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
• • 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
• • 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
  • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
  • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
  • C08G12/06—Amines
  • C08G12/08—Amines aromatic
• • 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
  • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
  • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic 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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
• • 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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
• • 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
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
  • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
• • 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
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
  • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
  • C09D161/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
• • 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
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
• • 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
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • 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
• • 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
  • H10P76/40—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials
  • H10P76/405—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their composition, e.g. multilayer masks

Definitions

• the present invention relates to a composition for forming a resist underlayer film.
• Patent Literature 1 discloses a resist underlayer film forming composition used in a multilayer resist process, which contains at least a novolak resin, and has a repeating unit in which the novolak resin is substituted with a predetermined group. Has been described.
• the resist underlayer film In order to suitably perform the multilayer resist process, the resist underlayer film must be insoluble in a photoresist solution (a solution for forming a photoresist film) and have high etching selectivity, and a resist underlayer film forming composition Is required to have a property that the polymer has good solubility in a solvent in the composition.
• a photoresist solution a solution for forming a photoresist film
• a resist underlayer film forming composition Is required to have a property that the polymer has good solubility in a solvent in the composition.
• the present invention is capable of forming a resist underlayer film having high etching selectivity on the insoluble in the photoresist solution, and includes a polymer having good solubility in a solvent in the resist underlayer film forming composition.
• An object of the present invention is to provide the composition for forming a resist underlayer film and a method for producing the same.
• Another object of the present invention is to provide a resist underlayer film, a method for manufacturing the same, a method for manufacturing a patterned substrate, and a method for manufacturing a semiconductor device, which are realized using the composition for forming a resist underlayer film.
• a first aspect of the present invention that solves the above-mentioned problems is a resist underlayer film forming composition including a polymer to which a group represented by the following formula (1) is added.
• R x , S y and S z are each independently a hydrogen atom or a monovalent organic group, and R y and R z are each independently a single bond or a divalent organic group.
• a group, the ring Ar y and ring Ar z are independently an aryl group of a cyclic alkyl group or a C 6 to 30 4 to 20 carbon atoms, and bonded to each other to form a ring Ar y and ring Ar the maximum number z may form a new ring during, n y is an integer up to the maximum number that can be replaced by 0 or more and ring Ar y, n z is be replaced to 0 or higher and the ring Ar z Is an integer up to and * is the bonding position with the polymer.
• At least one of the rings Ar y and the ring Ar z includes an aryl group having 6 to 30 carbon atoms, a resist underlayer film forming composition according to the first aspect.
• the group represented by the formula (1) is at least one selected from the following formulas (1-1) to (1-15):
• the polymer includes at least one of a unit represented by the following formula (1a) and a unit represented by the following formula (1b). 4.
• AU is each independently a group represented by the formula (1)
• R 1 is each independently a halogen group, a nitro group, an amino group, or a hydroxy group.
• glycidyl ether group, an aromatic hydrocarbon group, an alkenyl group of the alkyl group and 2 to 10 carbon atoms having 1 to 10 carbon atoms, and ethers may include at least one of ketones and esters
• R 2 is Each independently represents a hydrogen atom, an aromatic hydrocarbon group or a heterocyclic group
• R 3 each independently represents a hydrogen atom, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms
• aromatic hydrocarbon group and the heterocyclic group of R 2 and R 3 are each independently a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, an alkyl carboxylic
• a fifth aspect of the present invention is the resist underlayer film forming composition according to any one of the first to fourth aspects, wherein the polymer is a novolak resin.
• AU is a group represented by the formula (1), and R 1 is each independently a halogen group, a nitro group, an amino group, or an aromatic group.
• a hydrocarbon group, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms R 2 is each independently an aromatic hydrocarbon group or a heterocyclic group, and R 3 is each independently And when R 2 and R 3 are each a phenyl group, they may combine with each other to form a fluorene ring, and R 4 may be each independently a hydrogen atom, an acetal A group, an acyl group, a glycidyl group, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, ring Ar 1 is a benzene ring, X is each independently a benzene ring, And two of the benzene rings -C (CH 3)
• the resist underlayer film forming composition according to any one of the first to sixth aspects, wherein the polymer includes a polymer represented by the following formula (1a-3): Things.
• AU is a group represented by the formula (1), and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, a C 6-40 An aromatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and may contain at least one of ether, ketone and ester, and R 2 is a heterocyclic group or An aromatic hydrocarbon group having 6 to 40 carbon atoms, wherein the heterocyclic group or the aromatic hydrocarbon group is a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a hydroxy group, a C1 to C10 group; R 3 may be a hydrogen atom, a heterocyclic group, an aromatic group having 6 to 40 carbon atoms, an alkyl group, an alkoxy group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms.
• Group hydrocarbon group 1-10 carbon atoms
• R 2 and R 3 may combine with each other to form a ring
• R 5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl having 2 to 10 carbon atoms.
• At least one of a group and an aryl group having 6 to 40 carbon atoms may include at least one of an ether, a ketone and an ester, and the rings Ar 1 are each independently a benzene ring or a naphthalene ring; n 1 are each independently an integer of 0-3, the sum of n a + n b is an integer of 1 or more independently, the sum and the sum of n b + n 1 of n a + n 1 is Ring Ar It is an integer up to the maximum number that can be replaced by 1. )
• An eighth aspect of the present invention is a resist underlayer film forming composition according to any one of the first to seventh aspects, wherein the polymer comprises a polymer represented by the following formula (1b-1): Things.
• AU is a group represented by the formula (1), and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, a C 6-40 aromatic hydrocarbon group, an alkenyl group of the alkyl group and 2 to 10 carbon atoms having 1 to 10 carbon atoms, and ethers may include at least one of ketones and esters, R 2 is a hydrogen atom, a heterocyclic A ring group or an aromatic hydrocarbon group having 6 to 40 carbon atoms, wherein the heterocyclic group or the aromatic hydrocarbon group is a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group; , A phenyl group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and R 3 represents a hydrogen atom, a heterocyclic group,
• Another embodiment (ninth embodiment) of the present invention that solves the above-mentioned problems includes a compound containing a group represented by the above formula (1), an aldehyde and / or a ketone, a bisphenol, an amine and a complex.
• a fired product of a coating film containing the resist underlayer film forming composition according to any one of the first to eighth aspects is provided. Which is a resist underlayer film.
• the resist underlayer film forming composition according to any one of the first to eighth aspects is applied on a substrate.
• a method for producing a resist underlayer film comprising a step of forming a coating film and a step of baking the coating film.
• a resist is formed on a substrate by using the resist underlayer film forming composition according to any one of the first to eighth aspects.
• a step of processing a patterned substrate is formed on a substrate by using the resist underlayer film forming composition according to any one of the first to eighth aspects.
• a step of applying the resist underlayer film forming composition according to any one of the first to eighth aspects on a substrate a step of applying the resist underlayer film forming composition according to any one of the first to eighth aspects on a substrate. And a step of etching a resist underlayer film according to a predetermined pattern, and a step of processing a substrate based on the patterned resist underlayer film.
• a resist underlayer film having high etching selectivity on a photoresist solution and insoluble on a photoresist solution contains a polymer having good solubility in a solvent in a resist underlayer film forming composition.
• the composition for forming a resist underlayer film and a method for producing the same can be provided.
• composition for forming a resist underlayer film used in a multilayer resist process.
• the multi-layer resist process is also called a multi-layer process.
• an etching gas having different etching selectivity between an inorganic layer and an organic layer for example, an oxygen-based gas or a hydrogen-based gas, Etching is performed alternately using a halogen-based gas such as CF 4 gas, which has an opposite etching selectivity, thereby patterning the substrate.
• the laminate includes, for example, a semiconductor substrate (an inorganic layer in a multilayer resist process), a resist underlayer film formed on the semiconductor substrate (an organic layer in the multilayer resist process), and a hard mask formed on the resist underlayer film (multilayer).
• a semiconductor substrate an inorganic layer in a multilayer resist process
• a resist underlayer film formed on the semiconductor substrate an organic layer in the multilayer resist process
• a hard mask formed on the resist underlayer film (multilayer).
• An inorganic layer in a resist process) and a photoresist film organic layer in a multilayer resist process formed on a hard mask.
• the above composition is suitable for forming a resist underlayer film.
• composition contains a polymer to which a group represented by the following formula (1) is added (hereinafter, may be simply referred to as “polymer”).
• R x , S y and S z are each independently a hydrogen atom or a monovalent organic group, and R y and R z are each independently a single bond or a divalent organic group.
• the ring Ar y and ring Ar z are independently an aryl group of a cyclic alkyl group or a C 6 to 30 4 to 20 carbon atoms, and bonded to each other to form a ring Ar y and ring Ar z It may form a new ring during, n y is an integer up to the maximum number that can be replaced by 0 or more and ring Ar y, n z is up to the maximum number that can be replaced by 0 or more and the ring Ar z And * is a bonding site with the polymer. It is sufficient that one or more groups represented by the formula (1) are added to the polymer.
• the polymer to which the group represented by the formula (1) is added has good solubility in the solvent in the composition.
• a solvent eg, methyl 2-hydroxyisobutyrate
• the polymer is easily reprecipitated using an organic solvent such as methanol, and thus the purity thereof is easily increased.
• the group represented by the formula (1) is designed so that the content of the carbon component is relatively high. This is based on the tendency that the present inventors have noticed that the higher the content of the carbon component in the compound, the easier the etching selectivity is. Therefore, by using the above polymer, it is possible to form a resist underlayer film having high etching resistance to an etching gas (halogen-based gas such as CF 4 gas) used in a multilayer resist process, and furthermore, high etching selectivity. it can.
• etching gas halogen-based gas such as CF 4 gas
• the resist underlayer film obtained using the above composition is insoluble in a photoresist solution as evaluated in Examples described later.
• a resist underlayer film By using such a resist underlayer film, it becomes easy to prevent intermixing with a photoresist layer in a multilayer resist process.
• the composition is capable of forming a resist underlayer film having high etching selectivity on an insoluble in a photoresist solution, and includes a polymer having good solubility in a solvent in the composition. . Therefore, by using the above composition, it becomes easy to suitably carry out the multilayer resist process. It is expected that by appropriately performing the multilayer resist process, the patterning performed on the substrate becomes finer and that the substrate in which the patterning is deeply formed is easily manufactured.
• R x , S y and S z are each independently a hydrogen atom or a monovalent organic group.
• the monovalent organic group has 1 to 20 carbon atoms and may contain at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
• the monovalent organic group may have any of a linear skeleton and a branched skeleton, and may have a cyclic skeleton. Further, the monovalent organic group may contain an unsaturated bond.
• R y and R z are each independently a single bond or a divalent organic group.
• the divalent organic group has 1 to 20 carbon atoms and may contain at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
• the divalent organic group may be any of a linear skeleton and a branched skeleton, and may include a cyclic skeleton. Further, the divalent organic group may contain an unsaturated bond.
• each of the ring Ar 1 and the ring Ar 2 is independently a cyclic alkyl group having 4 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms.
• at least one of the ring Ar 1 and the ring Ar 2 is preferably an aryl group having 6 to 30 carbon atoms.
• the ring Ar y and Ring Ar z may form a new ring between the ring Ar y and ring Ar z bonded to each other.
• the group represented by formula (1) is preferably at least one of formulas (1-1) to (1-5).
• the group represented by the formula (1) is not limited to the above formula as long as the effects of the present invention can be obtained.
• the polymer includes at least one of a unit represented by the following formula (1a) and a unit represented by the following formula (1b).
• AU is each independently a group represented by the formula (1), and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, glycidyl ether group, an aromatic hydrocarbon group, an alkenyl group of the alkyl group and 2 to 10 carbon atoms having 1 to 10 carbon atoms, and ethers may include at least one of ketones and esters, R 2 is Each independently represents a hydrogen atom, an aromatic hydrocarbon group or a heterocyclic group; R 3 represents each independently a hydrogen atom, an aromatic hydrocarbon group, a heterocyclic group, an alkyl group having 1 to 10 carbon atoms or a carbon atom; an alkenyl group having 2 to 10, aromatic hydrocarbon group and the heterocyclic group of R 2 and R 3 are each independently a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, alkyl ether carboxylic acid Ether
• the polymer contains both the unit represented by the formula (1a) and the unit represented by the formula (1b), the polymer includes the unit represented by the formula (1a) and the unit represented by the formula (1b) In the case where it does not include, it does not include the unit represented by the formula (1a), and it includes the unit represented by the formula (1b).
• the lower limit of the weight average molecular weight of the polymer is, for example, 100, 400, or 600, and the upper limit is, for example, 50,000, 40,000, or 30,000. However, the upper and lower limits of these weight average molecular weights are examples.
• the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and converted into polystyrene.
• the above polymers include novolak resins.
• the novolak resin is obtained by a polymerization reaction using aldehydes and / or ketones and at least one of bisphenols, amines and heterocycles as raw materials.
• these raw materials and a compound containing a group represented by the formula (1) (hereinafter, sometimes referred to as an “addition unit”) are charged at once and a polymerization reaction is carried out.
• the reaction may proceed, or the polymerization reaction may be carried out using the raw materials, and an additional unit may be added to the obtained novolak resin.
• conditions such as the presence or absence and type of an acid catalyst, the presence or absence and type of a reaction solvent, the timing of mixing each component, the charging ratio of each component, the reaction time and the reaction temperature are appropriately determined according to the polymer to be produced Can be set.
• the acid catalyst include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as metasulfonic acid, p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. And the like.
• the reaction solvent is not limited as long as it does not inhibit the polymerization reaction, and known solvents such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 1,4-dioxane can be used.
• the acid catalyst can also serve as a reaction solvent.
• Each of the acid catalyst and the reaction solvent may be used alone or in combination of two or more.
• the lower limit of the molecular weight of the additional unit is, for example, 50, 100, or 150, and the upper limit is, for example, 500, 400, or 300. It is preferable that the molecular weight of at least one of the additional units used for producing the polymer, and the average value of the molecular weights of all the additional units used for producing the polymer are within the above range.
• aldehydes examples include aromatic aldehydes, saturated aliphatic aldehydes, unsaturated aliphatic aldehydes, and heterocyclic aldehydes. These may be used alone or in combination of two or more.
• aromatic aldehyde examples include 1-pyrenecarboxaldehyde, benzaldehyde, naphthylaldehyde, anthracenecarboxaldehyde, anisaldehyde, terephthalaldehyde, anthrylaldehyde, phenanthraldehyde, salicylaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde, and tolylaldehyde. , (N, N-dimethylamino) benzaldehyde and acetoxybenzaldehyde. These may be used alone or in combination of two or more.
• saturated aliphatic aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, caproaldehyde, 2-methylbutyraldehyde, hexylaldehyde, undecanealdehyde, 7-methoxy-3, 7- Examples thereof include dimethyloctylaldehyde, cyclohexanealdehyde, 3-methyl-2-butyraldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, glutaraldehyde, and adipaldehyde. These may be used alone or in combination of two or more.
• unsaturated aliphatic aldehydes examples include acrolein and methacrolein. These may be used alone or in combination of two or more.
• heterocyclic aldehyde examples include furfural, pyridine aldehyde, thiophenaldehyde, and the like. These may be used alone or in combination of two or more.
• Aromatic ketones include diphenyl ketone, phenyl naphthyl ketone, dinaphthyl ketone, phenyl tolyl ketone, ditolyl ketone, 9-fluorenone, and the like. These may be used alone or in combination of two or more.
• a first polymer is obtained by using bisphenols
• a second polymer is obtained by using amines
• a third polymer is obtained by using heterocycles.
• the units represented by the formulas (1a) and (1b) have a relatively flexible skeleton.
• the flexible skeleton is advantageous from the viewpoint of facilitating the contact of the composition up to the gap due to the step on the substrate having the step, and from the viewpoint of easily forming a coating film with high flatness even on the substrate having the step.
• the polymer is preferably at least one of a first polymer, a second polymer, and a third polymer.
• the first polymer is It contains a unit represented by the following formula (1a-1) and / or the following formula (1a-2).
• AU is as described above, and R 1 is each independently a halogen group, a nitro group, an amino group, an aromatic hydrocarbon group, and a group having 1 carbon atom.
• R 2 is independently an aromatic hydrocarbon group or a heterocyclic group, and R 3 is each independently a hydrogen atom or a phenyl group. Or when R 2 and R 3 are each a phenyl group, they may combine with each other to form a fluorene ring, and R 4 is each independently a hydrogen atom, an acetal group, an acyl group, or a glycidyl group.
• ring Ar 1 is a benzene ring
• X is each independently a benzene ring, and is bonded to the benzene ring.
• two -C to (CH ) 2 - group is in the relation of the meta or para position
• n 1 is 0 or 1 each independently
• the sum of n a + n b is an integer of 1 or more independently
• n a The sum of + n 1 and the sum of n b + n 1 are integers up to the maximum number that can be substituted for ring Ar 1 .
• the first polymer contains both the unit represented by the formula (1a-1) and the unit represented by the formula (1a-2), the first polymer contains the unit represented by the formula (1a-1), When the unit represented by the formula (1a-2) is not included, the case where the unit represented by the formula (1a-2) is not included, and the case where the unit represented by the formula (1a-2) is included is applicable. .
• the skeleton of the first polymer is not limited to the above specific examples as long as the effects of the present invention can be obtained.
• the first polymer is synthesized by a polymerization reaction of an additional unit, an aldehyde and / or a ketone, and a phenol.
• bisphenols include 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 2-phenylindole, 1-phenyl-2-naphthylamine, and 1,4-bis [2- ( 4-hydroxyphenyl) -2-propyl] benzene. These may be used alone or in combination of two or more.
• the second polymer includes a polymer represented by the following formula (1a-3).
• AU is as described above, and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, An alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms, and may include at least one of ether, ketone and ester, and R 2 is a heterocyclic group or an aromatic group having 6 to 40 carbon atoms.
• a heterocyclic group or an aromatic hydrocarbon group such as a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms
• R 3 may be a hydrogen atom, a heterocyclic group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, a carbon atom having 6 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms.
• 1 to 10 alkyl groups Is an alkenyl group having 2 to 10 carbon atoms, wherein the heterocyclic group, the aromatic hydrocarbon group, the alkyl group or the alkenyl group is at least one of a halogen group, a nitro group, an amino group and a hydroxy group
• R 2 and R 3 may combine with each other to form a ring
• R 5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and at least one aryl group having 6 to 40 carbon atoms
• ethers may include at least one of ketones and esters
• rings Ar 1 are each independently a benzene ring or a naphthalene ring
• n 1 are each independently an integer of 0-3
• the sum of n a + n b is an integer of 1 or more independently, the sum and the sum of n b + n 1 of n a + n 1,
• the second polymer includes a copolymer including a unit represented by the formula (1a-3) and a unit represented by the following formula (1a-4).
• AU, R 2 and R 3 are as defined above, the sum of n a + n b is an integer of 1 or more independently, each of n a and n 1 , Ring Ar 1 is an integer up to the maximum number that can be substituted.
• the skeleton of the second polymer is not limited to the above specific examples as long as the effects of the present invention can be obtained.
• the second polymer is synthesized by polymerizing an additional unit, an aldehyde and / or a ketone, and an amine.
• Amines include carbazoles and triphenylamines. These may be used alone or in combination of two or more.
• carbazoles examples include carbazole, N-methylcarbazole, N-ethylcarbazole, 1,3,6,8-tetranitrocarbazole, 3,6-diaminocarbazole, 3,6-dibromo-9-ethylcarbazole, 3,6 -Dibromo-9-phenylcarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3-amino-9-ethylcarbazole, 3-bromo-9-ethylcarbazole, 4,4'bis (9H-carbazole- 9-yl) biphenyl, 4-glycidylcarbazole, 4-hydroxycarbazole, 9- (1H-benzotriazol-1-ylmethyl) -9H-carbazole, 9-acetyl-3,6-diiodocarbazole, 9-benzoylcarbazole, 9-benzoylcarbazole-6-d
• triphenylamines examples include, for example, triphenylamine.
• Triphenylamine may include a substituent.
• substituents include a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 40 carbon atoms.
• Substituents may include ethers, ketones, or esters. These may be used alone or in combination of two or more.
• the third polymer includes a polymer represented by the following formula (1b-1).
• AU is as described above, and R 1 is each independently a halogen group, a nitro group, an amino group, a hydroxy group, an aromatic hydrocarbon group having 6 to 40 carbon atoms, alkyl and alkenyl groups having 2 to 10 carbon atoms having from 1 to 10, and ethers may include at least one of ketones and esters, R 2 is a hydrogen atom, a heterocyclic group or C 6 -C 40 aromatic hydrocarbon groups, the heterocyclic group or the aromatic hydrocarbon group is a halogen group, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, a hydroxy group, R 3 may include at least one substituent of an alkoxy group having 1 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and R 3 is a hydrogen atom, a heterocyclic group, or an aromatic hydrocarbon group having 6
• An alkyl group of prime 1 ⁇ 10, R 2 and R 3 may be bonded to each other to form a ring, the ring Ar 1 is a benzene ring, a naphthalene ring or an anthracene ring, R 5 is hydrogen At least one of an atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms and an aryl group having 6 to 40 carbon atoms, and may contain at least one of ether, ketone and ester.
• n a + n b is an integer of 1 or more independently
• n 1 and n 3 is an integer of 0 or more each independently
• a n a + n 1 of total and n b + n 1 is an integer up to the maximum number that can be substituted for the ring Ar 1 and n 3 is an integer up to the maximum number that can be substituted for the heterocycle to which it is attached.
• the skeleton of the third polymer is not limited to the above specific examples as long as the effects of the present invention can be obtained.
• the third polymer is synthesized by polymerizing an additional unit, an aldehyde and / or a ketone, and a heterocycle.
• the heterocycle is a compound containing a 5- to 6-membered heterocyclic group containing nitrogen, sulfur and oxygen, such as a pyrrole group, a furan group, a thiophene group, an imidazole group, an oxazole group, a thiazole group, and a pyrazole group.
• the composition contains a solvent.
• a solvent ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, Methyl cellosolve acetate, ethyl cellosolve acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutanoate Methyl 3-methoxypropionate, ethyl 3-methoxypropionat
• the lower limit of the ratio of the solid content is, for example, 0.1% by mass or more, 0.5% by mass or more, and 0.8% by mass or more
• the upper limit is, for example, , 70% by mass or less, 50% by mass or less, and 30% by mass or less.
• the content ratio of the total polymer in the solid content is 1 to 100% by mass, 20 to 99.9% by mass, and 50 to 99.9% by mass.
• the composition may include other components (for example, a crosslinking agent, an acidic compound, an acid generator, a surfactant, and other polymers) in addition to the polymer and the solvent.
• a crosslinking agent for example, a crosslinking agent, an acidic compound, an acid generator, a surfactant, and other polymers
• crosslinking agent examples include 4,4 ′-(1-methylethylidine) bis [2,6-bis [(2-methoxy-1-methylethoxy) methyl] -phenol, methoxymethylated glycoluril, and butoxymethylated glycol
• examples include uril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and methoxymethylated thiourea. Condensates of these compounds can also be used. These may be used alone or in combination of two or more.
• the content of the crosslinking agent is, for example, 80% by mass or less, 60% by mass or less, and 40% by mass or less based on the solid content of the composition.
• the acidic compound and / or the acid generator function as a catalyst for promoting a crosslinking reaction.
• the acidic compound include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-phenolsulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and the like. These may be used alone or in combination of two or more.
• Examples of the acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, other organic sulfonic acid alkyl esters, trifluoromethanesulfonic acid, quaternary ammonium salts, and TMOM.
• -BP 3,5 ', 5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl, manufactured by Honshu Chemical Industry Co., Ltd.
• the content ratio of the acidic compound and / or the thermal acid generator is, for example, 20% by mass or less, or 10% by mass or less based on the solid content of the composition.
• surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl.
• Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate
• Fatty acids such as sorbitan, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan Nonionic surfactants such as palmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, EFTOP EF301, EF303, EF352 (Mitsubishi Material Denka Kasei Co., Ltd.), Megafac F171, F173, R-30, R-30-N (DIC Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), As
• the content of the surfactant is, for example, 5% by mass or less, 2% by mass or less, and 1% by mass or less based on the solid content of the composition.
• Other polymers include polyacrylate compounds, polymethacrylate compounds, polyacrylamide compounds, polymethacrylamide compounds, polyvinyl compounds, polystyrene compounds, polymaleimide compounds, polymaleic anhydride, and polyacrylonitrile compounds.
• the content of the other polymer is 30% by mass or less and 10% by mass or less based on all the polymers contained in the composition.
• the composition obtained as described above can be suitably purified by performing reprecipitation using an organic solvent such as methanol, and can also be appropriately dried using a reduced-pressure drier or the like. it can.
• the above composition can be prepared by dissolving each of the above components in a solvent, and is used in a uniform solution state.
• the prepared composition is preferably used after being filtered using a filter or the like having a pore size of 0.02 ⁇ m.
• the resist underlayer film according to the present embodiment is a fired product of a coating film containing the above composition.
• the method for producing a resist underlayer film according to the present embodiment includes a step of applying the composition on a substrate to form a coating film, and a step of baking (baking) the coating film.
• the substrate examples include a so-called semiconductor substrate (a silicon wafer, a germanium wafer, or the like, which may be covered with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film).
• the application method include a spin coating method, a printing method, and an ink jet method, but are not limited thereto.
• ⁇ Arbitrary conditions can be set for the temperature and time for firing.
• the firing temperature is 150 ° C. to 600 ° C., or 350 ° C. to 450 ° C.
• the firing time is 0.5 minutes to 5 minutes, or 1 minute. ⁇ 3 minutes.
• the thickness of the resist underlayer film can be appropriately changed depending on the application of the resist underlayer film and the like, and is, for example, 50 nm or more, or 100 nm or more, 1000 nm or less, or 500 nm or less.
• the method for producing a patterned substrate includes a step of forming a resist underlayer film on the substrate using the composition, a step of forming a predetermined hard mask on the resist underlayer film, Forming a photoresist pattern thereon, forming a resist pattern by exposing and developing the photoresist film, etching the hard mask with the resist pattern, forming a mask pattern, and using the mask pattern to form the resist underlayer. Forming a resist underlayer pattern by etching the film; and processing a substrate using the resist underlayer pattern.
• the method for manufacturing a semiconductor device includes a step of applying the composition on a substrate, a step of etching a resist underlayer film according to a predetermined pattern, and a step of forming a patterned resist underlayer film (resist underlayer film). Processing the substrate based on the pattern).
• the hard mask for example, a silicon hard mask including silicon is used.
• the method of forming the hard mask is not limited. For example, a method of applying a material containing a silicon component on the resist underlayer film is used. A technique of depositing a hard mask on the resist underlayer film may be used.
• the photoresist film can be formed by a general method, that is, by applying a photoresist solution on a hard mask to form a coating film and baking it.
• the photoresist solution contains a composition for forming a photoresist film and a solvent for dissolving the composition.
• the solvent include ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone.
• a solution sensitive to a light source used for exposure is used. For the exposure, either light or electron beam can be used, and the developer used for development is not particularly limited.
• a halogen-based gas such as CF 4 gas
• an oxygen-based gas or a hydrogen-based gas is used.
• a halogen-based gas such as CF 4 gas is used.
• the resist underlayer film obtained by using the above composition has high etching resistance to, for example, a halogen-based gas, and therefore, the substrate can be suitably processed according to the resist underlayer pattern.
• the resist underlayer film itself is also suitably etched by an oxygen-based gas or a hydrogen-based gas whose etching selectivity is opposite to that of a halogen-based gas. Is done).
• PGME propylene glycol monomethyl ether
• PGMEA propylene glycol monomethyl ether acetate
• BPM-Py-TPM had a weight average molecular weight Mw of 18,260 and a polydispersity Mw / Mn of 12.85.
• BPM-Py-DP had a weight average molecular weight Mw of 22,380 and a polydispersity Mw / Mn of 12.61.
• the temperature was raised to 120 ° C. with stirring to dissolve, and the polymerization reaction was started. After 20 hours, the polymerization reaction was stopped. After allowing to cool to room temperature, TP (4.10 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanesulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and PGME was further added. (1.82 g, manufactured by Kanto Chemical Co., Ltd.) and PGMEA (4.24 g, manufactured by Kanto Chemical Co., Ltd.). The temperature was raised to 120 ° C. with stirring to dissolve, and the polymerization reaction was started. After 23 hours, the polymerization reaction was stopped.
• BPM-Py-TP had a weight average molecular weight Mw of 3,490 and a polydispersity Mw / Mn of 2.50.
• the temperature was raised to 120 ° C. with stirring to dissolve, and the polymerization reaction was started. After 20 hours, the polymerization reaction was stopped. After cooling to room temperature, FLO (2.63 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanesulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added. PGME (1.82 g, manufactured by Kanto Chemical Co., Ltd.) and PGMEA (4.24 g, manufactured by Kanto Chemical Co., Ltd.) were charged. The temperature was raised to 120 ° C. with stirring to dissolve, and the polymerization reaction was started. After 23 hours, the polymerization reaction was stopped.
• BPM-Py-FLO had a weight average molecular weight Mw of 6,720 and a polydispersity Mw / Mn of 3.11.
• the temperature was raised to 120 ° C. with stirring to dissolve, and the polymerization reaction was started. After 20 hours, the polymerization reaction was stopped. After cooling to room temperature, DPM (2.66 g, 0.0144 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and methanesulfonic acid (0.2774 g, 0.0029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and further PGME was added. (1.82 g, manufactured by Kanto Chemical Co., Ltd.) and PGMEA (4.24 g, manufactured by Kanto Chemical Co., Ltd.). The temperature was raised to 120 ° C. with stirring to dissolve, and the polymerization reaction was started. After 23 hours, the polymerization reaction was stopped.
• BPM-Py-DPM had a weight average molecular weight Mw of 15,080 and a polydispersity Mw / Mn of 12.11.
• Pid-Py-TPM had a weight average molecular weight Mw of 780 and a polydispersity Mw / Mn of 2.00.
• PNA-Py-TPM had a weight average molecular weight Mw of 1,495 and a polydispersity Mw / Mn of 2.63.
• BPM-Py had a weight average molecular weight Mw of 6,300 and a polydispersity Mw / Mn of 1.90.
• Pid-Py had a weight average molecular weight Mw of 880 and a polydispersity Mw / Mn of 1.69.
• Example 1 ⁇ Preparation of resist underlayer film forming composition> (Example 1) 0.06 g of Megafac R-30N (manufactured by DIC Corporation) as a surfactant was mixed with 20 g of the polymer obtained in Synthesis Example 1, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Megafac R-30N manufactured by DIC Corporation
• Example 2 0.06 g of Megafac R-30N (manufactured by DIC) as a surfactant was mixed with 20 g of the polymer obtained in Synthesis Example 2, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Example 3 0.06 g of Megafac R-30N (manufactured by DIC Corporation) as a surfactant was mixed with 20 g of the polymer obtained in Synthesis Example 3, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Megafac R-30N manufactured by DIC Corporation
• Example 4 0.06 g of Megafac R-30N (manufactured by DIC Corporation) as a surfactant was mixed with 20 g of the polymer obtained in Synthesis Example 4, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Megafac R-30N manufactured by DIC Corporation
• Example 5 0.06 g of Megafac R-30N (manufactured by DIC Corporation) as a surfactant was mixed with 20 g of the polymer obtained in Synthesis Example 5, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Megafac R-30N manufactured by DIC Corporation
• Example 6 To 1.227 g of the polymer obtained in Synthesis Example 6, 4,4 ′-(1-methylethylidine) bis [2,6-bis [(2-methoxy-1-methylethoxy) methyl] -phenol 0 was added as a crosslinking agent. .184 g, pyridinium-p-phenolsulfonate 0.018 g as an acidic compound, and Megafac R-30N (manufactured by DIC) 0.0012 g as a surfactant were mixed, and 3.53 g of PGME, 3.53 g of PGMEA, and cyclohexanone 10. Dissolved in 58 g. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Example 7 To 1.227 g of the polymer obtained in Synthesis Example 7, 4,4 ′-(1-methylethylidine) bis [2,6-bis [(2-methoxy-1-methylethoxy) methyl] -phenol 0 was used as a crosslinking agent. .184 g, pyridinium-p-phenolsulfonate 0.018 g as an acidic compound, and Megafac R-30N (manufactured by DIC) 0.0012 g as a surfactant were mixed, and 3.53 g of PGME, 3.53 g of PGMEA, and cyclohexanone 10. Dissolved in 58 g. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Comparative Example 1 0.06 g of Megafac R-30N (manufactured by DIC Corporation) as a surfactant was mixed with 20 g of the polymer obtained in Comparative Synthesis Example 1, and dissolved in 24 g of PGME and 66 g of PGMEA. Thereafter, the solution was filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m to prepare a resist underlayer film forming composition.
• Examples 1A to 7A and Comparative Examples 1A to 2A The resist underlayer film forming compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were each applied to a silicon wafer using a spin coater. The resist was baked on a hot plate at 400 ° C. for 90 seconds to form a resist underlayer film (film thickness 0.25 ⁇ m).
• ⁇ Dissolution test to photoresist solvent> The resist underlayer films formed in Examples 1A to 7A and Comparative Examples 1A to 2A were coated with a solvent usable for a photoresist solution, specifically, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone. And confirmed that it was insoluble in these solvents. The confirmation was performed by measuring the film thickness before and after the dissolution test.
• a solvent usable for a photoresist solution specifically, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone.
• a halogen-based etching gas specifically, CF 4 gas
• Table 1 shows the results of calculating the film thickness of the resist underlayer film reduced per unit time (1 minute) as a dry etching rate. The lower the dry etching rate, the higher the etching resistance to CF 4 gas.
• Examples 1A to 7A were compared with Comparative Examples 1A to 2A for oxygen-based gas and hydrogen-based gas because of their high etching resistance to CF 4 gas and the etching selectivity opposite to halogen-based etching gas. In comparison, it is expected that the dry etching rate will increase.
• ⁇ Drug mixing test> The resist underlayer film forming compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were mixed with methyl 2-hydroxyisobutyrate at a weight ratio (9: 1), and the presence or absence of a precipitate after mixing was determined. confirmed. Table 2 shows the results. The presence or absence of the precipitate was visually confirmed. When the solution was a transparent solution, no deposition was performed, and when the solution was a solution in which insolubles were generated, it was evaluated that there was precipitation.

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