) below (hereinafter also simply referred to as “compound (A7)”), a compound represented by formula (A8) below (hereinafter also simply referred to as “compound (A8)”), a compound represented by formula (A9) below (hereinafter also simply referred to as “compound (A9)”), and a compound represented by formula (A10) below (hereinafter also simply referred to as “compound (A10)”), and it is even more preferable that the compound represented by formula (A2) includes one or more compounds selected from the group consisting of compound (A6) and compound (A7).
• composition contains, as compound (A1) or (A2), one or more selected from the group consisting of compound (A6), compound (A7), compound (A8), compound (A9), and compound (A10), defects in the film tend to be further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be even more suitably formed.
• the composition contains, as compound (A1) or (A2), one or more selected from the group consisting of compound (A6) and compound (A7), defects in the film tend to be even further reduced, and a film for lithography having even more excellent EUV and EB sensitivity tends to be even more suitably formed.
• 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.
• content of compound (A1) is within the above range, film defects tend to be further reduced, and a film for lithography with better EUV and EB sensitivity tends to be more suitably formed.
• the composition contains a compound represented by the above formula (B1).
• R' represents an organic group that is not a functional group.
• the organic group is preferably a methyl group, an ethyl group, or a propyl group (including isomers; the same applies hereinafter).
• compound (B1) contains such an alkyl group as the organic group, film defects tend to be further reduced, and a film for lithography that is superior in EUV and EB sensitivity tends to be more suitably formed.
• R 1 ' represents a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, excluding iodine atoms and hydroxy groups.
• R 1 ' may refer to R 1 in formula (A1) above.
• R 1 ' is preferably an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group.
• it is an alkoxy group having 1 to 30 carbon atoms, an aldehyde group having 1 to 30 carbon atoms, a carboxy group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, or a hydroxyalkyl group having 1 to 30 carbon atoms.
• alkoxy groups having 1 to 30 carbon atoms More preferred are alkoxy groups having 1 to 30 carbon atoms, aldehyde groups having 1 to 30 carbon atoms, carboxy groups having 1 to 30 carbon atoms, carboxylic acid ester groups having 2 to 10 carbon atoms, and alkoxyalkyl groups having 2 to 30 carbon atoms, and even more preferred are alkoxy groups having 1 to 30 carbon atoms, and aldehyde groups having 1 to 30 carbon atoms.
• R 1 ' contains such a group, there is a tendency that defects in the film are further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.
• the alkoxy group having 1 to 30 carbon atoms is preferably a methoxy group or an ethoxy group.
• R 1 ' contains such a group, defects in the film tend to be further reduced, and a film for lithography having superior EUV and EB sensitivity can be more suitably formed.
• the aldehyde group having 1 to 30 carbon atoms is preferably a formyl group.
• R 1 ' contains such a group, defects in the film tend to be further reduced, and a film for lithography that is more excellent in EUV and EB sensitivity tends to be more suitably formed.
• A' represents a group having a protecting group.
• A' may refer to A in formula (A1) above.
• the group having a protecting group is preferably a group in which a hydroxy group or a carboxyl group is protected with an acid-dissociable group.
• a protecting group in formula (A1) above.
• Z' represents an iodine atom or a hydroxy group. It is preferable that formula (B1) contains both an iodine atom and a hydroxy group as Z', as this tends to reduce film defects, improve EUV and EB sensitivity, and more suitably form a film for lithography.
• X represents a single bond, a carbonyl group, or a divalent oxygen atom.
• single bond means that the repeating units are bonded by a single bond.
• divalent oxygen atom means an ether bond represented by "*-O-*”.
• R', R 1 ', A', Z', and X are bonded at any available position.
• groups other than the iodine atom, formyl group, R', R 1 ', A', Z', and X are hydrogen atoms.
• n1 represents an integer of 1 to 4.
• n1 is preferably an integer of 1 to 3, and more preferably 1 or 2.
• n1 which is the number of repeating units of compound (B1), is within the above range, defects in the film tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.
• Each r 1' independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• Each r 2' independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1.
• Each r 3' independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• Each r 4' independently represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2.
• the sum of r 1' to r 4' is an integer of 1 to 4 and is equal to or less than the valence of benzene minus 2.
• Formula (B1) contains at least one formyl group. At least one formyl group is bonded to any available position in formula (B1).
• the number of formyl groups is preferably an integer from 1 to 5, more preferably an integer from 1 to 4, and even more preferably an integer from 1 to 3.
• the number of formyl groups in compound (B1) is within the above range, film defects tend to be further reduced, and a film for lithography with better EUV and EB sensitivity tends to be more suitable for formation.
• the compound represented by formula (B1) preferably includes one or more compounds selected from the group consisting of a compound represented by formula (B2) below (hereinafter also referred to simply as “compound (B2)”), a compound represented by formula (B3) below (hereinafter also referred to simply as “compound (B3)”), and a compound represented by formula (B4) below (hereinafter also referred to simply as “compound (B4)”).
• compound (B2) a compound represented by formula (B3) below
• compound (B4) hereinafter also referred to simply as “compound (B4)”
• the composition includes one or more compounds selected from the group consisting of compound (B2), compound (B3), and compound (B4) as compound (B1), film defects tend to be further reduced, and a film for lithography having excellent EUV and EB sensitivity can be more suitably formed.
• groups other than iodine atoms, formyl groups, R', R 1 ', and Z' are hydrogen atoms.
• the formyl group is bonded to any available position.
• R', R 1 ', Z', and n 1 are defined the same as in formula (B1).
• r 1' and r 2' each independently represent an integer of 0 to 2
• r 4' each independently represent an integer of 1 to 3, provided that the sum of r 1' , r 2' , and r 4' represents an integer of 1 to 3.
• R', R 1 ', and Z' are bonded at any available position.
• one hydrogen atom is bonded, but groups other than the iodine atom, formyl group, R', R 1 ', and Z' are hydrogen atoms.
• n 1 represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
• Each r 1' independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
• Each r 2' independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1.
• Each r 4' independently represents an integer of 1 to 3, preferably 1 or 2, and more preferably 2.
• r 1' , r 2' , and r 4' is an integer of 1 to 3 and is equal to or less than "the valence of benzene minus 3".
• n 1 , r 1' , r 2' , and r 4' are within the above ranges, there is a tendency for the number of film defects to be further reduced, and for a film for lithography that has better EUV and EB sensitivity to be more suitably formed.
• R', R1 ', Z', and n1 are defined the same as in formula (B1).
• r1' and r2' each independently represent an integer of 0 to 3
• r4 ' each independently represent an integer of 1 to 4, provided that the sum of r1 ' , r2 ' , and r4 ' represents an integer of 1 to 4.
• R', R 1 ', and Z' are bonded to any available position.
• groups other than iodine atoms, carbonyl groups, formyl groups, R', R 1 ', and Z' are hydrogen atoms.
• n 1 represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2.
• Each r 1' independently represents an integer of 0 to 3, preferably an integer of 1 to 3, more preferably 0 or 1, and even more preferably 0.
• Each r 2' independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1.
• Each r 4' independently represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2.
• the sum of r 1' , r 2' , and r 4' is an integer of 1 to 4, and is equal to or less than the "valence of benzene minus 2."
• R', R1 ', Z', and n1 are defined the same as in formula (B1).
• r1' and r2' each independently represent an integer of 0 to 2
• r4 ' each independently represent an integer of 1 to 3, provided that the sum of r1 ' , r2 ' , and r4 ' represents an integer of 1 to 3.
• R', R 1 ', and Z' are bonded at any available position.
• groups other than the iodine atom, ether bond, formyl group, R', R 1 ', and Z' are hydrogen atoms.
• n 1 represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
• Each r 1' independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
• Each r 2' independently represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1.
• Each r 4' independently represents an integer of 1 to 3, preferably 1 or 2, and more preferably 2.
• r 1' , r 2' , and r 4' is an integer of 1 to 3 and is equal to or less than "the valence of benzene minus 3".
• n 1 , r 1' , r 2' , and r 4' are within the above ranges, there is a tendency for the number of film defects to be further reduced, and for a film for lithography that has better EUV and EB sensitivity to be more suitably formed.
• the compound represented by formula (B1) contains one or more compounds selected from the group consisting of compounds represented by the following formulas (B5) to (B26) (hereinafter also simply referred to as "compound (B5).”
• compound (B5) the group consisting of compounds represented by the following formulas (B5) to (B26)
• compound (B6) the same applies to compounds represented by formulas (B6) to (B26).
• the composition contains one or more compounds selected from the group consisting of compounds (B5) to (B26) as compound (B1), defects in the film are further reduced, and a film for lithography having even better EUV and EB sensitivity tends to be more suitably formed.
• 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.
• content of compound (B1) is within the above range, film defects tend to be further reduced, and a film for lithography with better EUV and EB sensitivity tends to be more suitably formed.
• the content of the compound represented by formula (B1) in the composition is preferably 4,000 ppm by mass or more and 8,000 ppm by mass or less.
• the content of the compound represented by formula (B1) in the composition is preferably 1 ppm by mass or more and 3,000 ppm by mass or less, and more preferably 2 ppm by mass or more and 30 ppm by mass or less.
• Compounds (A1) and (B1) can be produced by any method as long as their effects are not impaired. However, a production method including a step of introducing an iodine atom and a formyl group into a compound having a benzene ring is preferred. Note that commercially available products may be used as compounds having a formyl group on a benzene ring, such as benzaldehyde.
• Such compounds can also be obtained, for example, by oxidizing a compound having a hydroxy group on a benzene ring, such as phenol, using various formylating 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. This reaction can produce compounds (A1) and/or (B1).
• a preferred method for producing compounds (A1) and/or (B1) includes an iodination step in which an iodine atom is introduced into a raw material containing a compound having a benzene ring, a functional group capable of replacing an iodine atom by a substitution reaction, and optionally R1 .
• Another method for producing compounds (A1) and/or (B1) can include an iodination step in which iodine is introduced as a radical or as a cation or anion into a raw material containing a compound having a benzene ring and optionally R1. Note that a method for introducing an iodine atom into compound (A1) or (B1) as Z or Z', respectively, can also be carried out in a similar manner.
• the iodination step can be appropriately selected from the following methods: a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like; a method of reacting iodine chloride in an organic solvent (e.g., JP 2012-180326 A, JP 2000-256231 A, JP 2010-159233 A, J. Chem. Soc. 636, 1943); and a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of ⁇ -cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A).
• 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).
• the ratio of iodinating agent to substrate is preferably 1.2 molar or more, more preferably 1.5 molar or more, and even more preferably 2.0 molar or more.
• the iodination reaction can proceed by reacting at least an iodinating agent with a substrate, and the target compound can be obtained under known iodination reaction conditions using methods described in non-patent literature such as Adv. Synth. Catal. 2007, 349, 1159-1172, Organic Letters; Vol. 6; (2004); pp. 2785-2788, "Organic Synthesis Reagents and Synthesis Methods for Bromine and Iodine Compounds" (edited by Suzuki Hitomi, published by Manac Corporation Research Institute, Maruzen Publishing), and patent literature such as US Pat. No. 5,300,506, US Pat. No. 5,434,154, US Pat. No. 2009/281114, EP Pat. No.
• iodinating agents examples include, but are not limited to, iodine compounds, iodine monochloride, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetra-normal-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodine fluoride, tert-butylhypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetylhypoiodide, iodine-iodic acid, iodine-periodic acid
• additives can be added to the iodination reaction to promote the reaction or suppress by-products.
• additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate; bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate; oxidizing agents such as cerium (IV) ammonium nitrate and sodium peroxodisulfate; inorganic compounds such as sodium chloride, potassium chloride, mercury (II) oxide, and cerium oxide; organic compounds such as acetic anhydride; and porous substances such as zeolites.
• the ratio of additive to iodinating include acids such as hydrochloric acid
• iodine is preferably introduced into the benzene ring using at least an iodine source and an oxidizing agent.
• an iodine source and an oxidizing agent is preferred from the standpoint of reaction efficiency and improved purity.
• iodination sources include the iodinating agents listed above.
• oxidizing agents include iodic acid, periodic acid, hydrogen peroxide, and other additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, silver trifluoroacetate, and cerium (IV) ammonium nitrate (CAN)).
• the iodination reaction can also be carried out using an iodine source such as iodine combined with a silver salt or fuming sulfuric acid to form an iodine cation species.
• an iodine source such as iodine combined with a silver salt or fuming sulfuric acid to form an iodine cation species.
• the iodination reaction can be carried out by combining an iodine source with an inorganic salt to form hypoiodous acid and an iodine cation species.
• An example of an inorganic salt that can be used as appropriate is potassium peroxodisulfate.
• a method of introducing iodine into an aliphatic alcohol group via a substitution reaction can also be used as appropriate.
• iodinating agents examples include hydrogen halides, phosphorus halides, sulfonyl halides (a combination of NaI and acetone), thionyl halides, trimethylsilane halides, Vilsmeier reagents, and the Abbel reaction (a combination of triphenylphosphine and an iodine source).
• reaction solvents examples 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; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid; dimethylformamide; dimethyl sulfoxide; water, etc.
• halogenated solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride
• alkyl solvents such as hexane, cyclohexane, heptane,
• the reaction temperature for the iodination step is not particularly limited and can be any temperature between the freezing point and the boiling point of the solvent used in the reaction, but is preferably 0°C to 150°C, more preferably 20°C to 150°C, and even more preferably 50°C to 120°C.
• the reaction time for the iodination step is also not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.
• the reaction system may be refluxed to more efficiently proceed with iodination.
• a reflux condenser equipped with a Dean-Stark or similar device can be used to control the concentration of the iodinating agent in the reaction solution.
• the iodine substitution reaction in the iodination step can proceed by reacting at least an iodinating agent with a substrate.
• the target compound can be obtained under known iodine substitution reaction conditions, such as the Sandmeyer reaction, using the method described in Chemistry-A European Journal, 24 (55), 14622-14626; 2018, Synthesis (2007) (1), 81-84, etc.
• the protecting group represented by A or A′ can be introduced into a compound having a benzene ring by a known method, for example, a method appropriately selected from those described in Green's Protective Groups in Organic Synthesis (Peter G.M. Wuts, WILEY), pp. 17 to 553.
• the ratio of the protecting group introduction agent to the substrate is not particularly limited, but is preferably 0.5 molar or more, more preferably 1.0 molar or more, and even more preferably 1.5 molar or more.
• the reaction temperature in the protecting group introduction step is not particularly limited, but generally, a temperature of 0°C to 200°C is suitable. From the standpoint of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is even more preferred. The preferred temperature range is 0°C to 100°C.
• the reaction time in the protecting group introduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.
• the formyl group and the hydroxy group in Z can be obtained, for example, by introducing a carboxyl group or an ester group and then reducing it.
• reducing agents can be used, including, for example, methods using metal hydride complexes such as sodium borohydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (SBMEA), and diisobutylaluminum hydride (DIBAL); methods using metal hydrides such as aluminum hydride; and methods using these reducing agents in combination with reduction promoters such as aluminum chloride or ethanedithiol.
• the reducing agent's reducing ability can be adjusted by modifying a portion of its structure with an alkoxy group or hydrocarbon group, or by combining it with Lewis acids.
• the reaction temperature can be room temperature or heated, or cooled to adjust the reactivity. While the reaction temperature is not particularly limited, it is preferably between -20°C and 150°C, more preferably between 0°C and 150°C, and even more preferably between 20°C and 120°C.
• the ratio of reducing agent to substrate in the reduction step is not particularly limited, but is preferably 0.5 molar or more, more preferably 1.0 molar or more, and even more preferably 1.5 molar or more.
• the reaction time for the reduction 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 reducing agent used in the process of reducing the ester group to convert it to a hydroxy group is not particularly limited, but examples include boron-based reducing agents and lithium-based reducing agents.
• the reducing agent it is preferable to use a boron-based reducing agent such as sodium borohydride or borane, and it is more preferable to use a reducing agent in combination with calcium chloride or lithium chloride.
• the solvent is not particularly limited, but examples include THF (tetrahydrofuran), DMSO, chloroform, toluene, etc., with toluene being preferred, and it is more preferable to use it in combination with methanol.
• metal impurities may originate from reaction aids used in the manufacturing process of compounds (A1) and/or (B1), or from the reaction kettle and other manufacturing equipment used in the manufacturing process.
• the residual amount (content) of the above-mentioned 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.
• 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)
• transition metals such as Fe (iron), Ni (nickel), Sn (tin), Zn (zinc), Cu (copper), Sb (antimony), W (tungsten), and Al (aluminum)
• the residual metal amount is 1 ppm or more, there is a concern that interactions with other compounds may cause denaturation or deterioration of the material over time.
• alkali metals and alkalinity metals such as Na (sodium), K (potassium), Ca (calcium), and Mg (magnesium)
• the residual metal content in the resin is 1 ppm or more, it is not possible to sufficiently reduce the residual metal content when producing a resin for semiconductor processing using compounds (A1) and (B1), which could lead to defects and performance degradation due to residual metals in the semiconductor manufacturing process, resulting in a decrease in yield, and there is also concern about a decrease in characteristics due to the doping effect of the metal elements on the substrate.
• the purification method is not particularly limited, but may be the method described in International Publication No. 2015/080240 or International Publication No. 2018/159707. Specifically, this purification method involves dissolving compound (A1) and/or (B1) in an organic solvent that is immiscible with water to obtain an organic phase, contacting the organic phase with an acidic aqueous solution to perform an extraction process, thereby transferring metal components contained in the organic phase containing compound (A1) and/or (B1) and the organic solvent to the aqueous phase, and then separating the organic and aqueous phases.
• Organic solvents that are immiscible with water are typically organic solvents classified as water-insoluble solvents. While the organic solvent is not particularly limited, organic solvents that can be safely used in semiconductor manufacturing processes are preferred. The amount of organic solvent used is typically about 10% by mass relative to the compound used.
• organic solvents examples include those described in WO 2015/080240.
• 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.
• the acidic aqueous solution can be appropriately selected from aqueous solutions in which commonly known organic or inorganic compounds are dissolved in water. Examples include those described in International Publication WO 2015/080240. These acidic aqueous solutions can be used alone 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 acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
• organic acid aqueous solutions include aqueous solutions containing one or more acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
• the pH of the acidic aqueous solution is approximately 0 to 5, and more preferably approximately 0 to 3.
• the order and number of the iodination step, protecting group introduction step, and reduction step are not particularly limited and can be selected appropriately depending on the structure of the target compound.
• purification may be performed using, for example, a filter purification step or a treatment step using an ion exchange resin.
• a filter purification step known methods such as those described in WO2022/009966 and WO2017/038968 can be used.
• ion exchange resin treatment known methods such as those described in WO2017/038964 can be used.
• distillation process Other purification methods include distilling the compound itself.
• the distillation method is not particularly limited, and known methods such as atmospheric distillation, reduced pressure distillation, molecular distillation, and steam distillation can be used.
• composition (A) a composition for lithography
• one aspect of this embodiment may be a method of using compounds (A1) and (B1) to exhibit a sensitizing effect upon irradiation of a lithography composition with radiation.
• two or more types of compounds (A1) and (B1) are used. The reason for this is not limited, but it is believed that compounds (A1) and (B1) promote absorption of radiation. This effect is particularly pronounced with extreme ultraviolet (EUV) radiation.
• the sensitizing effect can take multiple forms.
• the effect can be confirmed, for example, as follows: 1) Using a patternless surface exposure method, the film thickness is measured after exposure, optionally followed by a PEB process (a process of performing a post-exposure heat treatment) and, optionally, a development process (a process of dissolving and removing exposed or unexposed areas with a developer). 2) The exposure dose is changed, the thickness of the resulting film is measured, and the exposure dose at which the film thickness changes drastically is defined as the sensitivity in the surface exposure method. 3) If sensitivity is confirmed on the low exposure dose side, a sensitizing effect can be confirmed.
• PEB process a process of performing a post-exposure heat treatment
• a development process a process of dissolving and removing exposed or unexposed areas with a developer.
• a pattern is formed by changing the exposure dose, and the sensitivity is defined as the exposure dose at which a specified line width is achieved after exposure. 2) If sensitivity is confirmed on the lower exposure dose side, a sensitizing effect can be confirmed.
• lithography compositions containing compounds (A1) and (B1) are useful for suppressing defects in resist patterns.
• EUV extreme ultraviolet
• defects such as pitting and bridging can be confirmed by reducing defects. These defects are caused by fluctuations in the optical exposure dose or exposure conditions where the exposure dose is low and the exposure state is essentially similar to defects.
• the composition of this embodiment can be used directly as a component of the lithography composition.
• the compounds (A1) and (B1) can be processed into a resin (substrate (A)) containing the compounds (A1) and (B1) as a partial structure, and additives (acid generator (C), crosslinking agent (G), acid diffusion inhibitor (E), other components (F), etc.) can be used as constituents of a composition for lithography.
• the composition for lithography contains compounds (A1) and (B1), and may contain other components, as needed, such as a base material (A), a solvent (S), an acid generator (C), a crosslinking agent (G), and an acid diffusion controller (E). Each component is described below.
• composition (A1) and (B1) The lithography composition contains compounds (A1) and (B1). It is preferable that composition (A) contains two or more types of compound (B1). When two or more types of compound (B1) are contained, etching defects shown in the examples below tend to be reduced. The reason for the reduction in etching defects is unclear, but it is thought that, for example, the compatibility between compounds (A1) and (B1) in composition (A) is improved, which may reduce fine defects when a film is formed. When two or more types of compound (B1) are contained, the structures of the repeating units may be the same or different.
• the substrate (A) refers to a compound other than compounds (A1) and (B1) that can be used as a resist.
• the substrate (A) may be a resin.
• the substrate (A) refers to a substrate (e.g., a substrate for lithography or a substrate for resist) that can be used as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB).
• Examples of the substrate (A) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof.
• phenol novolac resins cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives of these.
• the weight average molecular weight of the substrate (A) is preferably 2,000 to 49,900, more preferably 2,000 to 29,900, and even more preferably 2,000 to 14,900.
• the weight average molecular weight can be a value measured using GPC in terms of polystyrene.
• the solvent (S) in this embodiment may be any solvent capable of dissolving the compounds (A1) and (B1), and known solvents may be used as appropriate.
• Specific examples of the solvent (S) include ethylene glycol monoalkyl ether acetates; ethylene glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates (e.g., propylene glycol monomethyl ether acetate); propylene glycol monoalkyl ethers; lactate esters; aliphatic carboxylic acid esters; other esters; aromatic hydrocarbons; ketones; 3:9 amides; lactones, etc.
• Specific examples of these solvents include those disclosed in International Publication No. 2020/040161.
• 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.
• PGMEA propylene glycol monomethyl ether acetate
• PGME propylene glycol monomethyl ether
• CHN cyclohexanone
• CPN cyclopentanone
• 2-heptanone 2-heptanone
• anisole butyl acetate
• ethyl lactate 2-heptanone
• the amounts of the solid components and the solvent (S) are not particularly limited, but are preferably 1 to 80% by mass of the solid components and 20 to 99% by mass of the solvent relative to the total mass of the solid components and the solvent, more preferably 1 to 50% by mass of the solid components and 50 to 99% by mass of the solvent, even more preferably 2 to 40% by mass of the solid components and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid components and 90 to 98% by mass of the solvent.
• the total mass of the solid components (the sum of the solid components including optional components such as the base material (A), compound (A1), compound (B1), acid generator (C), crosslinking agent (G), acid diffusion controller (E), and other components (F); the same applies hereinafter) is defined as the amount of the solid components.
• the composition (A) of this embodiment preferably contains one or more acid generators (C).
• the acid generator (C) is a material that generates an acid directly or indirectly when irradiated with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays, and ion beam.
• the acid generator (C) may be one described in WO 2013/024778. Two or more acid generators (C) may also be used in combination.
• the amount of acid generator (C) used is preferably 0.001 to 49 mass% of the total mass of solid components, more preferably 1 to 40 mass%, even more preferably 3 to 30 mass%, and particularly preferably 5 to 25 mass%. Using acid generator (C) within this range tends to result in a pattern profile with high sensitivity and low edge roughness.
• the composition (A) of this embodiment preferably contains one or more crosslinking agents (G).
• the crosslinking agent (G) can crosslink at least any of the substrate (A), compound (A1), and compound (B1).
• the crosslinking agent (G) intramolecularly or intermolecularly crosslinks the substrate (A) in the presence of the acid generated from the acid generator (C).
• acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the substrate (A).
• crosslinkable groups capable of crosslinking the substrate (A).
• Examples of the crosslinking agent (G) having a crosslinkable group include those described in International Publication No. 2013/024778. Two or more crosslinking agents (G) can also be used in combination.
• the amount of crosslinking agent (G) used is preferably 0.5 to 50% by mass of the total mass of 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.
• the blending ratio of crosslinking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the resist film in an alkaline developer tends to be improved, and a decrease in the residual film rate and the occurrence of swelling or meandering of the pattern tend to be suppressed.
• the blending ratio is 50% by mass or less, a decrease in the heat resistance of the resist tend to be suppressed.
• the composition (A) of this embodiment may contain an acid diffusion controller (E).
• the acid diffusion controller (E) has the effect of controlling the diffusion of acid generated from the acid generator upon irradiation in the resist film, thereby preventing undesirable chemical reactions in unexposed areas.
• the use of the acid diffusion controller (E) tends to improve the storage stability of the composition (A) of this embodiment.
• the use of the acid diffusion controller (E) can improve the resolution of a film formed using the composition (A) of this embodiment.
• the use of the acid diffusion controller (E) can suppress changes in the line width of the resist pattern due to variations in the waiting time before and after radiation exposure, which tends to improve process stability.
• Examples of the acid diffusion controller (E) include radiation-decomposable basic compounds such as those described in WO 2013/024778. Two or more types of acid diffusion controllers (E) can also be used in combination.
• the amount of acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass, of the total mass of solid components.
• the amount of acid diffusion controller (E) is within this range, it tends to be possible to prevent degradation of resolution, pattern shape, dimensional fidelity, and the like.
• the exposure time between electron beam irradiation and post-exposure heating is long, it is possible to suppress degradation of the shape of the upper layer of the pattern.
• the amount is 10% by mass or less, it tends to be possible to prevent degradation of sensitivity, developability of unexposed areas, and the like.
• the use of such an acid diffusion controller (E) improves the storage stability and resolution of the resist composition, and also suppresses changes in the line width of the resist pattern due to variations in the exposure time before and after radiation exposure, tending to improve process stability.
• the composition (A) of the present embodiment may contain one or more of the following additives as other component (F).
• dissolution promoter When the solubility of a solid component in a developer is too low, the dissolution promoter increases the solubility and appropriately increases the dissolution rate of the compound during development.
• the dissolution promoter is preferably a low-molecular-weight compound, and examples thereof include low-molecular-weight phenolic compounds. Examples of low-molecular-weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. Two or more dissolution promoters can also be used in combination.
• the amount of dissolution promoter to be added is adjusted appropriately depending on the type of solid component 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.
• dissolution control agent When the solubility of the solid component in the developer is too high, the dissolution controller controls the solubility and appropriately reduces the dissolution rate during development.
• a dissolution controller is preferably one that does not undergo chemical changes during processes such as baking, irradiation, and development of the resist film.
• the dissolution controller is not particularly limited, but examples include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. Two or more dissolution controllers can also be used in combination.
• aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene
• ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone
• sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone.
• Two or more dissolution controllers can also be used in combination.
• the amount of dissolution controller is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
• 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.
• sensitizers include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. Two or more sensitizers can also be used in combination.
• the amount of sensitizer added is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
• the surfactant improves the coatability, striation, resist developability, and other properties of the composition (A) of this embodiment.
• the surfactant may be an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.
• Preferred surfactants include nonionic surfactants.
• Nonionic surfactants have good affinity with the solvent used in producing the composition (A) of this embodiment, thereby further enhancing the effects of the composition of this embodiment.
• nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol.
• surfactants described in Patent Document 1 can also be used.
• the amount of surfactant added is adjusted appropriately depending on the type of solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
• Organic carboxylic acids, phosphorus oxoacids, or derivatives of said oxoacids have effects such as preventing sensitivity degradation, improving resist pattern shape, or improving deposition stability.
• organic carboxylic acids include malonic acid as described in Patent Document 1.
• phosphorus oxo acids or derivatives thereof include phosphonic acid or derivatives thereof such as esters as described in Patent Document 1, and among these, phosphonic acid is particularly preferred.
• the above acids or derivatives can be used alone or in combination of two or more.
• the amount of the acid or derivative 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.
• composition (A) of this embodiment may contain additives other than the components described above, as necessary.
• additives include dyes, pigments, and adhesion promoters.
• the incorporation of a dye or pigment is preferred because it can visualize the latent image in the exposed area and mitigate the effects of halation during exposure.
• the incorporation of an adhesion promoter is preferred because it can improve adhesion to the substrate.
• other additives include antihalation agents, storage stabilizers, antifoaming agents, and shape modifiers, specifically 4-hydroxy-4'-methylchalcone.
• 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.
• the total mass of solid components refers to the sum of solid components including the base material (A), compound (A1), compound (B1), acid generator (C), crosslinking agent (G), acid diffusion controller (E), and other optional components (F).
• the mass ratio of the base material (A) to the total amount of compounds (A1) and (B1) is preferably 3:97 to 99.5:0.5, and more preferably 10:90 to 99:1. A mass ratio within this range tends to provide high sensitivity and minimize variation in exposure depth.
• the mass ratio is more preferably 30:70 to 98:2, and even more preferably 50:50 to 97:3.
• 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.
• content of compound (A1) is within the above range, film defects tend to be further reduced, and a film for lithography with better EUV and EB sensitivity tends to be more suitably formed.
• 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.
• content of compound (B1) is within the above range, film defects tend to be further reduced, and a film for lithography with better EUV and EB sensitivity tends to be more suitably formed.
• 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.
• content of compound (B1) is within the above range, film defects tend to be further reduced, and a film for lithography with better EUV and EB sensitivity tends to be more suitably formed.
• the total amount of base material (A), compound (A1), and compound (B1) is preferably 50 to 99.4 mass% of the total mass of the solid components, more preferably 55 to 95 mass%, even more preferably 60 to 95 mass%, and particularly preferably 70 to 95 mass%.
• the total amount is within the above range, resolution tends to be further improved and line edge roughness (LER) tends to be further reduced.
• the mass ratio (mass %) of the base material (A)/compounds (A1) and (B1)/acid generator (C)/crosslinking agent (G)/acid diffusion controller (E)/other component (F) relative to the total mass of the solid content of the composition (A) of this embodiment is: Preferably, 1.5 to 99.0/0.2 to 96.4/0.001 to 49/0 to 49/0.001 to 49/0 to 49, More preferably, it is 5 to 98.5/0.5 to 89/1 to 40/0 to 40/0.01 to 10/0 to 5, More preferably, it is 15 to 97.5/1 to 69/3 to 30/0 to 30/0.01 to 5/0 to 1, Particularly preferred are 25 to 96.5/1.5 to 50/3 to 30/0 to 30/0.01 to 3/0.
• the blending ratio of each component is selected from each range so that the total sum is 100% by mass. This blending ratio tends to result in excellent performance in terms of sensitivity, resolution, developability, etc.
• Solids refers to the components excluding the solvent
• total mass of solids refers to the sum of the components constituting the composition excluding the solvent, with 100% by mass.
• Composition (A) of this embodiment is typically prepared at the time of use by dissolving each component in a solvent to form a homogeneous solution, and then filtering the solution, if necessary, using a filter with a pore size of approximately 0.2 ⁇ m, for example.
• composition (A) of this embodiment can form an amorphous film by spin coating.
• the composition (A) of this embodiment can also be applied to general semiconductor manufacturing processes.
• the composition (A) of this embodiment can also form either a positive resist pattern or a negative resist pattern, depending on the type of developer used.
• Composition (A) exhibits a sensitizing effect when irradiated with radiation.
• Composition (A) also exhibits an excellent sensitizing effect when exposed to EUV light. Therefore, the present invention also provides a method for increasing the sensitivity of a lithography composition when irradiated with radiation or exposed to EUV light. As mentioned above, it is preferable to use two or more types of compound (B1) in this sensitizing method.
• the content of metal impurities (also referred to as "residual amount") in composition (A) is preferably less than 1 ppm relative to composition (A), 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.
• residual metal amount is 1 ppm or more, there is a concern that interactions with other compounds may cause denaturation or degradation of the material over time.
• the residual amount of alkali metals or alkalinity metals such as Na, K, Ca, and Mg is 1 ppm or more, the residual metal amount cannot be sufficiently reduced when the compound is used to produce resins for semiconductor manufacturing processes, and there is a concern that this may lead to defects and performance degradation due to residual metals, resulting in a decrease in yield during the semiconductor manufacturing process. It is preferable that the total content of Na, K, and Fe in composition (A) is within the above range.
• the molecular weight of the compound was measured by liquid chromatography-mass spectrometry (LC-MS) using a Waters Acquity UPLC/MALDI-Synapt HDMS.
• the white solid was purified by column chromatography to obtain compound (5IV). Measurement using a liquid chromatograph (Nexera (registered trademark)-i LC-2020C 3D (product name) manufactured by Shimadzu Corporation) at a detection wavelength of 254 nm confirmed that the purity of compound (5IV) was 99.9% or higher. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed that the molecular weight was 278. Furthermore, 1 H-NMR measurement of the white solid confirmed that it had the chemical structure of 4-hydroxy-5-iodo-3-methoxybenzaldehyde (compound (5IV)). 1 H-NMR assignments are shown below. ⁇ (ppm) (d 6 -DMSO): 10.8 (1H, -CHO), 9.8 (1H, -OH), 7.9 (1H, Ph), 7.5 (1H, Ph), 3.8 (3H, -CH 3 )
• a white solid was obtained in the same manner as in Synthesis Example 1, except that 1,420 g of ethyl vanillin was used instead of 1,300 g of vanillin.
• the white solid was purified by column chromatography to obtain compound (5IEV). As in Synthesis Example 1 above, measurement using liquid chromatography confirmed that the purity of compound (5IEV) was 99.9% or higher. Analysis by liquid chromatography-mass spectrometry (LC-MS) revealed that the molecular weight was 292. Furthermore, 1 H-NMR measurement of the white solid confirmed that it had the chemical structure of 4-hydroxy-5-iodo-3-ethoxybenzaldehyde (compound (5IEV)). The 1 H-NMR assignments are shown below.
• 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., Inc.) with a gradient of ethyl acetate and hexane (ethyl acetate:hexane) in a ratio of 1:9 to 9:1 as the developing solvent, to obtain compound (35DI4HBA), compound (3I4HBA), and compound (DM-3I4HBA) in a ratio of 1:0.9:0.5.
• column chromatography packing material: spherical and neutral silica gel 60N (product name) manufactured by Kanto Chemical Co., Inc.
• each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weights of compound (35DI4HBA) were 374, compound (3I4HBA) 248, and compound (DM-3I4HBA) 494. Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1 above, and the LC purity at 254 nm was confirmed to be 99.9% or higher for each component. Furthermore, 1 H-NMR measurements were carried out on each component, and it was confirmed that they had the chemical structures of compound (35DI4HBA), compound (3I4HBA), and compound (DM-3I4HBA), respectively. 1 H-NMR assignments for each component are shown below.
• each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weight of compound (35DI2HBA) was found to be 374, and that of compound (DM-3I2HBA) was 494. Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1 above, and the LC purity at 254 nm was confirmed to be 99.9% or higher. Furthermore, 1 H-NMR measurements were carried out on each component, and it was confirmed that they had the chemical structures of compound (35DI2HBA) and compound (DM-3I2HBA), respectively. 1 H-NMR assignments for each component are shown below.
• silica gel 60N (spherical, neutral) particle size 100-200 ⁇ m (product name) for column chromatography) with a gradient of ethyl acetate and hexane as the developing solvent in a ratio of 1:9 to 9:1 (ethyl acetate:hexane), yielding 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).
• each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weights were found to be 554 for compound (DM-5IV), 428 for compound (DM2-5IV), 578 for compound (DM3-5IV), 428 for compound (DM4-5IV), and 578 for compound (DM5-5IV). Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1 above, and it was confirmed that the LC purity at 254 nm was 99.9% or higher for each component. Furthermore, 1 H-NMR measurement was performed on each component, and it was confirmed that they had the chemical structures of compound (DM-5IV), compound (DM2-5IV), compound (DM3-5IV), compound (DM4-5IV), and compound (DM5-5IV), respectively. 1 H-NMR assignments for each component are shown below.
• each component was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the molecular weights were 582 for compound (DM-5IEV), 456 for compound (DM2-5IEV), 620 for compound (DM3-5IEV), 456 for compound (DM4-5IEV), and 620 for compound (DM5-5IEV). Furthermore, each component was measured using a liquid chromatograph in the same manner as in Synthesis Example 1 above, and it was confirmed that the LC purity at 254 nm was 99.9% or higher for each component.
• LC-MS liquid chromatography-mass spectrometry
• Examples 1 to 29 and Comparative Examples 1 to 5 The compounds obtained in Synthesis Examples 1 to 8 were mixed to obtain the compositions shown in Table 1, thereby obtaining compositions according to Examples 1 to 29 and Comparative Examples 1 to 5.
• Compound A1 is a compound represented by Formula (A1)
• Compounds B1 to B3 are each compounds represented by Formula (B1).
• the numerical values for each component indicate parts by mass. For components that were not included, the compound name is indicated as "none" and the parts by mass are indicated as "-”.
• the weight-average molecular weight (Mw) of this polymer was 11,500, and the polydispersity (Mw/Mn) was 1.90.
• MAR formula (MAR) is written in a simplified form to indicate the ratio of each structural unit, the arrangement order of the structural units is random, and it is not a block copolymer in which each structural unit forms an independent block.
• the molar ratio was determined based on the integral ratio of the main chain carbon directly bonded to benzene for the benzene-containing units, and the carbonyl carbon of the ester bond for the methacrylate-based units (2-methyl-2-adamantyl methacrylate, ⁇ -butyrolactone methacrylate, and hydroxyadamantyl methacrylate).
• Examples 30 to 60 and Comparative Examples 6 to 11 Lithography compositions according to Examples 30 to 60 and Comparative Examples 6 to 10 were obtained by mixing a base material, each of the compositions obtained in Examples 1 to 29 and Comparative Examples 1 to 5, an acid generator, an acid diffusion inhibitor, and an organic solvent so as to obtain the compositions shown in Table 2.
• a lithography composition according to Comparative Example 11 was obtained by mixing a base material, an acid generator, an acid diffusion inhibitor, and an organic solvent.
• the numerical values for each component indicate parts by mass. Components that were not included are indicated as "none" in the composition name and "-" in the parts by mass.
• the base material, acid generator, acid diffusion inhibitor, and organic solvent are as follows:
• MAR Polymer MAR represented by the above formula (MAR) (Acid Generator)
• TPS-109 Triphenylsulfonium nonafluorobutanesulfonate (manufactured by Midori Chemical Co., Ltd.) (Acid diffusion inhibitor)
• TOA Tri-n-octylamine (manufactured by Kanto Chemical Co., Ltd.) (organic solvent)
• PGMEA propylene glycol monomethyl ether acetate (Kanto Chemical Co., Ltd.)
• the resist film was heated at 110°C for 90 seconds and developed by immersion in an alkaline developer of 2.38 mass% tetramethylammonium hydroxide (TMAH) for 60 seconds.
• TMAH tetramethylammonium hydroxide
• EUV extreme ultraviolet
• EUVES-7000 (trade name), manufactured by Litho Tech Japan Co., Ltd.
• PEB post-exposure bake
• TMAH 2.38 mass% tetramethylammonium hydroxide
• the film thickness was measured using an optical interference film thickness meter (VM3200 (trade name), manufactured by SCREEN Semiconductor Solutions Co., Ltd.), and profile data of the film thickness versus exposure dose was obtained.
• the exposure dose at which the slope of the film thickness variation versus exposure dose was greatest was calculated as the sensitivity value (mJ/ cm2 ), which was used as an index of the EUV sensitivity of the resist.
• Each of the lithography compositions obtained in Examples 30 to 60 and Comparative Examples 6 to 11 was applied to an 8-inch silicon wafer having a 100 nm thick oxide film formed on its outermost surface, and baked at 110°C for 60 seconds to form a 100 nm thick photoresist layer.
• EUV extreme ultraviolet
• EUVES-7000 (trade name), manufactured by Litho Tech Japan Co., Ltd.
• shot exposure was performed on the entire surface of the wafer at an exposure amount that was 10% less than the EUV sensitivity value obtained in the above-mentioned EUV sensitivity evaluation, and the wafer was then baked (PEB) at 110°C for 90 seconds and developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, thereby obtaining a wafer that had been shot-exposed for 80 shots on the entire surface of the wafer.
• EUV extreme ultraviolet
• TMAH tetramethylammonium hydroxide
• the exposed wafers were subjected to an etching process using an etching apparatus (Telius SCCM (trade name), manufactured by Tokyo Electron Ltd.) with CF 4 /Ar gas until the oxide film was etched by 50 nm.
• the wafers produced by etching were subjected to defect evaluation using a defect inspection apparatus (Surfscan SP5 (trade name), manufactured by KLA Corporation), and the number of cone defects of 19 nm or more was determined as an index of etching defects. (Evaluation criteria) S: Number of cone defects ⁇ 6 A: 6 ⁇ Number of cone defects ⁇ 10 B: 10 ⁇ Number of cone defects ⁇ 80 C: 80 ⁇ Number of cone defects ⁇ 400 D: 400 ⁇ Number of cone defects
• Table 4 shows the evaluation results for EUV exposure sensitivity and etching defects.
• Treatment 2 Treatment without using acid
• a PGMEA solution of the composition according to Example 15 was obtained in the same manner as in Treatment 1, except that ultrapure water was used instead of the aqueous oxalic acid solution, and the concentration was adjusted to 10 mass %.
• 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 were each mixed with a base material, an acid generator, an acid diffusion inhibitor, and an organic solvent so as to obtain the compositions for lithography according to Examples 61 and 62, and Reference Example 1.
• a base material an acid generator, an acid diffusion inhibitor, and an organic solvent
• Table 6 the base material, acid generator, acid diffusion inhibitor, and organic solvent are as described above.
• etching defects In the same manner as in the above-described etching defect evaluation method, the lithography compositions of Examples 61 and 62 and Reference Example 1 were each evaluated for defects, and the number of cone defects of 19 nm or more was determined as an index of etching defects.
• Table 7 shows the evaluation results for EUV exposure sensitivity and etching defects.
• THF tetrahydrofuran
• the absorbance of each composition at 450 nm, 550 nm, and 650 nm was measured in the same manner as above, and the average value A1 was calculated.
• Table 9 shows the evaluation results for stability over time under conditions 1 and 2.
• Examples 88 to 105 The compounds obtained in Synthesis Examples 1 to 8 were mixed to obtain the compositions shown in Table 10, thereby obtaining compositions according to Examples 88 to 105.
• Table 10 Examples 1, 2, 4, 10, 11, 13, 15, 16, 18, 20, 21, 23, 25, 26, and 28, and Comparative Examples 1 to 5, respectively, are compositions obtained in the above-mentioned Examples or Comparative Examples. For these compositions, reference may be made to Table 1.
• Compound A1 is a compound represented by Formula (A1)
• Compound B1 is a compound represented by Formula (B1).
• the numerical values for each component indicate parts by mass. For components that were not included, the compound name is indicated as "none" and the parts by mass are indicated as "-.”
• Examples 106 to 123 Lithography compositions according to Examples 106 to 123 were obtained by mixing the base material, each of the compositions obtained in Examples 88 to 105, an acid generator, an acid diffusion inhibitor, and an organic solvent so as to obtain the compositions shown in Table 11.
• Table 11 Examples 30, 31, 33, 39, 40, 42, 44, 45, 47, 49, 50, 52, 54, 55, and 57, and Comparative Examples 6 to 11, respectively, are lithography compositions obtained in the above examples or comparative examples.
• the numerical values for each component are in parts by mass. For components that were not included, the composition name is marked "None" and the parts by mass are marked "-".
• the base material, acid generator, acid diffusion inhibitor, and organic solvent are as follows:
• MAR Polymer MAR represented by the above formula (MAR) (Acid Generator)
• TPS-109 Triphenylsulfonium nonafluorobutanesulfonate (manufactured by Midori Chemical Co., Ltd.) (Acid diffusion inhibitor)
• TOA Tri-n-octylamine (manufactured by Kanto Chemical Co., Ltd.) (organic solvent)
• PGMEA propylene glycol monomethyl ether acetate (Kanto Chemical Co., Ltd.)
• the resist film was heated at 110°C for 90 seconds and developed by immersion in an alkaline developer of 2.38 mass% tetramethylammonium hydroxide (TMAH) for 60 seconds.
• TMAH tetramethylammonium hydroxide
• etching defects Each of the compositions for lithography after storage was evaluated for defects in the same manner as in the above-described method for evaluating etching defects, and the number of cone defects of 19 nm or more was determined as an index of etching defects.
• Table 13 shows the evaluation results for EUV exposure sensitivity and etching defects.
• the present invention provides a composition capable of forming a lithography film with excellent EUV and EB sensitivity. For this reason, the composition of the present invention is particularly suitable for use in lithography techniques.

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