WO2023112672A1 - Procédé de production de substrat semi-conducteur et composition - Google Patents

Procédé de production de substrat semi-conducteur et composition Download PDF

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Publication number
WO2023112672A1
WO2023112672A1 PCT/JP2022/044114 JP2022044114W WO2023112672A1 WO 2023112672 A1 WO2023112672 A1 WO 2023112672A1 JP 2022044114 W JP2022044114 W JP 2022044114W WO 2023112672 A1 WO2023112672 A1 WO 2023112672A1
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ring
compound
aromatic
composition
group
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PCT/JP2022/044114
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English (en)
Japanese (ja)
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大貴 中津
嘉奈子 植田
亮太郎 田中
公佑 真弓
温子 永縄
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Jsr株式会社
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Priority to JP2023567667A priority Critical patent/JPWO2023112672A1/ja
Publication of WO2023112672A1 publication Critical patent/WO2023112672A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

Definitions

  • the present invention relates to a method and composition for manufacturing a semiconductor substrate.
  • a multilayer resist process is used in which a resist pattern is formed by exposing and developing a resist film laminated on a substrate via a resist underlayer film such as an organic underlayer film or a silicon-containing film. It is In this process, the resist underlayer film is etched using this resist pattern as a mask, and the substrate is further etched using the resist underlayer film pattern thus obtained as a mask, thereby forming a desired pattern on the semiconductor substrate (Japanese Laid-Open Patent Publication No. 2004-177668).
  • etching resistance and heat resistance are required for the organic underlayer film as the resist underlayer film.
  • the present invention has been made based on the above circumstances, and its object is to provide a method for manufacturing a semiconductor substrate using a composition capable of forming a film having excellent etching resistance and heat resistance, and the composition. be.
  • the present invention in one embodiment, a step of directly or indirectly applying a composition for forming a resist underlayer film onto a substrate; a step of directly or indirectly forming a resist pattern on the resist underlayer film formed by the coating step; and a step of performing etching using the resist pattern as a mask
  • the composition for forming a resist underlayer film is a compound having a partial structure represented by the following formula (1) (hereinafter also referred to as "[A] compound”); containing a solvent (hereinafter also referred to as "[B] solvent”) and
  • [A] compound containing a solvent
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted aromatic ring having 5 to 20 ring members that forms a condensed ring structure together with two adjacent carbon atoms in the above formula (1).
  • R 1 is at least one group selected from the group consisting of a monovalent group containing a substituted or unsubstituted aromatic ring having 5 to 60 ring members and a monovalent group containing an aromatic heterocycle having 5 to 20 ring members.
  • L is a single bond or a divalent linking group.
  • * and ** indicates a site that binds to a portion other than the partial structure represented by formula (1) in the above compound.
  • m and n are each independently an integer of 0-3. However, m+n is 1 or more.
  • the term "number of ring members” refers to the number of atoms forming a ring.
  • the biphenyl ring has 12 ring members
  • the naphthalene ring has 10 ring members
  • the fluorene ring has 13 ring members.
  • a “fused ring structure” refers to a structure in which adjacent rings share one side (two adjacent atoms).
  • the present invention in another embodiment, a compound having a partial structure represented by the following formula (1); containing a solvent and
  • the above compounds relate to compositions having a monovalent group containing at least one heteroaromatic ring having from 5 to 20 ring members.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted aromatic ring having 5 to 20 ring members that forms a condensed ring structure together with two adjacent carbon atoms in the above formula (1).
  • R 1 is at least one group selected from the group consisting of a monovalent group containing a substituted or unsubstituted aromatic ring having 5 to 60 ring members and a monovalent group containing an aromatic heterocycle having 5 to 20 ring members. is.
  • L is a single bond or a divalent linking group.
  • * and ** indicates a site that binds to a portion other than the partial structure represented by formula (1) in the above compound.
  • m and n are each independently an integer of 0-3. However, m+n is 1 or more.
  • the manufacturing method of the semiconductor substrate it is possible to form a resist underlayer film excellent in etching resistance and heat resistance.
  • a film having excellent etching resistance and heat resistance can be formed.
  • the composition has excellent solubility in a polar solvent, so clogging of the drainage pipe of the semiconductor manufacturing apparatus can be suppressed.
  • the composition since the composition has excellent solubility in a polar solvent, it is possible to suppress clogging of the drainage pipe of the semiconductor manufacturing apparatus. Therefore, these can be suitably used for the manufacture of semiconductor devices, etc., which are expected to be further miniaturized in the future.
  • the method for producing a semiconductor substrate includes a step of directly or indirectly coating a substrate with a composition for forming a resist underlayer film (hereinafter also referred to as a “coating step”), and a resist underlayer film formed by the coating step. a step of directly or indirectly forming a resist pattern (hereinafter also referred to as a “resist pattern forming step”), and a step of performing etching using the resist pattern as a mask (hereinafter also referred to as an “etching step”).
  • the method for manufacturing a semiconductor substrate by using the composition described later as a composition for forming a resist underlayer film in the coating step, clogging of a drainage pipe of a semiconductor manufacturing apparatus is suppressed, and etching resistance and Since a resist underlayer film having excellent heat resistance can be formed, semiconductor substrates having a favorable pattern shape can be manufactured with a high yield.
  • a semiconductor manufacturing apparatus there is a spin coater ("CLEAN TRACK ACT 12" by Tokyo Electron Co., Ltd.). , the resist composition, the silicon-containing film-forming composition, etc. are also discharged.
  • the composition for forming a resist underlayer film has low solubility in a polar solvent
  • the composition for forming a resist underlayer film differs from the solvent in the composition for forming a resist underlayer film in the drain pipe.
  • Contact with a polar solvent may precipitate the composition for forming a resist underlayer film, clogging a drainage pipe.
  • the method for manufacturing a semiconductor substrate may further include a step of forming a silicon-containing film directly or indirectly on the resist underlayer film (hereinafter also referred to as a "silicon-containing film forming step"), if necessary. .
  • composition and each step used in the method for manufacturing the semiconductor substrate will be described below.
  • composition as a composition for forming a resist underlayer film contains [A] compound and [B] solvent.
  • the composition may contain optional ingredients as long as the effects of the present invention are not impaired.
  • the composition can form a film with excellent etching resistance and heat resistance while suppressing clogging of drain pipes of semiconductor manufacturing equipment. Therefore, the composition can be used as a composition for forming a film. More specifically, the composition can be suitably used as a composition for forming a resist underlayer film in a multilayer resist process.
  • the compound has a partial structure represented by the following formula (1) (hereinafter also referred to as "partial structure (1)").
  • the compound may have two or more partial structures (1).
  • the multiple partial structures (1) may be the same or different.
  • the composition may contain one or more [A] compounds.
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted aromatic ring having 5 to 20 ring members that forms a condensed ring structure together with two adjacent carbon atoms in the above formula (1).
  • R 1 is at least one group selected from the group consisting of a monovalent group containing a substituted or unsubstituted aromatic ring having 5 to 60 ring members and a monovalent group containing an aromatic heterocycle having 5 to 20 ring members.
  • L is a single bond or a divalent linking group.
  • * and ** indicates a site that binds to a portion other than the partial structure represented by formula (1) in the above compound.
  • m and n are each independently an integer of 0-3. However, m+n is 1 or more. )
  • the aromatic ring having 5 to 20 ring members represented by Ar 1 and Ar 2 is, for example, an aromatic hydrocarbon ring such as benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring and perylene ring.
  • aromatic hydrocarbon ring such as benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring and perylene ring.
  • Ar 1 and Ar 2 are at least one aromatic hydrocarbon ring selected from the group consisting of benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring and perylene ring. is preferred, and the aromatic rings of Ar 1 and Ar 2 are more preferably benzene rings.
  • Ar 1 and Ar 2 may have a substituent.
  • substituents include monovalent chain hydrocarbon groups having 1 to 10 carbon atoms; halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy, ethoxy and propoxy; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, alkoxycarbonyloxy groups such as methoxycarbonyloxy group and ethoxycarbonyloxy group, acyl groups such as formyl group, acetyl group, propionyl group and butyryl group, cyano group, nitro group etc.
  • an aromatic ring obtained by expanding the aromatic ring having 5 to 20 ring members represented by Ar 1 and Ar 2 in the above formula (1) to 60 ring members is preferably employed.
  • Examples of aromatic rings having more than 20 ring members include condensed ring structures such as coronene ring, trinaphthylene ring, heptaphene ring, heptacene ring, pyranthrene ring, ovalene ring, and hexabenzocoronene ring, tetraphenylbenzene ring, pentaphenylbenzene ring, Aggregate ring structures (polycyclic structures in which rings are linked by single bonds) such as hexaphenylbenzene ring, and the like can be mentioned.
  • the monovalent group containing an aromatic ring having 5 to 60 ring members represented by R 1 includes groups obtained by removing one hydrogen atom from the above aromatic ring having 5 to 60 ring
  • the aromatic heterocyclic ring having 5 to 20 ring members in R 1 the aromatic heterocyclic ring having 5 to 20 ring members exemplified for Ar 1 and Ar 2 in the above formula (1) can be suitably employed.
  • the aromatic heterocycle for R 1 above preferably has a nitrogen atom.
  • an indole ring is preferable as the aromatic heterocyclic ring for R 1 .
  • the monovalent group containing an aromatic heterocycle having 5 to 20 ring members represented by R 1 includes groups obtained by removing one hydrogen atom from the above aromatic heterocycle having 5 to 20 ring members.
  • the divalent linking group represented by L includes, for example, a divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms and a divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms. , a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, -CO-, -O-, -NH-, -S- and one group selected from a cyclic acetal structure, or two of these groups A group formed by combining the above and the like can be mentioned.
  • Examples of the above-mentioned divalent linear or branched hydrocarbon group having 1 to 10 carbon atoms include methanediyl group, ethanediyl group, propanediyl group, butanediyl group, hexanediyl group, octanediyl group and the like. Among them, an alkanediyl group having 1 to 8 carbon atoms is preferred.
  • Examples of the divalent alicyclic hydrocarbon group having 4 to 12 carbon atoms include monocyclic cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group; polycyclic groups such as norbornanediyl group and adamantanediyl group; and the like. Among them, a cycloalkanediyl group having 5 to 12 carbon atoms is preferred.
  • Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a benzenediyl group and a naphthalenediyl group.
  • the above L is preferably a single bond.
  • n are each independently an integer of 0 to 2. m+n is preferably 1 or 2.
  • the compound has at least one monovalent group containing an aromatic heterocycle having 5 to 20 ring members.
  • a monovalent group containing an aromatic heterocycle having 5 to 20 ring members represented by R 1 above can be suitably employed.
  • the compound may have the group in the partial structure (1) or in a portion other than the partial structure (1), and the partial structure (1) and the partial structure (1) You may have it in both parts other than.
  • R 1 is a monovalent group containing a substituted or unsubstituted 6 to 60 ring-membered aromatic hydrocarbon ring. It is preferable to have partial structure (1) and partial structure (1) in which R 1 is a monovalent group containing an aromatic heterocycle having 5 to 20 ring members. In this case, the [A] compound has at least two partial structures (1).
  • the [A] compound is preferably a compound represented by the following formula (1-1) (hereinafter also referred to as “compound (1-1)”).
  • Ar 1 , Ar 2 , R 1 and L are synonymous with the above formula (1).
  • X is a (p+q)-valent group containing a substituted or unsubstituted 5 to 60-membered aromatic ring, an ethenediyl group or an ethynediyl group.
  • R 3 is a monovalent group containing an aromatic ring having 5 to 40 ring members.
  • p is an integer from 1 to 10; When p is 2 or more, the plurality of Ar 1 , Ar 2 , R 1 and L are the same or different.
  • q is an integer from 0 to 10; When q is 2 or more, the plurality of R3 's are the same or different from each other. )
  • the aromatic ring having 5 to 60 ring members in X the aromatic ring having 5 to 60 ring members in R 1 of the above formula (1) can be preferably employed.
  • X is a (p+q)-valent group containing a substituted or unsubstituted 5- to 60-membered aromatic ring, such as a group obtained by removing (p+q) hydrogen atoms from the above 5- to 60-membered aromatic ring. be done.
  • any substituent that Ar 1 and Ar 2 in the above formula (1) may have can be preferably employed.
  • the aromatic ring of X is at least one aromatic hydrocarbon ring selected from the group consisting of benzene, naphthalene, anthracene, phenalene, phenanthrene, pyrene, fluorene, perylene and coronene rings. is preferred. Among them, the aromatic ring of X is preferably a benzene ring.
  • an aromatic ring corresponding to 5 to 40 ring members among the aromatic rings having 5 to 60 ring members for X can be preferably used.
  • the monovalent group containing an aromatic ring having 5 to 40 ring members represented by R 3 includes groups obtained by removing one hydrogen atom from the above aromatic ring having 5 to 40 ring members.
  • the aromatic ring of R 3 is at least one aromatic hydrocarbon ring selected from the group consisting of benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring, perylene ring and coronene ring. is preferred.
  • Examples of the compound (1-1) include compounds represented by the following formulas (1-1-1) to (1-1-9).
  • R 11 and R 12 is a bond with the double bond at the 9-position of the fluorene skeleton.
  • the abundance ratio of R 11 and R 12 is on a molar basis. The abundance ratio can be changed by the charge amount of the raw materials that give R11 and R12 .
  • Compound (1-1) can be synthesized by a conventional method, for example, according to the following synthesis scheme.
  • a substituted fluorene is prepared as a starting material and cyclized in the presence of a catalyst or the like to obtain an intermediate (1-1-a) or (1-1-b).
  • the desired compound (1- 1-A) or (1-1-B) can be synthesized.
  • Other structures can also be synthesized by appropriately selecting starting materials, structures of aldehydes, and the like.
  • multiple types of aldehydes having different structures of R 1 are prepared at a predetermined ratio, and these are reacted with the intermediate (1-1-a) to obtain multiple types of R 1 at a predetermined abundance ratio. It is possible to synthesize a compound (1-1-A) having
  • the [A] compound is preferably a compound represented by the following formula (1-2) (hereinafter also referred to as “compound (1-2)”).
  • compound (1-2) a compound represented by the following formula (1-2)
  • Ar 1 , Ar 2 , R 1 and L are synonymous with the above formula (1).
  • R 4 and R 5 are each independently a monovalent group containing an aromatic ring having 5 to 40 ring members or a group containing an unsaturated carbon bond.
  • r and s are each independently an integer of 1-10.
  • Examples of the monovalent group containing an aromatic ring having 5 to 40 ring members represented by R 4 and R 5 include an aromatic ring having 5 to 40 ring members represented by R 3 in the above formula (1-2). can be preferably employed.
  • the aromatic rings of R 4 and R 5 are each independently selected from the group consisting of benzene ring, naphthalene ring, anthracene ring, phenalene ring, phenanthrene ring, pyrene ring, fluorene ring, perylene ring and coronene ring. At least one aromatic hydrocarbon ring is preferred.
  • the carbon-carbon unsaturated bond-containing groups represented by R 4 and R 5 include carbon-carbon double or carbon-carbon triple bond-containing groups having 2 to 10 carbon atoms, such as ethenyl, ethynyl, allyl, and propargyl groups. Examples include unsaturated chain hydrocarbon groups.
  • r and s are each independently preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • Examples of the compound (1-2) include compounds represented by the following formulas (1-2-1) to (1-2-3).
  • Compound (1-2) can be synthesized by a conventional method, for example, according to the following synthesis scheme.
  • Ar q is an aromatic hydrocarbon ring having 6 to 20 ring members .
  • Ar q may be fused with the cyclopentadienone structure shown in the scheme to form a condensed ring.
  • multiple Ar q may be fused together to form a condensed ring, u is an integer from 1 to 4.
  • 2,7-diethynylfluorene as a starting material is reacted with a cyclopentadienone having a structure corresponding to R 4 or R 5 in the above formula (1-2) to give an intermediate (1-2- a) is obtained.
  • the intermediate (1-2-a) is reacted with an aldehyde having the structure of R 1 of the above formula (1-1) to synthesize the desired compound (1-2-A). can be done.
  • Other structures can also be synthesized by appropriately selecting starting materials, structures of cyclopentadienone bodies, aldehyde bodies, and the like.
  • the compound is preferably a polymer having two or more partial structures (1) as repeating units.
  • the polymer is preferably represented by the following formula (1-3).
  • Ar 1 , Ar 2 , R 1 and L are synonymous with the above formula (1).
  • L 2 is a divalent group containing an aromatic ring having 5 to 60 ring members, an ethenediyl group, an ethynediyl group, a combination thereof, or a single bond.
  • the bivalent group containing an aromatic ring having 5 to 60 ring members represented by L 2 includes a monovalent group containing an aromatic ring having 5 to 60 ring members for R 1 in the above formula (1). Groups without hydrogen atoms are included.
  • the lower limit of the weight average molecular weight (Mw) of the polymer is not particularly limited, it is preferably 1,000, more preferably 1,500, and even more preferably 2,000.
  • the upper limit of the weight average molecular weight (Mw) is preferably 15,000, more preferably 10,000, even more preferably 8,000.
  • the method for measuring the weight average molecular weight (Mw) of the polymer is described in Examples.
  • Examples of the compound (1-2) include compounds represented by the following formulas (1-3-1) to (1-3-6).
  • the above polymer is typically obtained by an acid addition condensation reaction between (ethynyl group-substituted) fluorene and, if necessary, an aromatic ring compound that gives L2 by a conventional method to obtain an intermediate polymer.
  • the target polymer can be synthesized by reacting the intermediate polymer with an aldehyde having the structure of R 1 of formula (1-3) above.
  • Other structures can also be synthesized by appropriately selecting the starting materials, the aromatic ring compound that gives L2 , the structure of the aldehyde form, and the like.
  • the lower limit of the content of the [A] compound in the composition is preferably 2% by mass, more preferably 4% by mass, more preferably 6% by mass in the total mass of the [A] compound and [B] solvent, 8% by weight is particularly preferred.
  • the upper limit of the content ratio is preferably 30% by mass, more preferably 25% by mass, still more preferably 20% by mass, and particularly preferably 18% by mass, based on the total mass of the [A] compound and [B] solvent.
  • the [B] solvent is not particularly limited as long as it can dissolve or disperse the [A] compound and optionally contained optional components.
  • Solvents include, for example, hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, nitrogen-containing solvents, and the like.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as n-pentane, n-hexane and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene and xylene.
  • ester solvents include carbonate solvents such as diethyl carbonate, acetic acid monoester solvents such as methyl acetate and ethyl acetate, lactone solvents such as ⁇ -butyrolactone, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • carbonate solvents such as diethyl carbonate
  • acetic acid monoester solvents such as methyl acetate and ethyl acetate
  • lactone solvents such as ⁇ -butyrolactone
  • diethylene glycol monomethyl ether acetate diethylene glycol monomethyl ether acetate
  • propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate.
  • Valued alcohol partial ether carboxylate solvents such as methyl lactate and ethyl lactate, and the like are included.
  • alcoholic solvents examples include monoalcoholic solvents such as methanol, ethanol and n-propanol, and polyhydric alcoholic solvents such as ethylene glycol and 1,2-propylene glycol.
  • ketone solvents examples include chain ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and cyclic ketone solvents such as cyclohexanone.
  • ether solvents include chain ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran, and polyhydric alcohol partial ether solvents such as diethylene glycol monomethyl ether. .
  • nitrogen-containing solvents examples include linear nitrogen-containing solvents such as N,N-dimethylacetamide and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.
  • the [B] solvent is preferably an ester solvent or a ketone solvent, more preferably a polyhydric alcohol partial ether carboxylate solvent or a cyclic ketone solvent, and even more preferably propylene glycol monomethyl ether acetate or cyclohexanone.
  • the lower limit of the content of the [B] solvent in the composition is preferably 50% by mass, more preferably 60% by mass, and even more preferably 70% by mass.
  • the upper limit of the content ratio is preferably 99.9% by mass, more preferably 99% by mass, and even more preferably 95% by mass.
  • the composition may contain optional ingredients as long as they do not impair the effects of the present invention.
  • Optional components include, for example, an acid generator, a cross-linking agent, and a surfactant.
  • An arbitrary component can be used individually by 1 type or in combination of 2 or more types.
  • the content ratio of the optional component in the composition can be appropriately determined according to the type of the optional component.
  • composition is prepared by mixing the [A] compound, [B] solvent, and optional ingredients in a predetermined ratio as necessary, and preferably filtering the resulting mixture through a membrane filter having a pore size of 0.5 ⁇ m or less.
  • a membrane filter having a pore size of 0.5 ⁇ m or less.
  • the resist underlayer film-forming composition is applied directly or indirectly onto the substrate.
  • the composition described above is used as the composition for forming the resist underlayer film.
  • the method of coating the composition for forming a resist underlayer film is not particularly limited, and can be carried out by an appropriate method such as spin coating, casting coating, roll coating, or the like. As a result, a coating film is formed, and [B] a resist underlayer film is formed by volatilization of the solvent.
  • the substrate examples include metal or semi-metal substrates such as silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, and titanium substrates, among which silicon substrates are preferred.
  • the substrate may be a substrate on which a silicon nitride film, an alumina film, a silicon dioxide film, a tantalum nitride film, a titanium nitride film, or the like is formed.
  • Examples of the case of indirectly applying the composition for forming a resist underlayer film onto a substrate include the case of applying the composition for forming a resist underlayer film onto a silicon-containing film formed on the substrate, which will be described later.
  • the coating film formed by the coating step is heated.
  • the heating of the coating promotes the formation of the resist underlayer film. More specifically, heating the coating film promotes volatilization of the [B] solvent.
  • the coating film may be heated in an air atmosphere or in a nitrogen atmosphere.
  • the lower limit of the heating temperature is preferably 300°C, more preferably 320°C, and even more preferably 350°C.
  • the upper limit of the heating temperature is preferably 600°C, more preferably 500°C.
  • the lower limit of the heating time is preferably 15 seconds, more preferably 30 seconds.
  • the upper limit of the time is preferably 1,200 seconds, more preferably 600 seconds.
  • the resist underlayer film may be exposed after the coating step. After the coating step, the resist underlayer film may be exposed to plasma. After the coating step, ions may be implanted into the resist underlayer film. Exposure of the resist underlayer film improves the etching resistance of the resist underlayer film. Exposure of the resist underlayer film to plasma improves the etching resistance of the resist underlayer film. Ion implantation into the resist underlayer film improves the etching resistance of the resist underlayer film.
  • the radiation used for exposure of the resist underlayer film is appropriately selected from electromagnetic waves such as visible light, ultraviolet rays, deep ultraviolet rays, X-rays, and ⁇ rays; and particle beams such as electron beams, molecular beams, and ion beams.
  • the normal gas flow rate is 50 cc/min or more and 100 cc/min or less
  • the power supply is 100 W or more and 1,500 W or less.
  • the lower limit of plasma exposure time is preferably 10 seconds, more preferably 30 seconds, and even more preferably 1 minute.
  • the upper limit of the time is preferably 10 minutes, more preferably 5 minutes, and even more preferably 2 minutes.
  • Plasma is generated, for example, in a mixed gas atmosphere of H 2 gas and Ar gas.
  • a carbon-containing gas such as CF 4 gas or CH 4 gas may be introduced.
  • CF4 gas, NF3 gas , CHF3 gas , CO2 gas, CH2F2 gas, CH4 gas and C4F8 gas At least one of them may be introduced.
  • the ion implantation into the resist underlayer film injects the dopant into the resist underlayer film.
  • Dopants may be selected from the group consisting of boron, carbon, nitrogen, phosphorous, arsenic, aluminum, and tungsten. Implant energies used to voltage the dopants range from about 0.5 keV to 60 keV, depending on the type of dopant used and the depth of implantation desired.
  • the lower limit to the average thickness of the resist underlayer film to be formed is preferably 30 nm, more preferably 50 nm, and even more preferably 100 nm.
  • the upper limit of the average thickness is preferably 3,000 nm, more preferably 2,000 nm, and even more preferably 500 nm. The method for measuring the average thickness is described in Examples.
  • a silicon-containing film is formed directly or indirectly on the resist underlayer film formed in the coating step or the heating step.
  • the silicon-containing film is formed indirectly on the resist underlayer film include, for example, the case where a surface modification film of the resist underlayer film is formed on the resist underlayer film.
  • the surface modified film of the resist underlayer film is, for example, a film having a contact angle with water different from that of the resist underlayer film.
  • a silicon-containing film can be formed by coating a silicon-containing film-forming composition, chemical vapor deposition (CVD), atomic layer deposition (ALD), or the like.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • a method of forming a silicon-containing film by coating a silicon-containing film-forming composition for example, a coating film formed by directly or indirectly coating a silicon-containing film-forming composition on the resist underlayer film is formed. , a method of curing by exposure and/or heating, and the like.
  • Commercially available products of the silicon-containing film-forming composition include, for example, "NFC SOG01", “NFC SOG04", and "NFC SOG080" (manufactured by JSR Corporation).
  • Silicon oxide films, silicon nitride films, silicon oxynitride films, and amorphous silicon films can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).
  • Examples of the radiation used for the exposure include visible light, ultraviolet rays, far ultraviolet rays, X-rays, electromagnetic waves such as ⁇ -rays, and particle beams such as electron beams, molecular beams, and ion beams.
  • the lower limit of the temperature when heating the coating film is preferably 90°C, more preferably 150°C, and even more preferably 200°C.
  • the upper limit of the temperature is preferably 550°C, more preferably 450°C, and even more preferably 300°C.
  • the lower limit of the average thickness of the silicon-containing film is preferably 1 nm, more preferably 10 nm, and even more preferably 20 nm.
  • the upper limit is preferably 20,000 nm, more preferably 1,000 nm, even more preferably 100 nm.
  • the average thickness of the silicon-containing film is a value measured using the spectroscopic ellipsometer as in the case of the average thickness of the resist underlayer film.
  • resist pattern forming step In this step, a resist pattern is formed directly or indirectly on the resist underlayer film.
  • the method for performing this step include a method using a resist composition, a method using a nanoimprint method, a method using a self-assembled composition, and the like.
  • Examples of forming a resist pattern indirectly on the resist underlayer film include forming a resist pattern on the silicon-containing film.
  • the resist composition examples include a positive-type or negative-type chemically amplified resist composition containing a radiation-sensitive acid generator, a positive-type resist composition containing an alkali-soluble resin and a quinonediazide-based photosensitizer, an alkali-soluble Examples include a negative resist composition containing a resin and a cross-linking agent, and a metal-containing resist composition containing a metal such as tin or zirconium.
  • Examples of the coating method of the resist composition include a spin coating method and the like.
  • the pre-baking temperature and time can be appropriately adjusted depending on the type of resist composition used.
  • the radiation used for exposure can be appropriately selected according to the type of radiation-sensitive acid generator used in the resist composition, and examples thereof include visible light, ultraviolet light, deep ultraviolet light, X-rays, and ⁇ -rays. Examples include electromagnetic waves, electron beams, molecular beams, and particle beams such as ion beams.
  • KrF excimer laser light (wavelength 248 nm), ArF excimer laser light (wavelength 193 nm), F2 excimer laser light (wavelength 157 nm), Kr2 excimer laser light (wavelength 147 nm), ArKr excimer Laser light (wavelength: 134 nm) or extreme ultraviolet rays (wavelength: 13.5 nm, etc., hereinafter also referred to as "EUV”) are more preferred, and KrF excimer laser light, ArF excimer laser light, or EUV is even more preferred.
  • EUV extreme ultraviolet rays
  • post-baking can be performed to improve the resolution, pattern profile, developability, and the like.
  • the temperature and time of this post-baking can be appropriately determined according to the type of resist composition used.
  • the exposed resist film is developed with a developer to form a resist pattern.
  • This development may be either alkali development or organic solvent development.
  • the developer in the case of alkali development, basic aqueous solutions such as ammonia, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, etc. can be used. Suitable amounts of water-soluble organic solvents such as alcohols such as methanol and ethanol, surfactants, and the like can also be added to these basic aqueous solutions.
  • the developer includes, for example, various organic solvents exemplified as the [B] solvent of the composition.
  • a predetermined resist pattern is formed by washing and drying after development with the developer.
  • etching is performed using the resist pattern as a mask. Etching may be performed once or multiple times, that is, etching may be performed sequentially using a pattern obtained by etching as a mask. Multiple times are preferable from the viewpoint of obtaining a pattern with a better shape. When etching is performed multiple times, for example, the silicon-containing film, the resist underlayer film, and the substrate are sequentially etched. Etching methods include dry etching, wet etching, and the like. Dry etching is preferable from the viewpoint of improving the pattern shape of the substrate. For this dry etching, gas plasma such as oxygen plasma is used. A semiconductor substrate having a predetermined pattern is obtained by the etching.
  • Dry etching can be performed using, for example, a known dry etching apparatus.
  • the etching gas used for dry etching can be appropriately selected according to the mask pattern, the elemental composition of the film to be etched, etc. Examples include CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 and SF 6 .
  • Fluorine-based gases chlorine-based gases such as Cl 2 and BCl 3 , oxygen-based gases such as O 2 , O 3 and H 2 O, H 2 , NH 3 , CO, CO 2 , CH 4 , C 2 H 2 , C 2H4 , C2H6 , C3H4 , C3H6 , C3H8 , HF , HI, HBr, HCl, NO, NH3 , reducing gases such as BCl3 , He, N2 , Inert gas, such as Ar, etc. are mentioned. These gases can also be mixed and used. When etching a substrate using the pattern of the resist underlayer film as a mask, a fluorine-based gas is usually used.
  • composition contains [A] compound and [B] solvent.
  • composition used in the method for manufacturing a semiconductor substrate can be suitably employed.
  • Mw Weight average molecular weight
  • the average thickness of the resist underlayer film is determined by measuring the film thickness at arbitrary 9 points at intervals of 5 cm including the center of the resist underlayer film using a spectroscopic ellipsometer ("M2000D" manufactured by JA WOOLLAM). It was obtained as a calculated value of the average value of the film thickness.
  • D-2 a compound represented by the following formula (D-2)
  • composition (J-1) 15 parts by mass of (A-1) as a compound was dissolved in 85 parts by mass of (B-2) as a [B] solvent. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter with a pore size of 0.45 ⁇ m to prepare composition (J-1).
  • PTFE polytetrafluoroethylene
  • the composition prepared above was coated on a silicon wafer (substrate) by a spin coating method using a spin coater ("CLEAN TRACK ACT 12" available from Tokyo Electron Ltd.). Next, after heating at 350° C. for 60 seconds in an air atmosphere, by cooling at 23° C. for 60 seconds, a film having an average thickness of 200 nm was formed, and a film-coated substrate having a resist underlayer film formed on the substrate was obtained. Obtained.
  • etching rate (nm/min) was calculated from the average thickness of the film before and after the treatment.
  • the ratio to Comparative Example 1 was calculated based on the etching rate of Comparative Example 1, and this ratio was used as a measure of etching resistance.
  • the etching resistance is "A” (extremely good) when the above ratio is 0.90 or less, "B" (good) when it is more than 0.90 and less than 0.92, and "B” when it is 0.92 or more.
  • C (defective).
  • "-" in Table 2 indicates that it is an evaluation criterion for etching resistance.
  • the composition prepared above was coated on a silicon wafer (substrate) by a spin coating method using a spin coater ("CLEAN TRACK ACT 12" available from Tokyo Electron Ltd.). Next, after heating at 200° C. for 60 seconds in an air atmosphere, by cooling at 23° C. for 60 seconds, a film having an average thickness of 200 nm was formed to obtain a film-coated substrate having a film formed on the substrate. .
  • the powder was collected by scraping the film of the film-coated substrate obtained above, and the collected powder was placed in a container used for measurement with a TG-DTA device (“TG-DTA2000SR” by NETZSCH) and placed in a container before heating. Mass was measured.
  • the powder was heated to 400° C. at a heating rate of 10° C./min in a nitrogen atmosphere, and the mass of the powder at 400° C. was measured. Then, the mass reduction rate (%) was measured by the following formula, and this mass reduction rate was used as a measure of heat resistance.
  • M L ⁇ (m1 ⁇ m2)/m1 ⁇ 100
  • ML is the mass reduction rate (%)
  • m1 is the mass before heating (mg)
  • m2 is the mass at 400°C (mg).
  • the heat resistance the smaller the mass reduction rate of the sample powder, the less the sublimate and the decomposition product of the film generated during the heating of the film, and the better the heat resistance.
  • the heat resistance is "A” (very good) when the mass reduction rate is less than 5%, "B” (good) when it is 5% or more and less than 10%, and "C” when it is 10% or more ( bad).
  • the resist underlayer films formed from the compositions of Examples were excellent in solubility in polar solvents, etching resistance, and heat resistance.
  • a substrate with excellent patterning can be obtained.
  • the composition of the present invention has good solubility in polar solvents and can form a resist underlayer film with excellent etching resistance and heat resistance. Therefore, these can be suitably used for the manufacture of semiconductor devices, etc., which are expected to be further miniaturized in the future.

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Abstract

L'objet de la présente invention est de fournir un procédé de production de substrat semi-conducteur faisant appel à une composition à partir de laquelle peut être formé un film présentant une excellente résistance à la gravure et à la chaleur, et une composition. L'invention concerne un procédé de production de substrat semi-conducteur qui comprend une étape consistant à revêtir directement ou indirectement un substrat avec une composition de formation de film de sous-couche de réserve, une étape consistant à former directement ou indirectement un motif de réserve sur le film de sous-couche de réserve formé dans l'étape de revêtement, et une étape consistant à graver en utilisant le motif de réserve en tant que masque. La composition permettant de former le film de sous-couche de réserve contient un composé ayant une structure partielle représentée par la formule (1), et un solvant ; et le composé a au moins un groupe monovalent qui comprend un hétérocycle aromatique ayant un cycle doté de 5 à 20 chaînons. (Dans la formule (1), Ar1 et Ar2 représentent chacun indépendamment un cycle aromatique substitué ou non substitué qui a un cycle doté de 5 à 20 chaînons et qui forme une structure cyclique condensée et deux atomes de carbone adjacents dans la formule (1). R1 représente un ou plusieurs groupes parmi un cycle monovalent comprenant un cycle aromatique substitué ou non substitué ayant un cycle doté de 5 à 60 chaînons, et un groupe monovalent comprenant un hétérocycle aromatique ayant un cycle doté de 5 à 20 chaînons. L représente une liaison simple ou un groupe de liaison divalent. * et ** représentent chacun une position qui se lie à une section dudit composé qui est autre que la structure partielle représentée par la formule (1). m et n représentent chacun indépendamment un nombre entier de 0 à 3. Cependant, m + n est supérieur ou égal à 1.)
PCT/JP2022/044114 2021-12-15 2022-11-30 Procédé de production de substrat semi-conducteur et composition WO2023112672A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007270123A (ja) * 2006-03-09 2007-10-18 Ricoh Co Ltd π共役ポリマー
WO2018164267A1 (fr) * 2017-03-10 2018-09-13 Jsr株式会社 Composition de formation de pellicule de sous-couche de résine photosensible, pellicule de sous-couche de résine photosensible et procédé de production de substrat à motifs
CN110156616A (zh) * 2019-05-22 2019-08-23 吉林师范大学 基于芴乙烯桥联芳香环核的免掺杂空穴传输材料的合成方法及其在钙钛矿电池中的应用
WO2019208212A1 (fr) * 2018-04-23 2019-10-31 Jsr株式会社 Composition de formation de film de sous-couche de réserve, film de sous-couche de réserve et procédé de formation correspondant et procédé de formation de motif
WO2021054337A1 (fr) * 2019-09-17 2021-03-25 Jsr株式会社 Composition, film de sous-couche de réserve, procédé de formation de film de sous-couche de réserve, procédé de production de substrat à motifs et composé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007270123A (ja) * 2006-03-09 2007-10-18 Ricoh Co Ltd π共役ポリマー
WO2018164267A1 (fr) * 2017-03-10 2018-09-13 Jsr株式会社 Composition de formation de pellicule de sous-couche de résine photosensible, pellicule de sous-couche de résine photosensible et procédé de production de substrat à motifs
WO2019208212A1 (fr) * 2018-04-23 2019-10-31 Jsr株式会社 Composition de formation de film de sous-couche de réserve, film de sous-couche de réserve et procédé de formation correspondant et procédé de formation de motif
CN110156616A (zh) * 2019-05-22 2019-08-23 吉林师范大学 基于芴乙烯桥联芳香环核的免掺杂空穴传输材料的合成方法及其在钙钛矿电池中的应用
WO2021054337A1 (fr) * 2019-09-17 2021-03-25 Jsr株式会社 Composition, film de sous-couche de réserve, procédé de formation de film de sous-couche de réserve, procédé de production de substrat à motifs et composé

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