Classifications

• • 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
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3236—Heterocylic compounds
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3236—Heterocylic compounds
  • C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • 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
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • 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
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes

Definitions

• the present invention relates to a composition used in a lithography process in semiconductor manufacturing, particularly in a state-of-the-art (ArF, EUV, EB, etc.) lithography process.
• the present invention also relates to a method for manufacturing a substrate with a resist pattern to which the resist underlayer film is applied, and a method for manufacturing a semiconductor device.
• a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, and an active light beam such as ultraviolet rays is irradiated through a mask pattern on which a pattern of a device is drawn to develop the film.
• an active light beam such as ultraviolet rays
• This is a processing method for forming fine irregularities corresponding to the pattern on the surface of the substrate by etching the substrate using the obtained photoresist pattern as a protective film.
• Patent Document 1 discloses a resist underlayer film forming composition having a disulfide structure.
• Patent Document 2 discloses an antireflection film forming composition for lithography.
• the characteristics required for the resist underlayer film are, for example, that intermixing with the resist film formed on the upper layer does not occur (insoluble in the resist solvent) and that the dry etching rate is faster than that of the resist film. Can be mentioned.
• the line width of the formed resist pattern is 32 nm or less, and the resist underlayer film for EUV exposure is used with a thinner film thickness than before.
• pinholes, agglomeration, etc. are likely to occur due to the influence of the substrate surface, the polymer used, and the like, and it is difficult to form a uniform film without defects.
• a solvent capable of dissolving the resist film usually an organic solvent, is used to remove the unexposed portion of the resist film, and the exposed portion of the resist film is left as a resist pattern.
• improvement of the adhesion of the resist pattern is a major problem.
• LWR Line Width Roughness, line width fluctuation (roughness)
• An object of the present invention is to provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, which solves the above problems, and a resist pattern forming method using the resist underlayer film forming composition. ..
• the present invention includes the following.
• A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocycle
• A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocycle
• Compound (B) having two functional groups reactive with an epoxy group and A resist underlayer film forming composition comprising a reaction product of an epoxy group and a compound (C) having one functional group having reactivity.
• the compound (B) is a compound having two functional groups reactive with an epoxy group, which comprises an aliphatic ring, an aromatic ring, a heterocycle, a fluorine atom, an iodine atom or a sulfur atom, [1] to [3]
• the resist underlayer film forming composition according to any one item.
• the compound (C) is a compound having one functional group reactive with an epoxy group, which comprises an aliphatic ring or an aromatic ring which may be substituted with a substituent [1] to [4].
• the resist underlayer film forming composition according to any one item.
• A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocycle
• a resist underlayer film forming composition comprising a reaction product (a) with a compound (B) having two functional groups having reactivity with an epoxy group, which does not contain a disulfide bond.
• a resist underlayer film which is a fired product of a coating film comprising the resist underlayer film forming composition according to any one of [1] to [8].
• a method for producing a patterned substrate which comprises a step of forming a film, a step of exposing the resist underlayer film and a semiconductor substrate coated with the resist, and a step of developing and patterning the resist film after exposure.
• a method for producing a resist underlayer film forming composition which comprises a step of further mixing the same or different kinds of solvents with the reaction product according to [12].
• a method for producing a resist underlayer film forming composition which comprises a step of further mixing the same or different kinds of solvents with the reaction product according to [14].
• the resist underlayer film forming composition of the present invention has excellent coatability on a semiconductor substrate to be processed, and achieves improvement in adhesion between the resist and the resist underlayer film interface at the time of forming a resist pattern, and improvement in sensitivity. Can be done. In particular, it exerts a remarkable effect when exposed to EUV light (wavelength 13.5 nm) or EB (electron beam).
• the resist underlayer film forming composition of the present invention comprises a solvent and the following formula (1):
• A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocycle
• Compound (B) having two functional groups reactive with an epoxy group and It contains a reaction product soluble in the solvent, obtained by reacting a mixture containing an epoxy group with a compound (C) having one reactive functional group.
• the mixture of the compounds (A) to (C) has a molar ratio; (C) / ((A) + (B)) of 0.5 or more and 2 or less. Molar ratio; By reacting a mixture of compounds (A) to (C) in the range of (C) / ((A) + (B)) of 0.5 or more and 2 or less, the weight average molecular weight of the reaction product is increased. An excessive increase is suppressed, and a reaction product in which the compound (C) is present at a certain ratio at each end of the reaction product molecule can be produced. The presence of the compound (C) at the terminal improves the solubility in the solvent.
• reaction products of compound (A), compound (B) and compound (C) can be obtained, for example, by reacting by the method described in Examples.
• (C) / ((A) + (B)) is 0.5 or more and 2 or less, but 0.5 or more. It may be 1.9 or less, 0.5 or more and 1.8 or less, 0.5 or more and 1.7 or less, 0.5 or more and 1.6 or less, and 0. It may be 5 or more and 1.5 or less, 0.5 or more and 1.4 or less, 0.5 or more and 1.3 or less, and 0.5 or more and 1.2 or less. It may be 0.5 or more and 1.1 or less, and may be 0.5 or more and 1.0 or less.
• dissolvable in a solvent means that a state in which the reaction product is uniformly dissolved in a solvent described later is maintained, for example, under certain conditions (for example, in the range of 5 to 40 ° C. for one month).
• the composition used a microfilter having a pore size of 0.05 ⁇ m to 0.1 ⁇ m, and the entire 100 mL of the composition was used for 30 minutes. Say that it can be filtered within.
• Examples of the functional group reactive with the epoxy group include hydroxy group, acyl group, acetyl group, formyl group, benzoyl group, carboxy group, carbonyl group, amino group, imino group, cyano group, azo group, azi group and thiol.
• Examples thereof include a group, a sulfo group, an allyl group and an acid anhydride, but a carboxy group is preferable.
• the reaction product contains a partial structure represented by the following formula (1-1).
• A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocycle
• R 1 represents a residue derived from the compound (B)
• * represents the compound.
• the lower limit of the weight average molecular weight of the reaction product is, for example, 500, 1,000, 2,000, or 3,000
• the upper limit of the weight average molecular weight of the reaction product is, for example, 30,000, 20,000, or. It is 10,000.
• the R 1 is preferably a divalent organic group containing an aliphatic ring, an aromatic ring, a heterocycle or a sulfur atom, which will be described later.
• the resist underlayer film forming composition of the present invention has the following formula (1): (In the formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocycle) and the compound (A). It may contain a reaction product (a) obtained by reacting a mixture containing an epoxy group and a compound (B) having two reactive functional groups, which does not contain a disulfide bond, and a solvent.
• the molar ratio of the compound (B) having two functional groups reactive with an epoxy group, which does not contain any disulfide bond with the compound (A), is, for example, 1: 1. It is 0.1 to 10. It is preferably 1: 1 to 5, and more preferably 1: 3.
• the lower limit of the weight average molecular weight of the reaction product (a) is, for example, 500, 1,000, 2,000, or 3,000, and the upper limit of the weight average molecular weight of the reaction product is, for example, 30,000, 20, 000 or 10,000.
• Compound (A) contains an organic group containing an aliphatic ring, an aromatic ring or a heterocycle, and is not limited as long as it is a compound exhibiting the effects of the present application, but is not limited to the following, for example. Illustrated.
• a in the above formula (1) is a heterocycle.
• the heterocycle is preferably triazine.
• the heterocycle is preferably 1,2,3-triazine.
• the heterocycle is preferably triazinetrione.
• the compound (B) is not limited as long as it is a compound having the effect of the present application, but has two reactivity with an epoxy group containing an aliphatic ring, an aromatic ring, a heterocycle, a fluorine atom, an iodine atom or a sulfur atom. It is preferably a compound having a functional group.
• the sulfur atom is preferably contained in the compound as a sulfide bond, a disulfide bond or a sulfonyl group.
• the compound (B) is exemplified below, for example.
• the epoxy group and the unreacted carboxy group may be free and may react with at least one compound represented by the following formula (3d). ..
• R 1 represents a methyl group or an ethyl group.
• the compound (C) is not limited as long as it is a compound exhibiting the effects of the present application, but one functional group having reactivity with an epoxy group containing an aliphatic ring or an aromatic ring which may be substituted with a substituent is used. It is preferably a compound having.
• the compound (C) may contain an aliphatic ring which may be substituted with a substituent.
• the aliphatic ring is preferably a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.
• Examples of the monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, and bicyclo [ 2.1.0] Pentane, Bicyclo [3.2.1] Octane, Tricyclo [3.2.1.0 2,7 ] Octane, Spiro [3,4] Octane, Norbornane, Norbornene, Tricyclo [3.3] .1.1 3,7 ] Decane (adamantan) and the like can be mentioned.
• the polycyclic aliphatic ring is preferably a bicyclo ring or a tricyclo ring.
• bicyclo ring examples include norbornane, norbornene, spirobicyclopentane, bicyclo [2.1.0] pentane, bicyclo [3.2.1] octane, spiro [3,4] octane and the like.
• tricyclo ring examples include tricyclo [3.2.1.0 2,7 ] octane and tricyclo [3.3.1.1 3,7 ] decane (adamantane).
• the aliphatic ring which may be substituted with the substituent means that one or more hydrogen atoms of the aliphatic ring may be replaced with the substituent described below.
• substituents examples include a hydroxy group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and an oxygen atom. It is preferably selected from an acyloxy group and a carboxy group having 1 to 10 carbon atoms which may be interrupted.
• alkoxy group having 1 to 20 carbon atoms examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and n.
• -Pentyloxy group 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n -Propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-Methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n- Butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n -Butoxy group, 1,1,2-trimethyl-
• aryl group having 6 to 40 carbon atoms examples include a benzyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group or a pyrenyl group, and among these, a phenyl group is preferable.
• the acyloxy group having 1 to 10 carbon atoms has the following formula (4): (In the formula (4), Z is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms among the above alkyl groups having 1 to 10 carbon atoms, and the alkyl group is substituted with the substituent. It may be interrupted by an oxygen atom or an ester bond, and may have an allyl group or a propagyl group. * Represents a bonding portion with the above-mentioned "aliphatic ring"). Say.
• the aliphatic ring has at least one unsaturated bond (for example, a double bond or a triple bond).
• the aliphatic ring preferably has one to three unsaturated bonds.
• the aliphatic ring preferably has one or two unsaturated bonds.
• the unsaturated bond is preferably a double bond.
• the compound containing an aliphatic ring which may be substituted with the substituent include the compounds described below.
• the carboxy group of the following specific example is a hydroxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azi group, a thiol group, a sulfo group and Specific examples include compounds in which the allyl group is replaced.
• the compound (C) has the following formulas (11) and (12):
• R 1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogeno group or a hydroxy group
• R 3 represents a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, a hydroxy group or a halogeno group
• R 4 represents a direct bond or a divalent group having 1 to 8 carbon atoms.
• R5 represents an organic group
• R5 represents a divalent organic group having 1 to 8 carbon atoms
• A represents an aromatic ring or an aromatic heterocycle
• t represents 0 or 1
• u represents 1 or 2. It is preferably represented by.).
• the polymer terminal structure represented by the above formulas (11) and (12) is a reaction between the polymer and a compound represented by the following formula (1a) and / or a compound represented by the following formula (2a).
• the meanings of the symbols of the above formulas (1a) and (2a) are as described in the above formulas (11) and (12).
• a compound represented by the formula (1a) for example, a compound represented by the following formula can be mentioned.
• the carboxy group or hydroxy group of the following compounds are acyl group, acetyl group, formyl group, benzoyl group, carboxy group, carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group and allyl. Specific examples include compounds replaced by groups.
• the compound (C) may be a compound represented by the following formula (1-1) described in International Publication No. 2020/071361.
• X is a divalent organic group
• A is an aryl group having 6 to 40 carbon atoms
• R 1 is a halogen atom, an alkyl group having 1 to 40 carbon atoms or an alkyl group.
• the carboxy group of the formula (1-1) is a hydroxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azi group, a thiol group, It may be replaced with a sulfo group and an allyl group.
• ester bond is preferable.
• a above it is a group derived from benzene, naphthalene, anthracene, phenanthrene or pyrene, and among these, a group derived from benzene, naphthalene or anthracene is preferable.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• alkyl group having 1 to 10 carbon atoms examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a pentyl group, and among these, a methyl group is preferable.
• alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexoxy group or a pentoxy group, and among these, a methoxy group is preferable.
• substitution may mean that a part or all of the hydrogen atoms of the above-mentioned alkyl group having 1 to 10 carbon atoms may be substituted with, for example, a fluoro group or a hydroxy group.
• alkyl group having 1 to 10 carbon atoms examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a pentyl group, and a methyl group is preferable.
• the aryl group having 6 to 40 carbon atoms is as described above, but among these, the phenyl group is preferable.
• N1 and n3 are independently integers of 1 to 12, but integers of 1 to 6 are preferable.
• N2 is an integer of 0 to 11, but an integer of 0 to 2 is preferable.
• n2 is 0.
• the carboxy group of the compound described below is a hydroxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azi group, a thiol group and a sulfo group. And may be replaced with an allyl group.
• the compound (C) may be a compound represented by the following formula (2-1) described in International Publication No. 2020/071361.
• X is a divalent organic group
• A is an aryl group having 6 to 40 carbon atoms
• R 2 and R 3 are independently hydrogen atoms, even if they are substituted.
• n3 is an integer of 1 to 12).
• X, A, R 2 , R 3 and n 3, which are preferable in the present invention, are as described above.
• R 2 and R 3 are hydrogen atoms.
• the carboxy group of the compound described below is a hydroxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azi group, a thiol group and a sulfo group. And may be replaced with an allyl group.
• the solvent used in the resist underlayer film forming composition of the present application is not particularly limited as long as it is a solvent capable of uniformly dissolving the contained components such as solid components at room temperature such as the reaction product, but is generally semiconductor lithography.
• Organic solvents used in process chemicals are preferred. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl.
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferable.
• propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.
• thermoacid generator As the acid generator contained as an optional component in the resist underlayer film forming composition of the present invention, either a thermal acid generator or a photoacid generator can be used, but it is preferable to use a thermal acid generator.
• thermoacid generator include p-toluene sulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridiniumphenolsulfonic acid, and pyridinium-p-hydroxybenzenesulfonic acid (pyridinium-p-hydroxybenzenesulfonic acid).
• p-phenol sulfonic acid pyridinium salt pyridinium-trifluoromethane sulfonic acid
• salicyl acid camphor sulfonic acid
• 5-sulfosalicylic acid 4-chlorobenzene sulfonic acid
• 4-hydroxybenzene sulfonic acid 4-hydroxybenzene sulfonic acid
• benzene disulfonic acid 1-naphthalene sulfonic acid
• Examples thereof include sulfonic acid compounds and carboxylic acid compounds such as citrate, benzoic acid and hydroxybenzoic acid.
• photoacid generator examples include onium salt compounds, sulfoneimide compounds, disulfonyldiazomethane compounds and the like.
• onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphor sulfonate, and bis (4-tert-butylphenyl) iodonium camphor sulfonate.
• iodonium salt compounds such as bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butane sulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.
• sulfonium salt compounds and the like can be mentioned.
• sulfoneimide compound examples include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, N- (kanfersulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide. Can be mentioned.
• disulfonyl diazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl).
• Diazomethane methylsulfonyl-p-toluenesulfonyldiazomethane and the like.
• the acid generator can be used alone or in combination of two or more.
• the content ratio of the acid generator is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass, based on the following cross-linking agent. ..
• cross-linking agent examples include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, and 1,3,4,6-tetrakis (methoxymethyl) glycoluril (tetramethoxy).
• Methyl Glycoluryl (POWDERLINK® 1174), 1,3,4,6-tetrakis (butoxymethyl) glycoluryl, 1,3,4,6-tetrakis (hydroxymethyl) glycoluryl, 1,3-bis Examples thereof include (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea.
• cross-linking agent of the present application is a nitrogen-containing compound described in International Publication No. 2017/187969, which has 2 to 6 substituents represented by the following formula (1d) that bind to a nitrogen atom in one molecule. There may be.
• R 1 represents a methyl group or an ethyl group.
• the nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).
• each of the four R 1s independently represents a methyl group or an ethyl group
• R 2 and R 3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, respectively.
• Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).
• a nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule has 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom in one molecule. It is obtained by reacting a nitrogen-containing compound having one with at least one compound represented by the following formula (3d).
• R 1 represents a methyl group or an ethyl group
• R 4 represents an alkyl group having 1 to 4 carbon atoms.
• the glycoluril derivative represented by the formula (1E) is obtained by reacting the glycoluril derivative represented by the following formula (2E) with at least one compound represented by the formula (3d).
• the nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).
• R 2 and R 3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R 4 independently represents an alkyl group having 1 to 4 carbon atoms.
• Examples of the glycoluril derivative represented by the formula (2E) include compounds represented by the following formulas (2E-1) to (2E-4).
• examples of the compound represented by the formula (3d) include compounds represented by the following formulas (3d-1) and (3d-2).
• the content ratio of the cross-linking agent is, for example, 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass, based on the reaction product.
• the resist underlayer film forming composition of the present invention does not generate pinholes or striations, and a surfactant can be further added in order to further improve the coatability against surface unevenness.
• a surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether.
• Polyoxyethylene alkylallyl ethers such as polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc.
• Solbitan fatty acid esters polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
• Nonionic surfactants such as fatty acid esters, Ftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafuck F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd., product) Name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), etc.
• fatty acid esters Ftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafuck F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd., product) Name), Florard FC430, FC431 (manufact
• Fluorosurfactant organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned.
• the blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film forming composition of the present invention.
• These surfactants may be added alone or in combination of two or more.
• the solid content contained in the resist underlayer film forming composition of the present invention, that is, the component excluding the solvent is, for example, 0.01% by mass to 10% by mass.
• the resist underlayer film according to the present invention can be produced by applying the above-mentioned resist underlayer film forming composition on a semiconductor substrate and firing it.
• Examples of the semiconductor substrate to which the resist underlayer film forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. Will be.
• the inorganic film can be, for example, ALD (atomic layer deposition) method, CVD (chemical vapor deposition) method, reactive sputtering method, ion plating method, vacuum deposition. It is formed by a method, a spin coating method (spin-on-glass: SOG).
• ALD atomic layer deposition
• CVD chemical vapor deposition
• reactive sputtering method reactive sputtering method
• ion plating method vacuum deposition. It is formed by a method, a spin coating method (spin-on-glass: SOG).
• spin-on-glass: SOG spin-on-glass
• the inorganic film include a polysilicon film, a silicon oxide film, a silicon nitride film, a BPSG (Boro-Phospho Silicone Glass) film, a titanium nitride film, a titanium nitride film, a tungsten film, a gallium nitride film, and a gallium ar
• the resist underlayer film forming composition of the present invention is applied onto such a semiconductor substrate by an appropriate coating method such as a spinner or a coater. Then, the resist underlayer film is formed by baking using a heating means such as a hot plate.
• the baking conditions are appropriately selected from a baking temperature of 100 ° C. to 400 ° C. and a baking time of 0.3 minutes to 60 minutes.
• the bake temperature is preferably 120 ° C. to 350 ° C. and the bake time is 0.5 minutes to 30 minutes, and more preferably the bake temperature is 150 ° C. to 300 ° C. and the bake time is 0.8 minutes to 10 minutes.
• the film thickness of the resist underlayer film to be formed is, for example, 0.001 ⁇ m (1 nm) to 10 ⁇ m, 0.002 ⁇ m (2 nm) to 1 ⁇ m, 0.005 ⁇ m (5 nm) to 0.5 ⁇ m (500 nm), 0.001 ⁇ m (1 nm).
• the method for manufacturing the patterned substrate goes through the following steps. Usually, it is manufactured by forming a photoresist layer on a resist underlayer film.
• the photoresist formed by applying and firing on the resist underlayer film by a method known per se is not particularly limited as long as it is sensitive to the light used for exposure. Both negative photoresists and positive photoresists can be used.
• a positive photoresist consisting of a novolak resin and a 1,2-naphthoquinone diazidosulfonic acid ester, a chemically amplified photoresist consisting of a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, and an acid.
• a chemically amplified photoresist consisting of a low molecular weight compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate.
• photoresists composed of low molecular weight compounds and photoacid generators that decompose with acid to increase the alkali dissolution rate of photoresists, and resists containing metal elements.
• the product name V146G manufactured by JSR Corporation the product name APEX-E manufactured by Shipley Co., Ltd.
• the product name PAR710 manufactured by Sumitomo Chemical Co., Ltd. the product names AR2772 and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd.
• Proc. SPIE Vol. 3999,330-334 (2000)
• Proc. SPIE Vol. 3999,357-364
• Proc. SPIE Vol. Fluorine-containing atomic polymer-based photoresists as described in 3999,365-374 (2000) can be mentioned.
• WO2019 / 044259 WO2019 / 044331, WO2019 / 0246549, WO2018 / 193954, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP-A-2018-18525, WO2018 / 200888, JP-A-2018-075076, JP-A-2018.
• the so-called resist composition such as the radioactive resin composition, the high-resolution patterning composition based on the organic metal solution, and the metal-containing resist composition can be used. , Not limited to these.
• Examples of the resist composition include the following compositions.
• Sensitive photosensitivity or sensation which comprises a resin A having a repeating unit having an acid-degradable group whose polar group is protected by a protective group desorbed by the action of an acid, and a compound represented by the general formula (21). Radial resin composition.
• m represents an integer of 1 to 6.
• R 1 and R 2 independently represent a fluorine atom or a perfluoroalkyl group.
• L 1 represents -O-, -S-, -COO-, -SO 2- , or -SO 3- .
• L 2 represents an alkylene group or a single bond which may have a substituent.
• W 1 represents a cyclic organic group which may have a substituent.
• M + represents a cation
• Extreme ultraviolet rays or electron beams containing a compound having a metal-oxygen covalent bond and a solvent, and the metal elements constituting the compound belong to the 3rd to 7th periods of the 3rd to 15th groups of the periodic table.
• Metal-containing film-forming composition for lithography Metal-containing film-forming composition for lithography.
• Ar is a group obtained by removing (n + 1) hydrogen atoms from an arene having 6 to 20 carbon atoms.
• R 1 is a hydroxy group, a sulfanyl group or a monovalent group having 1 to 20 carbon atoms.
• N is an integer of 0 to 11.
• R 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
• R 3 is a monovalent group having 1 to 20 carbon atoms including the acid dissociative group.
• Z is a single bond, an oxygen atom or a sulfur atom.
• R 4 is. , Hydrogen atom, fluorine atom, methyl group or trifluoromethyl group.
• R 2 represents an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom or a halogen atom
• X 1 is a single bond, -CO-O- * or -CO-NR 4- *.
• * Represents a bond with -Ar
• R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• Ar represents one or more groups selected from the group consisting of a hydroxy group and a carboxyl group. Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have.
• Examples of the resist film include the following.
• RA is independently a hydrogen atom or a methyl group
• R1 and R2 are independently tertiary alkyl groups having 4 to 6 carbon atoms.
• R 3 is an independently fluorine atom or a methyl group.
• M is an integer of 0 to 4.
• X 1 is a single bond, a phenylene group or a naphthylene group, or an ester bond, a lactone ring, a phenylene. It is a linking group having 1 to 12 carbon atoms including at least one selected from a group and a naphthylene group.
• X 2 is a single bond, an ester bond or an amide bond.
• Examples of the resist material include the following.
• RA is a hydrogen atom or a methyl group.
• X 1 is a single bond or ester group.
• X 2 is a linear, branched or cyclic carbon. It is an alkylene group having a number of 1 to 12 or an arylene group having 6 to 10 carbon atoms, and a part of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group or a lactone ring-containing group. Further, at least one hydrogen atom contained in X 2 is substituted with a bromine atom.
• X 3 is a single bond, an ether group, an ester group, or a linear, branched or cyclic substance having 1 to 12 carbon atoms. It is an alkylene group, and a part of the methylene group constituting the alkylene group may be substituted with an ether group or an ester group.
• Rf 1 to Rf 4 are independently hydrogen atom, fluorine atom or trifluoro. Although it is a methyl group, at least one is a fluorine atom or a trifluoromethyl group. Further, Rf 1 and Rf 2 may be combined to form a carbonyl group.
• R 1 to R 5 are independent of each other.
• Aryl group, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups are hydroxy groups, carboxy groups, halogen atoms, and oxos.
• R 1 and R 2 may be bonded to form a ring together with the sulfur atom to which they are bonded.
• RA is a hydrogen atom or a methyl group.
• R 1 is a hydrogen atom or an acid unstable group.
• R 2 is a linear, branched or cyclic carbon number 1 to 1. The alkyl group of 6 or a halogen atom other than bromine.
• X 1 may contain a single bond or a phenylene group, or an ester group or a lactone ring.
• Linear, branched or cyclic carbon atoms 1 to 12 X 2 is -O-, -O-CH 2- or -NH-.
• M is an integer of 1 to 4.
• n is an integer of 0 to 3).
• a resist composition that generates acid by exposure and changes its solubility in a developing solution by the action of the acid.
• the fluorine additive component (F) has a constituent unit (f1) containing a base dissociative group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1).
• a resist composition comprising a resin component (F1).
• Rf 21 is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group.
• n is an integer from 0 to 2. * Is a bond.
• the structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).
• R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms, respectively.
• X is a divalent linking group having no acid dissociation site.
• a aryl is a divalent aromatic cyclic group which may have a substituent.
• X 01 is a single bond or divalent linking group.
• R 2 is an organic group each independently having a fluorine atom.
• Examples of the coating, the coating solution, and the coating composition include the following.
• Coating solution, organic solvent; first organic metal composition, formula R z SnO (2- (z / 2)-(x / 2)) (OH) x (where 0 ⁇ z). ⁇ 2 and 0 ⁇ (z + x) ⁇ 4), expressed by the formula R'n SnX 4-n ( where n 1 or 2), or a mixture thereof, where R and R'.
• RSnO (3 / 2-x / 2) (OH) x
• An aqueous solution of an inorganic pattern-forming precursor containing a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.
• the exposure is performed through a mask (reticle) for forming a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) are used.
• the resist underlayer film forming composition of the above is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and is preferably applied for EUV (extreme ultraviolet) exposure.
• An alkaline developer is used for development, and the development temperature is appropriately selected from 5 ° C to 50 ° C and the development time is 10 seconds to 300 seconds.
• alkaline developer examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and the like. Secondary amines such as g-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and the like.
• an aqueous solution of an alkali such as a quaternary ammonium salt, cyclic amines such as pyrrole and piperidine can be used.
• an alcohol such as isopropyl alcohol and a surfactant such as a nonionic surfactant can be added to the aqueous solution of the alkalis in an appropriate amount for use.
• the preferred developer is a quaternary ammonium salt, more preferably tetramethylammonium hydroxide and choline.
• a surfactant or the like can be added to these developers.
• a method of developing with an organic solvent such as butyl acetate to develop a portion of the photoresist in which the alkali dissolution rate has not been improved can also be used. Through the above steps, a substrate on which the above resist is patterned can be manufactured.
• the resist underlayer film is dry-etched using the formed resist pattern as a mask.
• the inorganic film is formed on the surface of the used semiconductor substrate, the surface of the inorganic film is exposed, and if the inorganic film is not formed on the surface of the used semiconductor substrate, the semiconductor substrate is exposed. Expose the surface.
• the semiconductor device can be manufactured through a step of processing the substrate by a method known per se (dry etching method or the like).
• the weight average molecular weights of the polymers shown in the following Synthesis Example 1 and Comparative Synthesis Example 1 of the present specification are measurement results by gel permeation chromatography (hereinafter abbreviated as GPC).
• GPC gel permeation chromatography
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1a), (2a) and (3a).
• the polymer solution does not cause cloudiness even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• the polymer in the obtained solution had a weight average molecular weight of 8,000 in terms of standard polystyrene.
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1a), (4a) and (3a).
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1a), (6a) and (7a).
• the reaction vessel was replaced with nitrogen and then reacted at 120 ° C. for 24 hours to obtain a polymer solution.
• the polymer solution does not cause cloudiness even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• the polymer in the obtained solution had a weight average molecular weight of 7,000 in terms of standard polystyrene.
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1a), (8a) and (7a).
• the reaction vessel was replaced with nitrogen and then reacted at 105 ° C. for 8 hours to obtain a polymer solution.
• the polymer solution does not cause cloudiness even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• the polymer in the obtained solution had a weight average molecular weight of 5,000 in terms of standard polystyrene.
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1b), (2a) and (3a).
• the reaction vessel was replaced with nitrogen and then reacted at 105 ° C. for 24 hours to obtain a polymer solution.
• the polymer solution does not cause cloudiness even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• the polymer in the obtained solution had a weight average molecular weight of 8,300 in terms of standard polystyrene.
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1b), (4a) and (3a).
• the reaction vessel was replaced with nitrogen and then reacted at 105 ° C. for 24 hours to obtain a polymer solution.
• the polymer solution does not cause cloudiness even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• the polymer in the obtained solution had a weight average molecular weight of 6,200 in terms of standard polystyrene.
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1b), (6a) and (7a).
• the reaction vessel was replaced with nitrogen and then reacted at 105 ° C. for 24 hours to obtain a polymer solution.
• the polymer solution does not cause cloudiness even when cooled to room temperature, and has good solubility in propylene glycol monomethyl ether.
• the polymer in the obtained solution had a weight average molecular weight of 8,300 in terms of standard polystyrene.
• the polymer obtained in this synthetic example has structural units represented by the following formulas (1b), (8a) and (7a).
• Example 1 To 0.43 g (solid content: 16.4% by weight) of the polymer solution obtained in the above synthesis example 1, 0.02 g of tetramethoxymethyl glycol uryl (manufactured by Nippon Cytec Industries Co., Ltd.) and 0.003 g of pyridinium phenol sulfonic acid. , 44.5 g of propylene glycol monomethyl ether and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, it was filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to obtain a resist underlayer film forming composition for lithography.
• Example 2 To 0.47 g (solid content: 17.8% by weight) of the polymer solution obtained in the above synthesis example 2, 0.02 g of tetramethoxymethyl glycol uryl (manufactured by Nippon Cytec Industries Co., Ltd.) and 0.003 g of pyridinium phenol sulfonic acid. , 44.6 g of propylene glycol monomethyl ether and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, it was filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to obtain a resist underlayer film forming composition for lithography.
• Example 3 To 0.47 g (solid content: 18.3% by weight) of the polymer solution obtained in the above synthesis example 3, 0.02 g of tetramethoxymethyl glycol uryl (manufactured by Nippon Cytec Industries Co., Ltd.) and 0.003 g of pyridinium phenol sulfonic acid. , 44.6 g of propylene glycol monomethyl ether and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, it was filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to obtain a resist underlayer film forming composition for lithography.
• Example 4 To 0.48 g (solid content: 17.7% by weight) of the polymer solution obtained in the above synthesis example 4, 0.02 g of tetramethoxymethyl glycol uryl (manufactured by Nippon Cytec Industries Co., Ltd.) and 0.003 g of pyridinium phenol sulfonic acid. , 44.4 g of propylene glycol monomethyl ether and 4.99 g of propylene glycol monomethyl ether acetate were added and dissolved. Then, it was filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to obtain a resist underlayer film forming composition for lithography.
• Example 1 and Example 2 As compared with Comparative Example 1 and Comparative Example 2, the pillar pattern can be suppressed from collapsing and peeling, and has a good pattern forming ability. Further, it was confirmed that the required exposure amount was also possible to form a pattern with a smaller exposure amount than in Comparative Example 1 and Comparative Example 2 in both Example 1 and Example 2.
• the resist underlayer film forming composition of the present invention exhibits better lithography performance as compared with the prior art.
• the resist underlayer film forming composition according to the present invention is a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for producing a substrate with a resist pattern using the resist underlayer film forming composition, and a semiconductor.
• a method of manufacturing an apparatus can be provided.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Architecture (AREA)
• Structural Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Materials For Photolithography (AREA)
• Epoxy Resins (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=81126956

Family Applications (1)

Country Status (6)

Cited By (1)

Citations (2)

Family Cites Families (18)

• 2021
  • 2021-10-06 JP JP2022555518A patent/JPWO2022075339A1/ja active Pending
  • 2021-10-06 US US18/029,314 patent/US20240004295A1/en active Pending
  • 2021-10-06 WO PCT/JP2021/036900 patent/WO2022075339A1/ja not_active Ceased
  • 2021-10-06 CN CN202180065966.1A patent/CN116234852A/zh active Pending
  • 2021-10-06 KR KR1020237009632A patent/KR102927084B1/ko active Active
  • 2021-10-07 TW TW110137303A patent/TWI902926B/zh active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events