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
  • 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
• • 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
  • G03F7/20—Exposure; 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
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
• • 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

Definitions

• the present invention relates to a resist underlayer film forming composition suitable for lithography in semiconductor substrate processing, a resist underlayer film obtained from the resist underlayer film forming composition, a method for forming a resist pattern using the resist underlayer film forming composition, and a method for manufacturing a semiconductor device using the composition.
• the resist underlayer film forming composition contains, in addition to the main component polymer resin, a crosslinking compound (crosslinking agent) and a catalyst for promoting the crosslinking reaction (crosslinking catalyst).
• Patent Document 2 states that in the formula (A ⁇ )(BH) + , A ⁇ is an anion of an organic or inorganic acid having a pKa of 3 or less, and (BH) + has a pKa between 0 and 5.0; and a monoprotonated form of nitrogen-containing base B having a boiling point below 170°C. Specifically, combinations of perfluorobutanesulfonate and ammonium, pyridinium, 3-fluoropyridinium, or pyridazinium are described.
• Patent Document 3 discloses a thermal acid generator having the formula X ⁇ YH + in which X is an anion component and Y is a substituted pyridine.
• Patent Document 4 discloses a thermal acid generator containing a sulfonic acid component having no hydroxyl group and a pyridinium component having a ring substituent. Specifically, combinations of methylbenzenesulfonate and methylpyridinium, methoxypyridinium, or trimethylpyridinium are described.
• Patent Document 5 discloses a thermal acid generator containing para-toluenesulfonic acid triethylamine salt, para-toluenesulfonic acid ammonium salt, mesitylenesulfonic acid ammonium salt, dodecylbenzenesulfonic acid ammonium salt, or para-toluenesulfonic acid dimethylamine salt.
• Patent Document 6 discloses thermal acid generators containing various sulfonic acids and NH 4 + or primary, secondary, tertiary, or quaternary ammonium ions.
• the thermal acid generator disclosed in the prior art is aimed at improving the resist shape, and there is no mention of embeddability and planarization of the stepped substrate.
• inventions have been disclosed regarding the relationship between storage stability and sublimated materials, there is no specific evaluation or mention of the modification of thermal acid generators and polymers, and there are no specific evaluations or references regarding the embeddability and planarization of stepped substrates. No consideration has been given.
• the thermal acid generator described above cannot suppress polymer modification unless an appropriate amine component is selected. Therefore, there is a need for a thermal acid generator that suppresses denaturation of the polymer while also achieving embeddability and flattening properties in stepped substrates.
• the problem to be solved by the present invention is to provide a resist underlayer film forming composition that has excellent embedding properties and planarization properties in a stepped substrate, and has high storage stability of a polymer that is a main component of the resist underlayer film.
• An object of the present invention is to provide a method for forming a resist pattern using a film-forming composition, and a method for manufacturing a semiconductor device using the composition.
• the present invention includes the following. [1] (a) The following formula (1): A thermal acid generator represented by; (b) Polymers containing aromatic rings; (c) one or more bases B 2 ; and (d) A resist underlayer film forming composition comprising a solvent,
• A1 is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, or an optionally substituted aromatic ring residue;
• n represents the number of sulfonic acid anion groups and is 1 or 2
• B1 is one or more types of pair bases, is a monoacid base, or represents a monoacid base moiety of a diacid base or a triacid base, A 1 and B 1 may be connected by a single bond or a connecting group, At least one or more bases in B 1 and B 2 have a pKa larger than pyridine, Resist underlayer film forming composition.
• the aromatic ring-containing polymer is a novolac resin containing a unit structure having an aromatic ring which may have a substituent, and the aromatic ring is (i) contains a heteroatom in the substituent on the aromatic ring, (ii) the unit structure includes a plurality of aromatic rings, at least two of the aromatic rings are connected to each other by a linking group, and the linking group contains a heteroatom, or (iii)
• the aromatic ring-containing polymer is (i) One or more types of unit structures having an aromatic ring which may have a substituent, and (ii) a 4- to 17-membered monocyclic, bicyclic, tricyclic, or tetracyclic organic group which may have a substituent, wherein the monocyclic ring is a non-aromatic monocyclic ring; At least one of the monocycles constituting the ring, tricycle, and tetracycle is a non-aromatic monocycle, and the remaining monocycles have a unit structure containing an organic group that may be an aromatic monocycle or a non-aromatic monocycle.
• a novolac resin The monocyclic, bicyclic, tricyclic or tetracyclic organic group may further form a condensed ring with one or more aromatic rings to form a pentacyclic or higher ring, At least (i) and (ii) are bonded by a covalent bond between the carbon atom on the non-aromatic monocycle of (ii) and the carbon atom of the aromatic ring of (i),
• the resist underlayer film forming composition according to any one of [2] to [4] above.
• the aromatic ring-containing polymer has the following formula (AB): Contains the structure represented by In formula (I), n represents the number of composite unit structures AB, Unit structure A is One or more types of unit structure having an aromatic ring which may have a substituent, The substituent may contain a heteroatom,
• the unit structure may include a plurality of aromatic rings, the plurality of aromatic rings may be connected to each other by a linking group, and the linking group may include a heteroatom;
• the aromatic ring may be an aromatic heterocycle, or an aromatic ring forming a condensed ring with one or more heterocycles,
• Unit structure B represents one or more unit structures including the structure represented by the following formula (B1), (B2) or (B3),
• the resist underlayer film forming composition according to any one of [2] to [4] above.
• R and R' each independently have a hydrogen atom, an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent, and a substituent. Represents a heterocyclic residue having 3 to 30 carbon atoms, or a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent.
• Z 0 is an aromatic ring residue having 6 to 30 carbon atoms, an aliphatic ring residue, or two aromatic ring residues or an aliphatic ring which may have a substituent.
• Z is a monocyclic, bicyclic, tricyclic or tetracyclic condensed ring having 4 to 25 carbon atoms which may have a substituent, and the monocyclic ring is a non-aromatic monocyclic ring; At least one of the monocycles constituting the ring, tricycle, and tetracycle is a non-aromatic monocycle, and the remaining monocycles may be aromatic monocycles or non-aromatic monocycles; A tricyclic or tetracyclic fused ring may further form a fused ring with one or more aromatic rings to form a pentacyclic or more fused ring, X and Y are the same or different and represent a -CR 31 R 32 - group, R 31 and R 32 are each the same or
• the above formula (B3) is the following formula (B31): [In formula (B31), Z is a 4- to 17-membered monocyclic, bicyclic, tricyclic, or tetracyclic organic group which may have a substituent, and the monocyclic ring is a non-aromatic monocyclic ring; , at least one of the monocycles constituting the tricycle and tetracycle is a non-aromatic monocycle, and the remaining monocycles may be aromatic monocycles or non-aromatic monocycles,
• the monocyclic, bicyclic, tricyclic or tetracyclic organic group may further form a condensed ring with one or more aromatic rings to form a pentacyclic or higher ring, C and C' each represent one carbon atom in the atomic group constituting the cyclic portion of any of the non-aromatic monocycles of Z, and the non-aromatic monocycles to which C and C' belong may or may not be the same.
• n is the number of the carbon atoms C' and represents an integer of 0 to 2; p, q, p', q' represent the number of bonds, each independently representing 0 or 1, If n is 0, p and q are 1, When n is 1 and 2, at least one of p and q, and at least one of p' and q' of each C' are each 1, When n is 2, the non-aromatic monocycles to which the two C's belong may be the same or different, and if they are the same, the two C's may or may not be directly bonded, X, Y, X', Y' are the same or different and represent a -CR 1 R 2 - group, and R 1 and R 2 are each the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
• the two X's may be the same or different, and the two Y's may be the same or different, x, y, x', and y' represent the numbers of X, Y, X', and Y', respectively, and each independently represents 0 or 1.
• the amount of base required to neutralize the same number of moles of sulfonic acid (monobasic acid) as the sulfonic acid anion group (SO 3 ⁇ ) contained in the thermal acid generator (a) is 1 equivalent, , the base having a pKa larger than pyridine in the pair base B 1 in formula (I) of component (a) and the base B 2 of component (c) is present in an amount of 1.05 equivalent or more, [1] to [7] ]
• the resist underlayer film forming composition according to any one of [1] to [7], wherein the amount of base B 2 added is 0.05 to 3.0 equivalents.
• Pair base B 1 in formula (1) of component (a) and/or base B 2 of component (c) is R I R II R III N
• R I and R II each independently represent a hydrogen atom, an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group
• R I and R II may form a ring through a hetero atom or without a hetero atom, or may form a ring through an aromatic ring
• R III represents a hydrogen atom, an optionally substituted aromatic ring residue, or an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group
• R III is a hydrogen atom or an optionally substituted aromatic ring residue
• the resist underlayer film forming composition according to any one of [1] to [9] above.
• the pair base B 1 in formula (1) of component (a) and/or the base B 2 of component (c) are: [In the formula, R 1 and R 2 each independently represent an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R 3 represents a hydrogen atom or an optionally substituted aromatic hydrocarbon group.
• R is hydrogen atom; 1 carbon number, which may be substituted with a nitro group, cyano group, amino group, carboxyl group, hydroxy group, amide group, aldehyde group, (meth)acryloyl group, halogen atom, or alkoxy group having 1 to 10 carbon atoms -10 alkyl groups, C2-10 alkenyl groups, C2-10 alkynyl groups, C1-10 hydroxyalkyl groups, C6-40 aryl groups, organic groups containing ether bonds, an organic group containing a ketone bond or an organic group containing an ester bond; or It is a group that combines them, R' is an aromatic ring forming a condensed ring with the cyclic amine ring in formula (II), or and R a and R b each independently represent an optionally substituted alkylene group, X is O, S, SO2 , CO, CONH,
• R 3 in the above formula (2) represents an optionally substituted phenyl, naphthyl, anthracenyl, pyrenyl or phenanthrenyl group
• R in the above formula (3) is a hydrogen atom, a methyl group, an ethyl group, an isobutyl group, an allyl group, or a cyanomethyl group
• R' in the above formula (3) is The resist underlayer film forming composition according to the above [11], wherein the base is a base represented by the following formula, and n and m are each independently 2, 3, 4, 5, or 6.
• Pair base B 1 in formula (1) of component (a) and/or base B 2 of component (c) is a type of N-methylmorpholine, N-isobutylmorpholine, N-allylmorpholine, or N,N-diethylaniline. or two or more kinds of resist underlayer film forming compositions according to any one of [1] to [12].
• a 1 in the above formula (1) is a methyl group, a trifluoromethyl group, a naphthyl group, a norbornanylmethyl group, a dimethylphenyl group, or a tolyl group.
• a composition for forming a resist underlayer film is a type of N-methylmorpholine, N-isobutylmorpholine, N-allylmorpholine, or N,N-diethylaniline. or two or more kinds of resist underlayer film forming compositions according to any one of [1] to [12].
• a 1 in the above formula (1) is a methyl group, a triflu
• the crosslinking agent is an aminoplast crosslinking agent or a phenoplast crosslinking agent.
• the aminoplast crosslinking agent is highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, or a polymer thereof.
• [25] forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of [1] to [22]; a step of forming a resist film thereon; a step of forming a resist pattern by irradiation with light or electron beam and development; A method for manufacturing a semiconductor device, comprising: etching the resist underlayer film using the formed resist pattern; and processing a semiconductor substrate using the patterned resist underlayer film.
• [26] forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of [1] to [22]; forming a hard mask thereon; Furthermore, a step of forming a resist film thereon, a step of forming a resist pattern by irradiation with light or electron beam and development; a step of etching the hard mask using the formed resist pattern; A method for manufacturing a semiconductor device, comprising: etching the resist underlayer film using a patterned hard mask; and processing a semiconductor substrate using the patterned resist underlayer film.
• [27] forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of [1] to [22]; forming a hard mask thereon; Furthermore, a step of forming a resist film thereon, a step of forming a resist pattern by irradiation with light or electron beam and development; a step of etching the hard mask using the formed resist pattern; etching the resist underlayer film using a patterned hard mask; A method for manufacturing a semiconductor device, including a step of removing a hard mask, and a step of processing a semiconductor substrate using a patterned resist underlayer film.
• [28] forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of [1] to [22]; forming a hard mask thereon; Furthermore, a step of forming a resist film thereon, a step of forming a resist pattern by irradiation with light or electron beam and development; a step of etching the hard mask using the formed resist pattern; etching the resist underlayer film using a patterned hard mask; a step of removing the hard mask, and a step of forming a deposited film (spacer) on the resist underlayer film after the hard mask has been removed, A process of processing the deposited film (spacer) by etching, A semiconductor device including: a step of removing a patterned resist underlayer film to leave a patterned deposited film (spacer); and a step of processing a semiconductor substrate via the patterned deposited film (spacer).
• one or more bases B2 which are additional base components, are separately added.
• the base traps the acid generated during firing, slowing down the curing speed, and as a result, it is possible to obtain cured films with high flatness and high embedding properties with various film types such as SiO 2 , TiN, and SiN. Can be done.
• a film can be formed that does not cause coloring and does not dissolve into photoresist solvents.
• the present invention provides a resist underlayer film obtained from the resist underlayer film forming composition, and a method for manufacturing a semiconductor device using the composition.
• Novolak resin refers not only to phenol formaldehyde resin (so-called novolak type phenol resin) and aniline formaldehyde resin (so-called novolak type aniline resin) in the narrow sense, but also generally in the presence of an acid catalyst or under similar reaction conditions.
• a functional group that enables covalent bonding with an aromatic ring e.g., aldehyde group, ketone group, acetal group, ketal group, hydroxyl group or alkoxy group bonded to secondary or tertiary carbon, ⁇ -position carbon of alkylaryl group
• Organic compounds having a hydroxyl group, alkoxy group or halo group bonded to an atom such as a benzylic carbon atom; a carbon-carbon unsaturated bond such as divinylbenzene or dicyclopentadiene
• a compound having an aromatic ring preferably By forming a covalent bond (substitution reaction, addition reaction, condensation reaction, addition condensation reaction, etc.) with an aromatic ring (having a substituent containing a hetero atom such as an oxygen atom, nitrogen atom, or sulfur atom on the aromatic ring) It is used in a broad sense to broadly encompass the polymerized polymers that are formed.
• the novolac resin referred to in this specification is a compound in which an organic compound containing a carbon atom derived from the functional group (sometimes referred to as a "linked carbon atom") has an aromatic ring via the linking carbon atom.
• an organic compound containing a carbon atom derived from the functional group sometimes referred to as a "linked carbon atom”
• the linking carbon atom By forming a covalent bond with an aromatic ring, compounds having a plurality of aromatic rings are connected to form a polymer.
• unit structure A is a unit structure derived from a compound having an aromatic ring.
• Unit structure B is a unit structure derived from a compound having a functional group that enables covalent bonding with the aromatic ring of unit structure A.
• Unit structure C is one unit structure that is equivalent in bonding mode to composite unit structure AB, has an aromatic ring, and has a functional group that enables covalent bonding with the aromatic ring of unit structure A. It is a unit structure derived from a compound. Since the bonding mode is the same, unit structure C can be replaced with composite unit structure AB.
• Residue refers to an organic group in which the hydrogen atom bonded to a carbon atom or a heteroatom (nitrogen atom, oxygen atom, sulfur atom, etc.) is replaced with a bond, and even if it is a monovalent group, it is a polyvalent group. It may be. For example, if one hydrogen atom is replaced by one bond, it becomes a monovalent organic group, and if two hydrogen atoms are replaced by one bond, it becomes a divalent organic group.
• Aromatic ring refers to aromatic hydrocarbon rings, aromatic heterocycles, and their residues ["aromatic group”, “aryl group” (in the case of monovalent groups), or "arylene group” (divalent group). It is a concept that includes not only monocyclic (aromatic monocyclic) but also polycyclic (aromatic polycyclic). In the case of a polycyclic system, at least one monocycle is an aromatic monocycle, but the remaining monocycles forming a condensed ring with the aromatic monocycle may be monocyclic heterocycles (heteromonocycles) or monocyclic rings. It may also be an alicyclic hydrocarbon (alicyclic monocyclic ring).
• Aromatic rings include benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, triphenylene, benzanthracene, pyrene, chrysene, fluorene, biphenyl, corannulene, perylene, fluoranthene, benzo [k Aromatic hydrocarbon rings such as fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, coronene, dibenzo[g,p]chrysene, acenaphthylene, acenaphthene, naphthacene, pentacene, cyclooctatetraene, more typically Aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, pyrene; furan, pyran,
• Group heterocycles more typically include, but are not limited to, furan, thiophene, pyrrole, indole, phenylindole, bisindolefluorene, phenothiazine, carbazole, indolocarbazole.
• Aromatic rings may optionally have a substituent, and such substituents include halogen atoms, saturated or unsaturated straight chain, branched or cyclic hydrocarbons.
• group (-R) (which may be interrupted one or more times by an oxygen atom in the hydrocarbon chain; includes an alkyl group, alkenyl group, alkynyl group, propargyl group, etc.), an alkoxy group or an aryloxy group ( -OR, where R represents the hydrocarbon group -R), alkylamino group [-NHR or -NR 2 (two R may be the same or different), where R represents the hydrocarbon group -R represents an alkyl group, an alkenyl group, an alkynyl group, a propargyl group, etc. which may be interrupted by an oxygen atom one or more times in the hydrocarbon chain.
• organic groups having a condensed ring of one or more aromatic rings (benzene, naphthalene, anthracene, pyrene, etc.) and one or more aliphatic rings or heterocycles are also included.
• the aliphatic ring here include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene
• examples of the heterocycle include furan, thiophene, pyrrole, and imidazole.
• It may also be an organic group having a structure in which two or more aromatic rings are connected by a divalent linking group such as an alkylene group.
• heterocycle includes both aliphatic heterocycles and aromatic heterocycles, and is a concept that includes not only monocyclic rings (heteromonocycles) but also polycyclic rings (heteropolycycles). In the case of a polycyclic ring, at least one monocycle is a heteromonocycle, but the remaining monocycles may be an aromatic hydrocarbon monocycle or an alicyclic monocycle.
• aromatic heterocycle reference can be made to the examples given in (I-3) above. Like the aromatic ring in (I-3) above, it may have a substituent.
• Non-aromatic ring (aliphatic ring)
• a “non-aromatic monocyclic ring” refers to a monocyclic hydrocarbon that does not belong to the aromatic group, and is typically a monocyclic ring of an alicyclic compound. It may also be called an aliphatic monocycle (which may include an aliphatic heteromonocycle and may contain an unsaturated bond as long as it does not belong to aromatic compounds). Like the aromatic ring in (I-3) above, it may have a substituent.
• non-aromatic monocycles examples include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, cycloheptene, and the like.
• Non-aromatic polycyclic refers to a polycyclic hydrocarbon that does not belong to the aromatic group, and is typically a polycyclic alicyclic compound.
• Aliphatic polycycles may include aliphatic heteropolycycles (at least one of the monocycles constituting the polycycle is an aliphatic heterocycle), and even if they contain unsaturated bonds as long as they do not belong to aromatic compounds You can also call it ⁇ good''. Includes non-aromatic bicyclic rings, non-aromatic tricyclic rings, and non-aromatic tetracyclic rings.
• Non-aromatic bicyclic ring refers to a condensed ring composed of two monocyclic hydrocarbons that do not belong to aromatics, and is typically a condensed ring of two alicyclic compounds. In this specification, it is sometimes referred to as an aliphatic bicyclic ring (which may include an aliphatic heterobicyclic ring and may contain an unsaturated bond as long as it does not belong to an aromatic compound). Examples of the non-aromatic bicyclic ring include bicyclopentane, bicyclooctane, and bicycloheptene.
• Non-aromatic tricyclic refers to a fused ring composed of three monocyclic hydrocarbons that do not belong to aromatics, and typically consists of three alicyclic compounds (each of which is a heterocyclic ring). or may contain an unsaturated bond as long as it does not belong to aromatic compounds).
• Examples of the non-aromatic tricyclic ring include tricyclooctane, tricyclononane, tricyclodecane, and the like.
• Non-aromatic tetracycle is a condensed ring composed of four monocyclic hydrocarbons that do not belong to aromatics, and typically consists of four alicyclic compounds (each of which is a heterocycle). or may contain an unsaturated bond as long as it does not belong to aromatic compounds).
• Examples of the non-aromatic tetracyclic ring include hexadecahydropyrene and the like.
• Carbon atoms constituting a ring (part) means carbon atoms constituting a hydrocarbon ring (which may be an aromatic ring, aliphatic ring, or heterocycle) without a substituent. do.
• Hydrocarbon group refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.
• a 1 is an optionally substituted linear, branched, or cyclic saturated or unsaturated aliphatic hydrocarbon group, an optionally substituted aromatic ring residue, preferably a methyl group, A trifluoromethyl group, a naphthyl group, a norbornanylmethyl group, a dimethylphenyl group, or a tolyl group.
• aromatic ring is a concept that includes aromatic hydrocarbon rings and aromatic heterocycles
• reduce refers to bonds bonded to carbon atoms or heteroatoms (nitrogen atoms, oxygen atoms).
• n represents the number of sulfonic acid anion groups, and is 1 or 2, preferably 1.
• B 1 is one or more types of pair bases, and is a monoacid base, or represents a monoacid base moiety of a diacid base or a triacid base.
• B 1 is a diacid base or a triacid base
• B 1 there are two or three equivalents to B 1 , which are covalently bonded to each other.
• a 1 and B 1 may be connected by a single bond or a connecting group.
• at least one base has a pKa larger than that of pyridine. Note that the pKa requirements and the equivalent ratio of base B 1 to base B 2 of component (c), etc. will be explained in (IV-2) to (IV-3) below.
• the counter base B 1 in formula (1) of component (a) and/or the base B 2 of component (c) is R I R II R III N.
• R I and R II each independently represent a hydrogen atom, an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R I and R II may form a ring with or without a hetero atom, or may form a ring with an aromatic ring, and the hetero atom is preferably an oxygen atom, a nitrogen atom or a sulfur atom, R III represents a hydrogen atom, an optionally substituted aromatic ring residue, or an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group; When R I and R II do not form a ring, R III is a hydrogen atom or an optionally substituted aromatic ring residue].
• the pair base B 1 in formula (1) of component (a) and/or the base B 2 of component (c) are: [In the formula, R 1 and R 2 each independently represent an optionally substituted linear or branched saturated or unsaturated aliphatic hydrocarbon group, R 3 represents a hydrogen atom, an optionally substituted aromatic group, preferably an optionally substituted phenyl, naphthyl, anthracenyl, pyrenyl, or phenanthrenyl group.
• R is hydrogen atom; Nitro group, cyano group, amino group, carboxyl group, hydroxy group, amide group, aldehyde group, (meth)acryloyl group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), or a carbon number of 1 to Alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, hydroxyalkyl group having 1 to 10 carbon atoms, which may be substituted with 10 alkoxy groups, carbon An aryl group of 6 to 40, an organic group containing an ether bond, an organic group containing a ketone bond, or an organic group containing an ester bond; or a group combining these; R' is an aromatic ring that forms a condensed ring with the ring of the cyclic
• R in formula (3) is a hydrogen atom, a methyl group, an ethyl group, an isobutyl group, an allyl group, or a cyanomethyl group.
• R' in formula (3) is where n and m are each independently 2, 3, 4, 5, or 6.
• Examples of the "cyclic saturated aliphatic hydrocarbon group" in the definition of A1 in formula ( 1 ) include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, Cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3- Ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3
• Examples of the "straight chain, branched unsaturated aliphatic hydrocarbon group” include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2 -butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl -3-butenyl
• Examples of the "cyclic unsaturated aliphatic hydrocarbon group" in the definition of A1 in formula ( 1 ) include 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-methyl- 2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl- 4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclo Examples include pentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group. It will be done.
• aromatic hydrocarbon groups include, for example, phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4- Dimethylphenyl group, 3,5-dimethylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group , p-nitrophenyl group, p-cyanophenyl group, ⁇ -naphthyl group,
• aromatic heterocyclic residues among the "aromatic ring residues" in the definition of A1 in formula ( 1 ) include furanyl groups, thiophenyl groups, pyrrolyl groups, imidazolyl groups, pyranyl groups, and pyridinyl groups.
• pyrimidinyl group pyrazinyl group, pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholinyl group, quinuclidinyl group, indolyl group, purinyl group, quinolinyl group, isoquinolinyl group, chromenyl group, thianthrenyl group, phenothiazinyl group, phenoxazinyl group, xanthenyl group, Examples include acridinyl group, phenazinyl group, carbazolyl group, and the like.
• "Aromatic ring” or "aromatic ring” in the definition of R III in R I R II R III N or in the definition of R 3 in R 1 R 2 R 3 N also refers to the above-mentioned ring. It is similar to
• substituents corresponding to “optionally substituted” include a nitro group, an amino group, a cyano group, a sulfo group, a hydroxy group, and a carboxyl group.
• alkynyl group having 10 carbon atoms an aryl group having 6 to 40 carbon atoms
• an organic group containing an ether bond an organic group containing a ketone bond, an organic group containing an ester bond, or a combination thereof.
• examples of (II-3-9) below can be referred to.
• Examples of the "alkoxy group" in the definition of R in formula (3) include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t -butoxy group, 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
• alkynyl group in the definition of R in formula (3), it may be bonded to an aliphatic hydrocarbon chain (bonded to the end of the chain or inserted in the middle of the chain), or may be further heterogeneous in the above embodiments. It includes embodiments containing atoms (oxygen atoms, nitrogen atoms, etc.), embodiments in which a plurality of alkynyl groups are connected, and examples thereof include the following organic groups.
• * in the formula represents a carbon atom from which a bond extends.
• R 11 is each independently an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, It can be a residue of an ether compound represented by an alkylene group, a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, an anthranyl group, or a pyrenyl group. Examples include organic groups containing an ether bond.
• thermal acid generator represented by formula (1) examples include arbitrary combinations of at least one of the examples of anti-base cations and the examples of sulfonate anions shown below so that the charge is neutral. However, it is not limited to these.
• thermal acid generators that are a combination of a base cation and a sulfonic acid anion can be mentioned below, but the invention is not limited thereto.
• the amount of the thermal acid generator is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total solid content in the resist underlayer film forming composition. be.
• the thermal decomposition start temperature that is, the thermal acid generation temperature of the thermal acid generator according to one aspect of the present invention is preferably 50° C. or higher, more preferably 100° C. or higher, and still more preferably 150° C. or higher; Preferably it is 400°C or lower.
• Polymers containing aromatic rings are not particularly limited, but examples include polyvinyl alcohol, polyacrylamide, (meth)acrylic resins, polyamic acid, polyhydroxystyrene, polyhydroxystyrene derivatives, and polymethacrylates, each containing an aromatic ring.
• the aromatic ring containing polymer is preferably a novolac resin.
• the "novolac resin" referred to in the present specification has already been referred to in the above-mentioned [I. Definition of Terms] (I-1).
• the aromatic ring-containing polymer is a novolac resin containing a unit structure having an aromatic ring which may have a substituent, and the aromatic ring is (i) contains a heteroatom in the substituent on the aromatic ring, (ii) the unit structure includes a plurality of aromatic rings, at least two of the aromatic rings are connected to each other by a linking group, and the linking group contains a heteroatom, or (iii) The aromatic ring is an aromatic heterocycle, or an aromatic ring formed with one or more heterocycles and a condensed ring.
• aromatic rings (i) to (iii) correspond to the unit structure A in the novolac resin mentioned in (I-1) above.
• the unit structure (i) or (ii) each has at least one, more preferably two, aromatic rings having an oxygen-containing substituent, or a plurality of units connected by at least one -NH-. It is a unit structure having an aromatic ring.
• Oxygen-containing substituents include hydroxyl groups; hydroxyl groups in which a hydrogen atom is replaced by a saturated or unsaturated straight-chain, branched, or cyclic hydrocarbon group (i.e., an alkoxy group); and saturated or It includes unsaturated straight chain, branched or cyclic hydrocarbon groups, aromatic ring residues, etc.
• the aromatic ring-containing polymer is (i) One or more types of unit structure having an aromatic ring which may have a substituent, and (ii) A 4- to 12-membered monocyclic or bicyclic ring which may have a substituent. , a tricyclic or tetracyclic organic group unit structure,
• the monocycle is a non-aromatic monocycle; At least one of the monocycles constituting the bicycle, tricycle, and tetracycle is a non-aromatic monocycle, and the remaining monocycles may be aromatic monocycles or non-aromatic monocycles.
• Unit structure containing an organic group. has.
• Such unit structures also include unit structures in which two or three of the same or different organic groups are linked by a divalent or trivalent linking group to form a dimer or trimer.
• the monocyclic, bicyclic, tricyclic, or tetracyclic organic group may further form a condensed ring with one or more aromatic rings to form a pentacyclic or more ring.
• the novolac resin at least the carbon atom (linked carbon atom) on the non-aromatic monocycle of (ii) and the carbon atom of the aromatic ring of (i) are covalently bonded to (i). and (ii) are combined.
• the unit structure (i) corresponds to the unit structure A of the novolak resin mentioned in (I-1), and the monocyclic, bicyclic, tricyclic, or tetracyclic organic group in (ii) is This corresponds to the unit structure B of the novolac resin mentioned in (I-1) above.
• Typical examples of (ii) include, for cyclic ketones, a unit structure in which the keto group is replaced with two bonding hands; for cyclic ketones, an organic group is added to the keto group and the unit structure is converted to a tertiary alcohol. Examples include a unit structure in which the tertiary hydroxyl group of the compound is replaced with one bond.
• the unit structure (ii) contains an aromatic ring
• the aromatic ring is bonded to each of the connecting carbon atoms of the other two unit structures (ii), the unit structure (i) ), that is, it can also be used as a unit structure A.
• the unit structure (ii) includes an aromatic ring X
• the connecting carbon atom of the unit structure (ii) is bonded to the aromatic ring Y of another unit structure (i)
• the unit structure If a bonding mode is adopted in which the aromatic ring It can be used as one unit structure equivalent to the composite unit structure by replacing at least a part of the composite unit structure. This corresponds to the unit structure C referred to in the novolac resin (I-1) above.
• Novolak resin containing composite unit structure AB Preferably, the novolak resin has the following formula (AB): It includes a composite unit structure AB represented by:
• n represents the number of composite unit structures AB.
• the unit structure A is one or more types of unit structures having an aromatic ring which may have a substituent.
• the substituent may contain a heteroatom; the unit structure contains a plurality of aromatic rings, the plurality of aromatic rings are connected to each other by a linking group, and the linking group contains a heteroatom.
• the aromatic ring may be an aromatic heterocycle or an aromatic ring formed with one or more heterocycles and a condensed ring.
• the unit structure B is one or more unit structures containing a connecting carbon atom [see above (I-1) "Novolac resin”] bonded to the aromatic ring in the unit structure A, and is -3-B10) to (III-3-B14), (III-3-B20) to (III-3-B23), and (III-3-B30) to (III-3-B35), respectively. It includes a structure represented by (B1), (B2) or (B3). Such unit structures also include unit structures in which two or three identical or different structures represented by these formulas are connected via a divalent or trivalent linking group. Unit structure B can connect two unit structures A by covalently bonding to a carbon atom on the aromatic ring of unit structure A.
• At least one composite unit structure A-B is explained as one unit structure equivalent to it in (III-3-B13), (III-3-B22), and (III-3-B34), respectively. It may be replaced with one or more types of unit structures C including structures represented by formulas (C1), (C2), (C3) and (C4).
• (III-3-A0) Unit structure A The "aromatic ring" in unit structure A includes not only aromatic hydrocarbon rings but also aromatic heterocycles, and is a concept that includes not only monocyclics but also polycyclics, and in the case of polycyclics, Although at least one monocycle is an aromatic monocycle, it was already explained in (I-3) above that the remaining monocycles may be a heteromonocycle or an alicyclic monocycle.
• the description of the aromatic ring in (I-3) above and the description of the heterocycle in (I-4) above can be referred to. You can refer to It may also be an organic group having a structure in which two or more aromatic rings are connected by a linking group such as an alkylene group.
• the "aromatic ring" in unit structure A has 6 to 30 or 6 to 24 carbon atoms.
• the "aromatic ring" in unit structure A is one or more benzene ring, naphthalene ring, anthracene ring, pyrene ring; or a benzene ring, naphthalene ring, anthracene ring, pyrene ring, and a heterocycle or aliphatic ring. It is a fused ring with.
• the aromatic ring in unit structure A may optionally have a substituent, but it is preferable that the substituent contains a heteroatom.
• the aromatic ring in the unit structure A two or more aromatic rings may be connected by a connecting group, and it is preferable that a hetero atom is contained in the connecting group.
• the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and the like.
• the "aromatic ring" in the unit structure A has 6 to 30 carbon atoms, or has 6 to 30 carbon atoms, and contains at least one heteroatom selected from N, S, and O on the ring, within the ring, or between the rings. 24 organic groups.
• Heteroatoms contained on the ring include, for example, amino groups (e.g., propargylamino groups), nitrogen atoms contained in cyano groups; oxygen-containing substituents such as formyl, hydroxy, carboxyl, alkoxy groups (e.g., Examples include the oxygen atom contained in the propargyloxy group, the nitrogen atom and oxygen atom contained in the oxygen-containing substituent and the nitro group, which is a nitrogen-containing substituent.
• Examples of the heteroatom contained in the ring include an oxygen atom contained in xanthene and a nitrogen atom contained in carbazole.
• Heteroatoms contained in the linking group of two or more aromatic rings include -NH- bond, -NHCO- bond, -O- bond, -COO- bond, -CO- bond, -S- bond, -SS - bond, -SO 2 - nitrogen atom, oxygen atom, and sulfur atom contained in the bond.
• the unit structure A is a unit structure having an aromatic ring having the above-mentioned oxygen-containing substituent, a unit structure having two or more aromatic rings connected by -NH-, or one or more aromatic rings. It is a unit structure having a condensed ring of a hydrocarbon ring and one or more heterocycles.
• the unit structure A is at least one selected from the following. (Example of amine skeleton)
• H in NH of the amine skeleton and H in OH of the phenol skeleton may be replaced with substituents described below.
• the unit structure A is at least one selected from the following. (Example of unit structure derived from heterocycle) (Example of unit structure derived from aromatic hydrocarbon having oxygen-containing substituent) (Example of unit structure derived from aromatic hydrocarbons linked by -NH-)
• the unit structure B is one or more unit structures containing a connecting carbon atom [see above (I-1) "Novolac resin”] bonded to the aromatic ring in the unit structure A, and is -B10) to (III-3-B14), (III-3-B20) to (III-3-B23), and (III-3-B30) to (III-3-B35), respectively. ), (B2) or (B3).
• R and R' are each independently a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have a substituent, and a heterocycle having 3 to 30 carbon atoms which may have a substituent. , or a straight chain, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent.
• R and R' in formula (B1) "substituent”, “aromatic ring”, and “heterocycle” are explained in (I-3), (I-4), etc. above. It is similar to .
• the two bonding hands of formula (B1) can be covalently bonded to the aromatic ring in unit structure A.
• alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i- Butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl- n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl -n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl
• R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenanthrenyl, naphthacenyl, pyrenyl.
• Examples of such a linking group include a linking group having two or three aromatic rings (corresponding to unit structure A).
• Specific examples of divalent or trivalent linking groups include the following divalent linking groups (L1) exemplified by the above formula (B11): [X 1 represents a single bond, methylene group, oxygen atom, sulfur atom, -N(R 5 )-, R 5 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (chain hydrocarbon, cyclic hydrocarbon Represents hydrogen (including aromatic or non-aromatic). ] In addition to these, examples include divalent or trivalent linking groups of the following formulas (L2) and (L3).
• X 2 represents a methylene group, an oxygen atom, -N(R 6 )-, and R 6 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 20 carbon atoms represents a group.
• a divalent linking group such as the following formula (L4) that can form a covalent bond with a linking carbon atom by an addition reaction between acetylide and a ketone can also be exemplified.
• the following formula (C1) As in etc.), it can be replaced with at least one composite unit structure AB as one unit structure C equivalent to the composite unit structure AB. That is, the aromatic ring [Ar in formula (C1)] in formula (C1) is bonded to another unit structure B, and the bonding hand from the remaining connecting carbon atoms shown in formula (C1) is The polymer chain may be extended by bonding with the aromatic ring of the unit structure A.
• a bond with the unit structure A when a bond with the unit structure A is mentioned, it may be interpreted as including a bond with the aromatic ring in the unit structure C even if it is not explicitly stated.
• a bond with unit structure B when a bond with unit structure B is mentioned, it may be interpreted as including a bond with a connecting carbon atom in unit structure C, even if it is not explicitly stated.
• unit structure B including the structure represented by formula (B1) are as follows. * basically indicates a binding site with unit structure A. Needless to say, the structure may include the illustrated structure as a part of the whole.
• Z 0 is an aromatic ring residue having 6 to 30 carbon atoms, which may have a substituent, an aliphatic ring residue, or an organic group in which two aromatic or aliphatic rings are connected by a single bond. represents.
• Examples of the organic group in which two aromatic or aliphatic rings are connected by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and bicyclohexyl.
• J 1 and J 2 each independently represent a direct bond or a divalent organic group which may have a substituent.
• the divalent organic group preferably has 1 to 6 carbon atoms and may be substituted with a hydroxyl group, an aryl group (phenyl group, substituted phenyl group, etc.) or a halo group (e.g. fluorine).
• the unit structure including the structure represented by formula (B2) includes two or three of the above formula (B2) that are the same or different from each other, as in (III-3-B12) above for formula (B1).
• the structure may include a dimeric or trimeric structure combined with a divalent or trivalent linking group.
• formula (B2) includes an embodiment containing an aromatic ring [Z 0 in formula (B2)], as in (III-3-B13) of formula (B1), the aromatic ring
• the ring [for example, the aromatic ring in Z 0 Ar in the following formula (B21)] may be additionally bonded to another unit structure B [vertical bonding hand in formula (B21)].
• formula (B2) includes an embodiment containing an aromatic ring
• the aromatic ring of formula (B2) and another unit structure B are bonded, and the formula (B2 ) is bonded to the aromatic ring of unit structure A with one bonding hand
• the unit structure represented by formula (B2) can be viewed as one unit structure C equivalent to composite unit structure AB.
• such unit structure C may include the structure represented by formula (B2) in composite unit structure AB.
• the other bonding arm of formula (B2) may be bonded to, for example, a polymer terminal group or bonded to an aromatic ring in another polymer chain to form a crosslink.
• Z 0 Ar is an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent, or an organic group in which two aromatic rings or aliphatic rings are connected by a single bond, an organic group having at least one aromatic ring, wherein the bonding hand extending downward from Z 0 Ar extends from the aromatic ring in Z 0 Ar ; J 1 and J 2 are the same as defined in formula (B2).
• unit structures including the structure represented by formula (B2) are as follows. * indicates a binding site with unit structure A. Needless to say, a unit structure including the illustrated structure as a part of the whole may be used.
• Z is a monocyclic, bicyclic, tricyclic or tetracyclic condensed ring having 4 to 25 carbon atoms, which may have a substituent.
• the number of carbon atoms herein means only the number of carbon atoms constituting the ring skeleton of a monocyclic ring, or a bicyclic, tricyclic, or tetracyclic fused ring excluding substituents, and When the ring is a heterocycle, the number of heteroatoms constituting the heterocycle is not included.
• the monocycle is a non-aromatic monocycle; at least one of the monocycles constituting the bicycle, tricycle, and tetracycle is a non-aromatic monocycle, and the remaining monocycles may be aromatic monocycles or non-aromatic monocycles. It may be an aromatic monocyclic ring.
• the monocyclic, bicyclic, tricyclic or tetracyclic fused ring may further form a fused ring with one or more aromatic rings to form a pentacyclic or more fused ring, and
• the number of carbon atoms in the pentacyclic or larger fused ring is preferably 40 or less, and the number of carbon atoms herein refers to the number of carbon atoms only that constitute the ring skeleton of the pentacyclic or larger fused ring excluding substituents. and does not include the number of heteroatoms constituting the heterocycle when the pentacyclic or higher fused ring is a heterocycle.
• X and Y are the same or different and represent a -CR 31 R 32 - group
• R 31 and R 32 are each the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• x and y represent the numbers of X and Y, respectively, and each independently represents 0 or 1.
• carbon atom 1 and carbon atom 2 may be the same or different, and if different, they may belong to the same non-aromatic monocycle or to different non-aromatic monocycles. .
• formula (B3) may optionally contain a connecting carbon atom other than carbon atom 1 and carbon atom 2 [see (III-3-B33) below]
• Z is a tricyclic or more fused ring
• in the fused ring of one or two non-aromatic monocycles to which carbon atoms 1 and 2 belong, respectively, and the remaining monocycle in formula (B3) The permutation positional relationship is arbitrary, and when carbon atom 1 and carbon atom 2 belong to different non-aromatic monocycles (referred to as "non-aromatic monocycle 1" and “non-aromatic monocycle 2", respectively), the non-aromatic monocycle is The permuted positional relationship of the aromatic monocycle 1 and the non-aromatic monocycle 2 in the condensed ring is also arbitrary.
• Z is a 4- to 17-membered monocyclic, bicyclic, tricyclic, or tetracyclic organic group which may have a substituent, and among the one or more monocycles constituting the organic group, At least one monocycle is a non-aromatic monocycle, and has a maximum of four non-aromatic monocycles.
• the other monocycle is an aromatic ring, and may form a condensed ring with an additional aromatic monocycle to form a polycyclic organic group of pentacyclic or higher ring type.
• non-aromatic monocyclic ring non-aromatic bicyclic ring, non-aromatic tricyclic ring, and non-aromatic tetracyclic ring
• aromatic monocycles or aromatic rings include the same as those exemplified in (I-3) above, but include benzene ring, naphthalene ring, anthracene ring, and pyrene ring which may have substituents. etc. are listed as preferred.
• C and C' in formula (B31) each representing one carbon atom in the atomic group constituting the cyclic portion [so-called linked carbon atoms in (I-1) above] can exist.
• the connected carbon atom C is always present, but the connected carbon atom C' is optional, and n in formula (B31) representing the number of C' is 0 to 2, preferably n is 0.
• X, Y, X', Y' are the same or different and represent a -CR 1 R 2 - group, and R 1 and R 2 are each the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
• x, y, x', and y' representing the number (0 or 1) of X, Y, X', and Y' may all be 0.
• p, q, p', and q' represent the number of bonds, and each independently represents 0 or 1, and when it is 0, it means that it is replaced with a hydrogen atom.
• these bonding hands bond with the aromatic ring of another structure having an aromatic ring (corresponding to unit structure A), but at the polymer end, the polymer terminal group [described later (III-3- See B4)].
• At least two bonding hands are required to form a polymer chain, so when n is 0, p and q are 1; when n is 1, C and C' (so-called linking carbon atoms)
• n is 0, C and C'
• these extra bonding hands may be bonded, for example, to polymer end groups or to aromatic rings in other polymer chains to form crosslinks. It will be done.
• organic groups containing the structure represented by formula (B3) are as follows.
• the binding site with unit structure A is not particularly limited. Needless to say, the structure may include the illustrated structure as a part of the whole.
• Some examples include examples in which the number of bonding hands (*) exceeds 2, but these extra bonding hands can be used for bonding with an aromatic ring in another polymer chain, crosslinking, etc. .
• Z 1 represents at least one non-aromatic monocycle
• Ar 1 represents at least one aromatic monocycle forming a condensed ring with the non-aromatic monocycle of Z 1
• Z and Ar 1 as a whole represent a substituent constitutes a bicyclic, tricyclic, tetracyclic or pentacyclic fused ring having 8 to 25 carbon atoms, which may have
• the number of carbon atoms herein means only the number of carbon atoms constituting the ring skeleton of a bicyclic, tricyclic or tetracyclic condensed ring excluding substituents, and When the condensed ring in the formula is a heterocycle, the number of heteroatoms constituting the heterocycle is not included.
• the above-mentioned bicyclic, tricyclic, tetracyclic or pentacyclic organic group may further form a fused ring with one or more aromatic rings to form a hexacyclic or more ring, and the hexacyclic or more
• the number of carbon atoms in the fused ring is preferably 40 or less, and the number of carbon atoms here means only the number of carbon atoms constituting the ring skeleton of the fused ring of five or more rings excluding substituents;
• the number of heteroatoms constituting the heterocycle when the fused ring of cyclic or higher type is a heterocycle is not included.
• the ordinal positional relationship of the one or more non-aromatic monocycles belonging to Z 1 and the one or more aromatic monocycles belonging to Ar 1 in the cyclic organic group is arbitrary.
• the non-aromatic monocycle belonging to Z 1 and the aromatic monocycle belonging to Ar 1 may be arranged alternately to form a condensed ring.
• the following formula (C3) [In formula (C3), Z 1 , Ar 1 , X, Y, x and y are the same as defined in formula (B32), T represents the polymer terminal. ]
• another unit structure C equivalent to the composite unit structure AB may include a unit structure including the structure of the following formula (C4).
• Z 1 represents at least one non-aromatic monocycle
• Ar 1 represents at least one aromatic monocycle
• Z and Ar 1 as a whole represent an 8- to 17-membered bicyclic or higher ring that may have a substituent.
• C in any non-aromatic monocyclic ring of Z 1 , C [so-called (I- 1) exists.
• X, Y, x, and y are the same as defined in formula (B31).
• T represents a polymer terminal group or an aromatic ring residue Ar2 .
• p represents one bonding hand for a covalent bond with the aromatic ring of the unit structure A (which may also include the aromatic ring in the second unit structure C).
• k and m represent the number of bonds for covalent bonding with the unit structure B (which may include a third unit structure C), and each independently k is 0 to 2 and m is 0. or 1, and at least one of k and m is not 0 (when k and m are 0, it means that the bonding hand is replaced with a hydrogen atom).
• the two bonds of k may extend from the same aromatic monocycle or may extend from different aromatic monocycles.
• k is 2
• k is 1 and m is 1
• the extra bond will form a polymer end group or a crosslink with another polymer chain.
• T in formula (C3) is a hydrogen atom which is a terminal group, and p, k 1 which can be a bonding hand and k 2 , p and k 1 or p and k 2 can form one unit structure C equivalent to the composite unit structure AB.
• k 1 and k 2 can also function as a unit structure A.
• T in formula (C3) is an example of a phenyl group.
• p and k 1 , p and k 2 , or p and m form one unit structure equivalent to the composite unit structure AB. It can be C.
• unit structure C one unit structure equivalent to the composite unit structure AB
• formula (C3) Some more specific examples of the unit structure C (one unit structure equivalent to the composite unit structure AB) of formula (C3) are as follows. * indicates a binding site with unit structure A.
• a bond that connects to the unit structure B separately extends from the aromatic ring in these structures, but in the specific example below, such a bond is omitted.
• a unit structure including the illustrated structure as a part of the whole may be used.
• this can be a specific example of a polymer terminal.
• the unit structure B forms a covalent bond with the end group (polymer end group).
• polymer terminal groups may or may not be aromatic rings derived from unit structure A.
• Such polymer terminal groups include a hydrogen atom, an optionally substituted aromatic ring residue, an optionally substituted organic group containing an unsaturated aliphatic hydrocarbon residue [(III-3- Refer to the substituent corresponding to T in formula (C3) or (C4) in the specific example of B35)].
• a and B have the same meanings as above.
• R represents halogen or an alkyl group having about 1 to 3 carbon atoms.
• One kind of the ring-containing compound and the oxygen-containing compound may be used, or two or more kinds thereof may be used in combination.
• the oxygen-containing compound can be used in a ratio of 0.1 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of the ring-containing compound.
• catalysts used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid, and organic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid.
• Carboxylic acids such as sulfonic acids, formic acid and oxalic acid can be used.
• the amount of the catalyst to be used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.001 to 10,000 parts by mass, per 100 parts by mass of the ring-containing compound (or the total of them if there are multiple types). 0.01 to 1,000 parts by weight, more preferably 0.05 to 100 parts by weight.
• the condensation reaction can be carried out without a solvent, it is usually carried out using a solvent.
• the solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit the reaction.
• 1,2-dimethoxyethane diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, dioxane, 1,2-dichloromethane, 1,2-dichloroethane, toluene, Examples include N-methylpyrrolidone and dimethylformamide.
• the condensation reaction temperature is usually 40°C to 200°C, preferably 100°C to 180°C.
• the reaction time varies depending on the reaction temperature, but is usually 5 minutes to 50 hours, preferably 5 minutes to 24 hours.
• the weight average molecular weight of the novolac resin according to one embodiment of the present invention is usually 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.
• One or more bases B 2 (IV-1)
• One or more bases B2 which are additional base components, are separately added to the underlayer film-forming composition according to the present invention.
• the base traps the acid generated during firing, slowing down the curing speed, and as a result, it is possible to obtain cured films with high flatness and high embedding properties with various film types such as SiO 2 , TiN, and SiN. I can do it.
• a film can be formed that does not cause coloring and does not dissolve into photoresist solvents.
• the amount of base B 2 added is such that the amount of sulfonic acid (When the amount of base required to neutralize a monobasic acid is defined as 1 equivalent, it is preferably 0.05 to 3.0, more preferably 0.1 to 2.5, More preferably, it is 0.2 to 2.0. Similarly, the amount of base required to neutralize the same number of moles of sulfonic acid (monobasic acid) as the sulfonic acid anion group (SO 3 - ) contained in the thermal acid generator (a) is defined as 1 equivalent.
• a base having a pKa larger than that of pyridine in base B 1 and base B 2 is present in an amount of 1.05 equivalent or more, and 1.1 equivalent or more. It is more preferable that the compound is present in an amount of 1.2 equivalents or more, and even more preferably that it is present in an amount of 1.2 equivalents or more.
• a base having a larger pKa than pyridine in base B 1 and base B 2 is present in an amount of 2 equivalents or less.
• a base having a pKa of 6.5 or more is present in an amount of 2 equivalents or less.
• bases having a pKa greater than pyridine preferably having a pKa of 6.5 or higher, include N-methylmorpholine, N,N-diethylaniline, N-isobutylmorpholine, and N-allylmorpholine. etc.
• the pKa value in water preferably by potentiometric titration [see, for example, S.Xu et al., “Dissociation constants of alkanolamines”, Can. J. Chem. can be compared by measuring pKa values in water at 25°C. R.Linnell, J. Org. Chem.
• the resist underlayer film forming composition according to the present invention contains a solvent.
• the solvent is particularly suitable as long as it can dissolve (a) the thermal acid generator, (b) the polymer containing an aromatic ring, and (c) the base, as well as optional components added as necessary. Not limited. In particular, when the solution is used in a uniform solution state for nanoimprinting, it is recommended to use a solvent commonly used in lithography processes in consideration of its coating performance.
• Such solvents include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2 -Methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate,
• (V-2) In addition, from the viewpoint of uniform solubility of (a) acid heat generator, (b) polymer containing an aromatic ring, and (c) base, as well as optional components (such as aminoplast crosslinking agent or phenoplast crosslinking agent).
• a solvent a compound having an alcoholic hydroxyl group or a compound having a group capable of forming an alcoholic hydroxyl group is preferable, and examples of preferable solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve.
• a solvent having a boiling point of 160° C. or higher can be included.
• the following compound described in International Publication No. 2018/131562 (A1) can be used.
• R 1 , R 2 and R 3 in formula (i) each represent a hydrogen atom, an oxygen atom, a sulfur atom, or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and are the same as each other.
• dipropylene glycol monomethyl ether acetate (boiling point 213°C), diethylene glycol monoethyl ether acetate (boiling point 217°C), diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol dimethyl ether (boiling point 247°C), and 171°C), dipropylene glycol monomethyl ether (boiling point 187°C), dipropylene glycol monobutyl ether (boiling point 231°C), tripropylene glycol monomethyl ether (boiling point 242°C), ⁇ -butyrolactone (boiling point 204°C), benzyl alcohol (boiling point 205°C), propylene carbonate (boiling point 242°C), tetraethylene glycol dimethyl ether (boiling point 275°C), 1,6-diacetoxyhexane (boil
• the resist underlayer film forming composition according to the present invention may optionally contain a crosslinking agent, a surfactant, a light absorbing agent, a rheology modifier, an adhesion aid, etc. in addition to the above.
• Aminoplast crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated melamines, benzoguanamines, glycolurils, ureas, polymers thereof, and the like.
• the crosslinking agent has at least two crosslinking substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, These are compounds such as methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Moreover, condensates of these compounds can also be used. Moreover, as the above-mentioned crosslinking agent, a crosslinking agent with high heat resistance can be used.
• a crosslinking agent with high heat resistance a compound containing a crosslinking substituent having an aromatic ring (eg, benzene ring, naphthalene ring) in the molecule can be preferably used. Preferably, it is at least one selected from the group consisting of tetramethoxymethylglycoluril and hexamethoxymethylmelamine.
• the aminoplast crosslinking agents may be used alone or in combination of two or more.
• the aminoplast crosslinking agent can be manufactured by a method known per se or a method analogous thereto, or a commercially available product may be used.
• the amount of the aminoplast crosslinking agent used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but the total solid content of the resist underlayer film forming composition according to the present invention varies. 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, and 80% by mass or less, 50% by mass or less , 40% by mass or less, 20% by mass or less, or 10% by mass or less.
• Phenoplastic crosslinking agents include highly alkylated, alkoxylated, or alkoxyalkylated aromatics, polymers thereof, and the like.
• the crosslinking agent has at least two crosslinking substituents in one molecule, such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2- Hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl) Propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, ⁇ , ⁇ -bis(4-hydroxy-2,5-dimethylphenyl)-4 -Compounds such as formyltoluene.
• condensates of these compounds can also be used.
• a crosslinking agent with high heat resistance can be used.
• a compound containing a crosslinking substituent having an aromatic ring (eg, benzene ring, naphthalene ring) in the molecule can be preferably used.
• the phenoplast crosslinking agents may be used alone or in combination of two or more.
• the phenoplast crosslinking agent can be produced by a method known per se or a method analogous thereto, or a commercially available product may be used.
• the amount of the phenoplast crosslinking agent used varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but it depends on the total solid content of the resist underlayer film forming composition according to the present invention. 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, and 80% by mass or less, 50% by mass or less , 40% by mass or less, 20% by mass or less, or 10% by mass or less.
• examples of such compounds include a compound having a partial structure of the following formula (4), and a polymer or oligomer having a repeating unit of the following formula (5).
• the above R 11 , R 12 , R 13 and R 14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and the above-mentioned examples can be used for these alkyl groups.
• n1 is an integer of 1 to 4
• n2 is an integer of 1 to (5-n1)
• (n1+n2) is an integer of 2 to 5.
• n3 is an integer of 1 to 4
• n4 is 0 to (4-n3)
• (n3+n4) is an integer of 1 to 4.
• Oligomers and polymers can have repeating unit structures ranging from 2 to 100, or from 2 to 50.
• the resist underlayer film forming composition according to the present invention does not generate pinholes or striations, and can contain a surfactant in order to further improve coating properties against surface unevenness.
• surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and polyoxyethylene nonyl.
• Polyoxyethylene alkyl allyl ethers such as phenol ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristear Sorbitan fatty acid esters such as esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
• Nonionic surfactants such as ethylene sorbitan fatty acid esters, EFTP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-30, R-40 (manufactured by Dainippon Ink Co., Ltd.) Co., Ltd., product name), Florado FC430, FC431 (Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) , trade name), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
• ethylene sorbitan fatty acid esters EFTP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd
• 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 according to the present invention.
• These surfactants may be added alone or in combination of two or more.
• acidic compounds such as citric acid, 2,4,4,6-tetrabromo Thermal acid generators such as cyclohexadienone, benzointosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, etc.
• acidic compounds such as citric acid, 2,4,4,6-tetrabromo Thermal acid generators such as cyclohexadienone, benzointosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, etc.
• Onium salt-based photoacid generators halogen-containing compound-based photoacid generators such as phenyl-bis(trichloromethyl)-s-triazine, sulfonic acid-based photoacids such as benzointosylate, N-hydroxysuccinimide trifluoromethanesulfonate, etc. Generating agents and the like can also be blended.
• the light absorbing agent include commercially available light absorbing agents described in "Technology and Market of Industrial Colorants” (CMC Publishing) and “Dye Handbook” (edited by the Organic Synthetic Chemistry Association), such as C.I. I.
• SolventRed 1, 3, 8, 23, 24, 25, 27 and 49; C. I. PigmentGreen 10;C. I. Pigment Brown 2 etc. can be suitably used.
• the above-mentioned light absorbing agent is usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film forming composition according to the present invention.
• the rheology modifier mainly improves the fluidity of the resist underlayer film forming composition, and improves the uniformity of the resist underlayer film thickness and the filling ability of the resist underlayer film forming composition into the holes, especially in the baking process. It is added for the purpose of enhancing.
• phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butylisodecyl phthalate
• adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate
• maleic acid derivatives such as normal butyl maleate, diethyl maleate, and dinonyl maleate
• oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate
• stearic acid derivatives such as normal butyl stearate and glyceryl stearate.
• the adhesion auxiliary agent is added mainly for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film forming composition, and particularly for preventing the resist from peeling off during development.
• chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and Alkoxysilanes such as enyltriethoxysilane, silazane such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, ⁇ -chloropropyltrimethoxysilane, ⁇ - Silanes such as aminopropyltriethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, benzotriazole,
• adhesion aids are generally blended in an amount of less than 5% by mass, preferably less than 2% by mass, based on the total solid content of the resist underlayer film forming composition according to the present invention.
• the solid content of the resist underlayer film forming composition according to the present invention is 0.1 to 70% by mass, or 0.1 to 60% by mass.
• the solid content is the content of all components in the resist underlayer film forming composition excluding the solvent.
• the crosslinkable resin can be contained in the solid content in a proportion of 1 to 99.9% by mass, or 50 to 99.9% by mass, or 50 to 95% by mass, or 50 to 90% by mass.
• the resist underlayer film can be formed as follows using the resist underlayer film forming composition according to the present invention.
• Substrates used in the manufacture of semiconductor devices e.g. silicon wafer substrates, silicon dioxide coated substrates (SiO 2 substrates), silicon nitride substrates (SiN substrates), silicon nitride oxide substrates (SiON substrates), titanium nitride substrates (TiN
• the present invention is coated onto substrates (substrates), tungsten substrates (W substrates), glass substrates, ITO substrates, polyimide substrates, low dielectric constant material (low-k material) coated substrates, etc.) using an appropriate coating method such as a spinner or coater.
• a resist underlayer film is formed by applying the resist underlayer film forming composition, which is one embodiment of the above, and then baking it using a heating means such as a hot plate.
• the firing conditions are appropriately selected from among a firing temperature of 80° C. to 600° C. and a firing time of 0.3 to 60 minutes.
• the firing temperature is 150°C to 400°C, more preferably 150°C to 350°C; firing time is 0.5 to 2 minutes.
• Air may be used as the atmospheric gas during firing, or an inert gas such as nitrogen or argon may also be used. In one embodiment, it is particularly preferable that the oxygen concentration is 1% or less.
• the thickness of the lower layer film to be formed is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm.
• a quartz substrate is used as the substrate, a replica of a quartz imprint mold (mold replica) can be produced.
• an adhesion layer and/or a silicone layer containing 99% by mass or less, or 50% by mass or less of Si can also be formed on the resist underlayer film, which is one embodiment of the present invention, by coating or vapor deposition.
• a Si-based inorganic material film can be formed using a CVD method or the like.
• the resist underlayer film forming composition which is an embodiment of the present invention, is applied onto a semiconductor substrate (so-called step substrate) having a portion with a step and a portion without a step, and then baked to remove the step. It is possible to reduce the difference in level between the part having the step and the part not having the step.
• a method for manufacturing a semiconductor device includes: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition that is one aspect of the present invention; forming a resist film on the formed resist underlayer film; forming a resist pattern by irradiating the formed resist film with light or electron beam and developing; etching the resist underlayer film through the formed resist pattern; and processing the semiconductor substrate through the patterned resist underlayer film. including.
• a method for manufacturing a semiconductor device includes: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition that is one aspect of the present invention; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating the formed resist film with light or electron beam and developing; etching the hard mask through the formed resist pattern; etching the resist underlayer film through the patterned hard mask; and processing the semiconductor substrate through the patterned resist underlayer film.
• a method for manufacturing a semiconductor device includes: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition that is one aspect of the present invention; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating the formed resist film with light or electron beam and developing; a step of etching the hard mask using the formed resist pattern; etching the resist underlayer film using a patterned hard mask; a step of removing the hard mask, and a step of processing the semiconductor substrate with the patterned resist underlayer film, including.
• a method for manufacturing a semiconductor device includes: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition that is one aspect of the present invention; forming a hard mask on the formed resist underlayer film; forming a resist film on the formed hard mask; forming a resist pattern by irradiating the formed resist film with light or electron beam and developing; a step of etching the hard mask using the formed resist pattern; etching the resist underlayer film using a patterned hard mask; a step of removing the hard mask, and a step of forming a deposited film (spacer) on the resist underlayer film after the hard mask has been removed, A process of processing the deposited film (spacer) by etching, a step of removing the patterned resist underlayer film to leave a patterned deposited film (spacer); and a step of processing the semiconductor substrate via the patterned deposited film (spacer). including.
• the step of forming a resist underlayer film using the resist underlayer film forming composition that is one embodiment of the present invention is as described in [VII: Resist Underlayer Film] above.
• a hard mask such as a silicon-containing film may be formed as a second resist underlayer film on the resist underlayer film formed in the above step, and a resist pattern may be formed thereon.
• This second resist underlayer film may be a coating film, or may be a SiON film, SiN film, or SiO 2 film formed by a vapor deposition method such as CVD or PVD.
• an anti-reflection coating may be formed as a third resist under-layer film on this second resist under-layer film, and the third resist under-layer film is a resist shape correction film having no anti-reflection ability.
• the exposure source for example, g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, or electron beam can be used. After exposure, post-exposure baking is performed as needed.
• a developer for example, 2.38% by mass aqueous tetramethylammonium hydroxide solution, butyl acetate
• a rinse solution or pure water to remove the used developer.
• post-baking is performed to dry the resist pattern and improve its adhesion to the base.
• the etching process performed after forming the resist pattern is performed by dry etching.
• the following gases are used to process the hard mask (silicon-containing layer), resist underlayer film, and substrate: CF 4 , CHF 3 , CH 2 F 2 , CH 3 F, C 4 F 6 , C 4 F 8 , O2 , N2O , NO2 , H2 , He can be used. These gases may be used alone or in combination of two or more.
• argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon, or nitrogen trifluoride can be used in combination with these gases.
• the resist film may be patterned by a nanoimprint method or a self-assembled film method.
• a resist composition is molded using a patterned mold that is transparent to irradiation light.
• a pattern is formed using a self-assembled film that naturally forms a regular structure on the order of nanometers, such as a diblock polymer (polystyrene-polymethyl methacrylate, etc.).
• a silicon layer (hard mask layer) is optionally formed by coating or vapor deposition on the resist underlayer film, and then a silicon layer (hard mask layer) is optionally formed on the resist underlayer film or silicone.
• An adhesion layer may be formed on the layer (hard mask layer) by coating or vapor deposition, and a curable composition that becomes a resist film may be applied on the adhesion layer.
• alkaline components include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, and ethyltrimethylammonium.
• an inorganic base may be used in combination with quaternary ammonium hydroxide.
• alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, and rubidium hydroxide are preferred, and potassium hydroxide is more preferred.
• the resist underlayer film forming composition according to the present invention is characterized in that one or more bases B2 , which are additional base components, are separately added.
• bases B2 which are additional base components
• the addition of such a base slows down the curing rate as the base traps the acid generated during firing, resulting in high performance in various film types such as SiO 2 , TiN, and SiN.
• a cured film with flattening and high embedding properties can be obtained.
• a film can be formed that does not cause coloring and does not dissolve into photoresist solvents.
• resist underlayer film materials (M1 to M29, Comparative M1 to Comparative M18) were prepared by filtering with a 0.1 ⁇ m polytetrafluoroethylene microfilter.
• the numerical values of the crosslinking agent, acid generator, and surfactant represent the number of grams of the crosslinking agent, acid generator, and surfactant used when 100 g of the polymer was used.
• the numerical value of the base is a molar multiplier with respect to the number of moles of the acid generator, and since the standard is different, it is expressed in parentheses.
• the numerical value of each solvent represents the number of grams of each solvent used when the total amount of solvent is 100 g.
• the planarity of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the film thickness of the trench area (patterned part) and open area (patterned part) of the step substrate was Flattenability was evaluated by measuring the difference (the difference in coating level between the trench area and the open area, which is called a bias).
• flatness refers to the part where a pattern exists (trench area (pattern part)) and the part where no pattern exists (open area (pattern part)), and the coated coating that exists on top of it. This means that the film thickness difference (Iso-dense bias) is small.
• a sample with improved bias compared to a comparative example was judged as ⁇ .
• the numerical values of the crosslinking agent, acid generator, and surfactant represent the number of grams of the crosslinking agent, acid generator, and surfactant used when 100 g of the polymer was used.
• the numerical value of the base is a molar multiplier with respect to the number of moles of the acid generator, and since the standard is different, it is expressed in parentheses.
• the numerical value of each solvent represents the number of grams of each solvent used when the total amount of solvent is 100 g.
• the planarity of this substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Technologies Corporation, and the film thickness of the trench area (patterned part) and open area (patterned part) of the step substrate was Flattenability was evaluated by measuring the difference (the difference in coating level between the trench area and the open area, which is called a bias).
• a bias refers to the part where a pattern exists (trench area (pattern part)) and the part where no pattern exists (open area (pattern part)). This means that the film thickness difference (Iso-dense bias) is small.
• a sample with improved bias compared to a comparative example was judged as ⁇ .

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