Coating agent composition for nitrogen atom-containing substrate

Abstract

Provided is a coating agent composition which is suitable for forming a resist underlayer film, and which does not impair the resolution of a resist even when a substrate containing nitrogen atoms is used, and which is capable of obtaining a good resist shape even when a resist film is developed after a long period of time after the formation of the resist film. A coating agent composition for a nitrogen-atom-containing substrate, which contains a solvent and a novolac resin that contains a unit structure A having a carbazole skeleton or a phenol / phenoxy skeleton at least as a partial structure, the substrate containing a nitrogen atom is formed from a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing a nitrogen atom formed from a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom; a resist underlayer film on a substrate containing nitrogen atoms, which is a fired product of a coating film formed from the composition; and a method for manufacturing a semiconductor device using the composition.

Description

Technical Field

[0001] The present invention relates to a coating agent composition suitable as a composition for forming an underlayer film for a resist used in lithography for processing a semiconductor substrate, an underlayer film for a resist obtained from the composition, a method for forming a resist pattern using the composition, and a method for manufacturing a semiconductor device using the composition. Background Art

[0002] The development of semiconductor manufacturing processes has been rapid, and along with this, there has been a strong demand for higher quality and improved characteristics of underlayer films for resists. For example, it is known that when a substrate containing nitrogen atoms is used as the base of an underlayer film for a resist, the resolution of the resist is impaired due to the diffusion of amine components (Patent Documents 1 to 3). Generally, the resist film is immediately subjected to an exposure process and then developed after formation, but due to manufacturing processes, development may sometimes be performed after a long time has passed since the resist film was formed. It is known that in such processes, a problem of change in the resolution of the resist occurs compared to the case of exposure immediately after coating. Furthermore, in existing processes, when an underlayer film for a resist is applied to suppress the diffusion of amine components, if the processes during or after resist imaging are considered, the formation of the underlayer film for a resist causes a change in reflectance, deterioration of the pattern shape, and a high process load during pattern processing. Therefore, it is required that the underlayer film for a resist be as thin as possible.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-39811

[0006] Patent Document 2: Japanese Patent Application Laid-Open No. 2008-39815

[0007] Patent Document 3: Japanese Patent Application Laid-Open No. 2010-134437 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] Therefore, the problem to be solved by the present invention is to provide a suitable coating agent composition that, when using a substrate containing nitrogen atoms, can maintain stable resolution even after a long time has passed since the resist film was formed by applying a thin underlayer film for a resist, and does not affect reflectance or pattern processing, thereby enabling a reduction in the process load.

[0010] Means for Solving the Problems

[0011] The present invention includes the following aspects. [1]

[0013] A coating agent composition for a substrate containing a nitrogen atom, which is a coating agent composition for a substrate containing a nitrogen atom and comprises a novolak resin and a solvent.

[0014] The novolak resin contains a unit structure A having at least a carbazole skeleton or a phenol / phenoxy skeleton as part of its structure.

[0015] The above-mentioned substrate containing a nitrogen atom is a substrate formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing a nitrogen atom, and the above-mentioned film containing a nitrogen atom is formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom. [2]

[0017] The coating agent composition for a substrate containing a nitrogen atom according to [1] above is a composition for forming an underlayer film of a resist. [3]

[0019] The coating agent composition for a substrate containing a nitrogen atom according to [2] above, and the above-mentioned underlayer film of the resist is a thin underlayer film of the resist with a film thickness of less than 10 nm. [4]

[0021] The coating agent composition for a substrate containing a nitrogen atom according to any one of [1] to [3] above, and the above-mentioned film containing a nitrogen atom constitutes the outermost layer of the substrate containing a nitrogen atom. [5]

[0023] The coating agent composition for a substrate containing a nitrogen atom according to any one of [1] to [4] above, and the above-mentioned metal atom or metalloid atom is

[0024] (i) silicon,

[0025] (ii) titanium, or

[0026] (iii) tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or their alloys. [6]

[0028] The coating agent composition for a substrate containing a nitrogen atom according to any one of [1] to [5] above, and the above-mentioned compound having a bond between a metal atom or a metalloid atom and a nitrogen atom is SiON, SiN, TiON or TiN. [7]

[0030] The coating agent composition for a substrate containing a nitrogen atom according to any one of [1] to [6] above, wherein the above unit structure A having at least a carbazole skeleton or a phenol / phenoxy skeleton as part of the structure is a structural unit derived from one or more compounds selected from the following structural formulas (A-1) to (A-9).

[0031]

[0032] Among them,

[0033] In formulas (A-1) to (A-9),

[0034] R N and R O each independently represents

[0035] (i) a hydrogen atom or a hydroxymethyl group,

[0036] (ii) an aryl group having 6 to 30 carbon atoms, or

[0037] (iii) a linear, branched or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms,

[0038] Among them, R N is bonded to the nitrogen atom on the carbazole skeleton, and R O is bonded to the oxygen atom of the aryloxy group of Ar B ring.

[0039] In addition, regarding the above (ii) and (iii), the hydrogen atoms in these groups may be further substituted by a substituent containing an oxygen atom, a substituent containing a sulfur atom, a substituent containing a nitrogen atom, an aryl group or a halogen-containing group, and the hydrocarbon chain portion of the above (iii) may be further interrupted by a substituent containing an oxygen atom, a substituent containing a sulfur atom, a substituent containing a nitrogen atom or an arylene group.

[0040] In formulas (A-8) to (A-9),

[0041] Ar B each independently represents a benzene ring, a naphthalene ring or a condensed ring containing one or more benzene rings.

[0042] In formula (A-8), m represents the number of R O O groups of 1 or more.

[0043] In formulas (A-7) and (A-9),

[0044] L represents a single bond or a polyvalent linking group having a valence of 2 to 8.

[0045] In formula (A-7),

[0046] n1 represents the number of carbazole skeletons to which L is bonded to the carbon atoms on the aromatic ring of the carbazole skeleton, and n2 represents the number of carbazole skeletons to which L is bonded to the nitrogen atoms on the carbazole skeleton. n1 and n2 are each greater than 0, but the sum of n1 and n2 is an integer of 2 to 8. When L is a single bond, the sum of n1 and n2 is 2.

[0047] In formula (A-9),

[0048] m21 is Ar B The carbon atom on the ring that is bound to L (R O O) m11 Ar B The number of bases, m11 each independently represents R O O-based numbers,

[0049] m22 represents Ar B The oxygen atom of the aryloxy group of the ring is bonded to OAr B (OR O ) m12 The number of bases, m12 each independently represents R O The number of O groups, m11, m21, m12 and m22 are each 0 or more, but the sum of m21 m11 and m22 is 1 or more, and the sum of m21 and m22 is 2 to 8. When L is a single bond, the sum of m21 and m22 is 2.

[0050] In each of the aromatic rings in the formulae (A-1) to (A-9), further substituents may be optionally present. [8]

[0052] According to the coating composition for a substrate containing a nitrogen atom described in [7], the above L is selected from a single bond, -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, -NH-, -(CR 1 R 2 ) m1 -、-(Ar) m2 -、-CH2-(Ar) m2 -CH2- and -(cyclo-R)-,

[0053] R 1 and R 2 are the same or different, and each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and m1 represents an integer of 1 to 10,

[0054] Ar represents an arylene group having 6 to 30 carbon atoms, m2 represents an integer of 1 to 3 which is the number of aromatic rings bonded to each other via single bonds,

[0055] cyclo-R represents a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which can form a condensed ring with one or two benzene rings or naphthalene rings. [9]

[0057] In the coating agent composition for a substrate containing a nitrogen atom as described in [7] or [8] above, as R N or R O at least a part thereof contains the following substituents.

[0058] -R 3 —C≡C—R 4

[0059] [wherein,

[0060] * represents a bonding site,

[0061] R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms,

[0062] R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ]]

[10]

[0064] In the coating agent composition for a substrate containing a nitrogen atom as described in any one of [1] to [9] above, the novolak resin contains a composite unit structure A-B represented by the following formula (AB),

[0065]

[0066] In the above formula (AB),

[0067] n represents the number of the composite unit structure A-B,

[0068] The unit structure A is the unit structure A described in [1],

[0069] The unit structure B represents one or more unit structures including the structures represented by the following formulae (B1), (B2) or (B3),

[0070] * represents a bonding site.

[0071]

[0072] [In the formula (B1),

[0073] R and R' each independently represent a hydrogen atom, an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent; a heterocyclic residue having 3 to 30 carbon atoms which may have a substituent; a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent; or a formyl group,

[0074] * represents a bonding bond.]

[0075] *-J 1 -Z 0 -J 2 -*(B2)

[0076] [In formula (B2),

[0077] Z 0 represents an aromatic ring residue or an aliphatic ring residue having 6 to 30 carbon atoms which may have substituents, or an organic group in which two aromatic ring residues or aliphatic ring residues are connected by a single bond,

[0078] J 1 and J 2 each independently represents a direct bond or a divalent organic group which may have substituents,

[0079] * represents a bonding bond.]

[0080]

[0081] [In formula (B3),

[0082] Z is a monocyclic, bicyclic, tricyclic or tetracyclic fused ring having 4 to 25 carbon atoms which may have substituents, and the above monocyclic ring is a non-aromatic monocyclic ring; at least one of the monocyclic rings constituting the above bicyclic, tricyclic and tetracyclic rings is a non-aromatic monocyclic ring, and the remaining monocyclic rings may be aromatic monocyclic rings or non-aromatic monocyclic rings, and the above monocyclic or bicyclic, tricyclic or tetracyclic fused ring may further form a fused ring with one or more aromatic rings to form a fused ring of five rings or more,

[0083] X and Y are the same or different and represent -CR 31 R 32 - group, R 31 and R 32 each being the same or different represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms,

[0084] x and y each represent the number of X and Y, and each independently represents 0 or 1,

[0085] *——X x In the case of x = 1, it binds to any carbon atom of the above non-aromatic monocyclic ring constituting Z, that is, carbon atom 1, and in the case of x = 0, it extends from carbon atom 1,

[0086] Y y ——* In the case of y = 1, it binds to any carbon atom of the above non-aromatic monocyclic ring constituting Z, that is, carbon atom 2, and in the case of y = 0, it extends from carbon atom 2,

[0087] The above carbon atom 1 and carbon atom 2 may be the same or different, and in different cases, they may belong to the same non-aromatic single ring or different non-aromatic single rings.

[0088] * represents a bonding site.

[11]

[0090] According to the coating agent composition for a substrate containing a nitrogen atom described in any one of the above [1] to

[10] , the above solvent contains a solvent having a boiling point of 160 °C or higher.

[12]

[0092] According to the coating agent composition for a substrate containing a nitrogen atom described in any one of the above [1] to

[11] , it further contains an acid and / or its salt and / or an acid generator.

[13]

[0094] According to the coating agent composition for a substrate containing a nitrogen atom described in any one of the above [1] to

[12] , it further contains a crosslinking agent.

[14]

[0096] According to the coating agent composition for a substrate containing a nitrogen atom described in the above

[13] , the above crosslinking agent is an amino plastic crosslinking agent or a phenolic plastic crosslinking agent.

[15]

[0098] According to the coating agent composition for a substrate containing a nitrogen atom described in any one of the above [1] to

[14] , it further contains a surfactant.

[16]

[0100] A resist underlayer film on a substrate containing a nitrogen atom is a fired product of a coating film formed from the coating agent composition for a substrate containing a nitrogen atom described in any one of the above [1] to

[15] .

[17]

[0102] According to the resist underlayer film on a substrate containing a nitrogen atom described in the above

[16] , its film thickness is less than 10 nm.

[18]

[0104] A method for forming a resist pattern for manufacturing a semiconductor includes a step of coating the coating agent composition for a substrate containing a nitrogen atom described in any one of the above [1] to

[15] on a semiconductor substrate containing a nitrogen atom, and then performing firing to form a resist underlayer film.

[19]

[0106] A method for manufacturing a semiconductor device includes the following steps:

[0107] A step of forming an underlayer resist film on a semiconductor substrate containing a nitrogen atom by using the coating agent composition according to any one of [1] to

[15] above;

[0108] A step of forming a resist film on the underlayer resist film; and

[0109] A step of forming a resist pattern on the resist film by irradiation with light or an electron beam and development.

[20]

[0111] The method for manufacturing a semiconductor device according to

[19] above further includes a step of etching the underlayer resist film via the resist pattern.

[21]

[0113] The method for manufacturing a semiconductor device according to

[20] above further includes a step of processing the semiconductor substrate through the patterned underlayer resist film.

[22]

[0115] The method for manufacturing a semiconductor device according to any one of

[19] to

[21] above, wherein the step of forming a resist pattern on the resist film is performed by nanoimprint lithography or a self-assembled monolayer method.

[23]

[0117] An underlayer resist film forming agent composition, which is an underlayer resist film forming agent composition containing a novolak resin and a solvent,

[0118] The novolak resin contains a repeating unit structure A having at least a carbazole skeleton or a phenol / phenoxy skeleton as part of the structure,

[0119] The film thickness of the underlayer resist film is less than 10 nm.

[0120] Effects of the Invention

[0121] When a novolak resin containing a carbazole structure in the skeleton or a novolak resin containing a phenol structure or a phenoxy structure in the skeleton is coated on a substrate containing a nitrogen atom, even for an ultrathin film of less than 10 nm, diffusion of the amine component contained in the substrate can be suppressed. When a resist film is provided on the underlayer resist film containing the resin, a beautiful resist pattern with a vertical shape can be formed without impairing the resolution of the resist film.

[0122] Furthermore, the so-called vertical resist pattern is related to the ability to suppress the diffusion of the amine component from the base film, that is, the substrate. Therefore, it can be said that excellent resolution is exhibited even when exposure is performed after a long time has passed after the formation of the resist film.

[0123] Furthermore, since good coatability is exhibited for various substrate types and substrates with height differences even when coated with an ultrathin film, and sufficient curability is shown, film thickness fluctuations within the same wafer can be suppressed. Detailed Embodiments

[0124] [I. Definitions of Terms]

[0125] In this specification, the definitions of the main terms related to the novolak resin, which is one aspect of the invention of this application, are described below. Unless otherwise specifically stated, the following definitions of each term are applied to the novolak resin.

[0126] (I-1) "Novolak resin"

[0127] The so-called "novolak resin" includes not only the narrow-sense phenol / formaldehyde resin (so-called novolak-type phenolic resin) and aniline / formaldehyde resin (so-called novolak-type aniline resin), but also widely includes, in the presence of an acid catalyst or under reaction conditions equivalent thereto, through an organic compound having a functional group capable of covalently bonding to an aromatic ring [for example, aldehyde group, ketone group, acetal group, ketal group, hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon; hydroxyl group, alkoxy group or halogen-containing group bonded to the α-position carbon atom (such as benzyl-position carbon atom) of an alkylaryl; carbon-carbon unsaturated bond such as divinylbenzene and dicyclopentadiene, etc.] and an aromatic ring of an aromatic compound (preferably having a substituent containing a heteroatom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. on the aromatic ring), the covalent bond formation (substitution reaction, addition reaction, condensation reaction or addition-condensation reaction, etc.) of the aromatic ring is used in a broad sense to form a polymer.

[0128] Therefore, the novolak resin in the specification of this application forms a covalent bond between the aromatic ring of an aromatic compound and an organic compound containing a carbon atom (sometimes called "linking carbon atom") derived from the above functional group through the linking carbon atom, thereby connecting multiple aromatic compounds to form a polymer.

[0129] In this specification, as the unit structures constituting the "novolak resin", the terms of unit structure A, unit structure B and unit structure C are used. Unit structure A is the unit structure derived from an aromatic compound. Unit structure B is the unit structure derived from a compound having a functional group capable of covalently bonding to the aromatic ring of unit structure A. Unit structure C is a single unit structure with a bonding mode equivalent to the composite unit structure A-B, and is the unit structure derived from a compound having an aromatic ring and a functional group capable of covalently bonding to the aromatic ring of unit structure A. Since the bonding modes are the same, unit structure C can be replaced by the composite unit structure A-B.

[0130] (I-2) "Residue"

[0131] The so-called "residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or a heteroatom (such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.) is replaced by a bonding moiety, and it can be a monovalent group or a polyvalent group. For example, if one hydrogen atom is replaced by one bonding moiety, it becomes a monovalent organic group, and if two hydrogen atoms are replaced by bonding moieties, it becomes a divalent organic group.

[0132] (I-3) "Aromatic ring" (aromatic group, aryl group, arylene group)

[0133] The so-called "aromatic ring" is a concept that includes aromatic hydrocarbon rings, aromatic heterocycles, and their residues [sometimes also referred to as "aromatic groups", "aryl groups" (in the case of monovalent groups), or "arylene groups" (in the case of divalent groups)], and includes not only monocyclic (aromatic monocycles) but also polycyclic (aromatic polycycles). In the case of polycycles, at least one monocyclic ring is an aromatic monocyclic ring, and the remaining monocyclic rings that form a fused ring with this aromatic monocyclic ring can be monocyclic heterocycles (heteromonocycles) or monocyclic alicyclic hydrocarbons (alicyclic monocycles).

[0134] Examples of aromatic rings include benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, isopropylbenzene, anthracene, phenanthrene, benzo[9,10]phenanthrene, benzanthracene, pyrene, fluorene, biphenyl, coronene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, coronene, dibenzo[g,p] acenaphthene, acenaphthylene, tetracene, pentacene, cyclooctatetraene and other aromatic hydrocarbon rings, more typically aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, pyrene; furan, pyran, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindolylfluorene, bisindolylbenzofluorene, bisindolyldibenzofluorene, purine, quinoline, isoquinoline, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, indolocarbazole and other aromatic heterocycles, more typically furan, thiophene, pyrrole, indole, phenylindole, bisindolylfluorene, phenothiazine, carbazole, indolocarbazole, imidazole, pyran, pyridine, pyrimidine, pyrazine, etc., but not limited to these.

[0135] The aromatic ring (such as benzene ring, naphthalene ring, etc.) may optionally have substituents. Examples of such substituents include a halogen atom, a saturated or unsaturated straight-chain, branched-chain or cyclic hydrocarbon group (-R) (which may be interrupted by an oxygen atom more than once in the middle of the hydrocarbon chain. It includes an alkyl group, an alkenyl group, an alkynyl group, a propargyl group), an alkoxy group or an aryloxy group (-OR, where R represents the above-mentioned hydrocarbon group -R), an alkylamino group [-NHR or -NR2 (the two Rs may be the same or different from each other), where R represents the above-mentioned hydrocarbon group -R, including an alkyl group, an alkenyl group, an alkynyl group, a propargyl group, etc. that may be interrupted by an oxygen atom more than once in the middle of the hydrocarbon chain], a hydroxyl group, an amino group (-NH2), a carboxyl group, a cyano group, a nitro group, an ester group (-CO2R or -OCOR, where R represents the above-mentioned hydrocarbon group -R), an amide group (-NHCOR, -CONHR, -NRCOR (the two Rs may be the same or different from each other) or -CONR2 (the two Rs may be the same or different from each other), where R represents the above-mentioned hydrocarbon group -R), a group containing sulfonyl (-SO2R, where R represents the above-mentioned hydrocarbon group -R or a hydroxyl group -OH), a mercapto group (-SH), a group containing thioether (-SR, where R represents the above-mentioned hydrocarbon group -R); an organic group containing an ether bond [R 11 -O-R 11 (R 11 (each independently represents an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a naphthyl group, an anthraniloyl group, a pyrenyl group, etc.) the residue of an ether compound shown; for example, an organic group containing an ether bond including a methoxy group, an ethoxy group, a phenoxy group], an aryl group and other substituents.

[0136] Furthermore, the aromatic group also includes an organic group having a condensed ring of one or more aromatic rings (benzene, naphthalene, anthracene, pyrene, etc.) and one or more aliphatic rings or heterocycles. Furthermore, examples of the so-called aliphatic ring here include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, cycloheptene, etc., and examples of the heterocycle include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, etc.

[0137] It may 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.

[0138] (I-4) "Heterocycle"

[0139] "Heterocycle" is a concept that includes both aliphatic heterocycles and aromatic heterocycles, and includes not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic). In the case of polycyclic, at least one monocyclic ring is a heteromonocyclic ring, and the remaining monocyclic rings may be an aromatic hydrocarbon monocyclic ring or an alicyclic monocyclic ring. For aromatic heterocycles, reference can be made to the examples in the above (I-3). Similar to the aromatic ring in the above (I-3), it may have substituents.

[0140] (I-5) "Non-aromatic ring" (aliphatic ring)

[0141] The so-called "non-aromatic monocyclic ring" is a monocyclic hydrocarbon system that does not belong to the aromatic group, typically a monocyclic ring of an alicyclic compound. It can be called an aliphatic monocyclic ring (an aliphatic hetero-monocyclic ring can be included as long as it does not belong to the aromatic compound and can contain unsaturated bonds). Similar to the aromatic ring in the above (I-3), it can have substituents.

[0142] Examples of the non-aromatic monocyclic ring (aliphatic ring or aliphatic monocyclic ring) include, for example, cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, cycloheptene, etc.

[0143] The so-called "non-aromatic polycyclic ring" is a polycyclic hydrocarbon that does not belong to the aromatic group, typically a polycyclic ring of an alicyclic compound. It can be called an aliphatic polycyclic ring [an aliphatic hetero-polycyclic ring (at least one of the monocyclic rings constituting the polycyclic ring is an aliphatic heterocyclic ring) can be included as long as it does not belong to the aromatic compound and can contain unsaturated bonds]. The non-aromatic polycyclic ring includes non-aromatic bicyclic rings, non-aromatic tricyclic rings, and non-aromatic tetracyclic rings.

[0144] The so-called "non-aromatic bicyclic ring" is a fused ring composed of two monocyclic hydrocarbon systems that do not belong to the aromatic group, typically a fused ring of two alicyclic compounds. In this specification, it is sometimes also called an aliphatic bicyclic ring (an aliphatic hetero-bicyclic ring can be included as long as it does not belong to the aromatic compound and can contain unsaturated bonds). Examples of the non-aromatic bicyclic ring include bicyclopentane, bicyclooctane, bicycloheptene, etc.

[0145] The so-called "non-aromatic tricyclic ring" is a fused ring composed of three monocyclic hydrocarbon systems that do not belong to the aromatic group, typically a fused ring of three alicyclic compounds (each can be a heterocyclic ring as long as it does not belong to the aromatic compound and can contain unsaturated bonds). Examples of the non-aromatic tricyclic ring include tricyclooctane, tricyclononane, tricyclodecane, etc.

[0146] The so-called "non-aromatic tetracyclic ring" is a fused ring composed of four monocyclic hydrocarbon systems that do not belong to the aromatic group, typically a fused ring of four alicyclic compounds (each can be a heterocyclic ring as long as it does not belong to the aromatic compound and can contain unsaturated bonds). Examples of the non-aromatic tetracyclic ring include hexadecahydropyrene, etc.

[0147] (1-6)

[0148] The so-called "carbon atoms constituting the ring (part)" refers to the carbon atoms constituting the ring for a hydrocarbon ring in the unsubstituted state (which can be any of an aromatic ring, an aliphatic ring, or a heterocyclic ring).

[0149] (I-7)

[0150] The so-called "hydrocarbyl group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such a hydrocarbon includes saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0151] (1-8)

[0152] In the chemical structural formula representing the unit structure of the novolak resin in the specification of the present application, a bonding bond (represented by *) is sometimes described for convenience, but as long as there is no special description, such a bonding bond can adopt any bonding position capable of bonding in the unit structure, and the bonding position in the unit structure is not limited at all.

[0153] [II. Coating Agent Composition for Substrate Containing Nitrogen Atom]

[0154] A coating agent composition for a substrate containing a nitrogen atom according to one aspect of the present invention is a coating agent composition for a substrate containing a nitrogen atom, which comprises a novolak resin and a solvent, and the novolak resin comprises a unit structure A or a repeating unit structure A having at least a carbazole skeleton or a phenol / phenoxy skeleton as a partial structure.

[0155] The coating agent composition for a substrate containing a nitrogen atom is a coating agent used in the application of forming a coating film on a substrate containing a nitrogen atom. It is preferably used in the application of forming an underlayer film for a resist, so that the following advantages can be provided: even when exposure is performed after a long time has passed after forming the resist film, the resolution of the resist film is not impaired, and a beautiful resist pattern having a vertical shape can be formed. Generally, it is considered that by using a thick film material as the underlayer film for the resist, the diffusion of amine components in the substrate containing a nitrogen atom can be suppressed, but it leads to an increase in the process load, an increase in the material cost, and a deterioration in the resist shape due to the deterioration of the reflection suppression ability in the subsequent processing. Therefore, it is very important to avoid the above-mentioned adverse effects and suppress the diffusion of amine components at the same time. The coating agent composition for a substrate containing a nitrogen atom of the present invention can sufficiently provide the above advantages even when used for forming an ultrathin underlayer film for a resist with a film thickness of less than 10 nm.

[0156] Although not bound by theory, it can be considered that the reason why the novolak resin containing a carbazole skeleton or a phenol / phenoxy skeleton suppresses the diffusion of amine components is different from that of neutralizing amine components with an acidic additive as shown in the patent literature to prevent diffusion. It can be considered that the above novolak resin has a large number of aromatic rings with a high carbon content in the skeleton and high rigidity, so that the intermolecular gaps through which amine components can diffuse from the substrate are significantly reduced, thereby preventing the diffusion of amine components.

[0157] (II-1) Substrate Containing Nitrogen Atom

[0158] The substrate containing a nitrogen atom is a substrate formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing a nitrogen atom, and the film containing a nitrogen atom is formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom.

[0159] Examples of the metal atom or the metalloid atom include

[0160] (i) silicon,

[0161] (ii) titanium, or

[0162] (iii) tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[0163] Furthermore, as the compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, typical examples include SiON, SiN, TiON, or TiN.

[0164] In addition, the effects of the coating agent composition as one aspect of the present invention can be most effectively exerted in the following aspects: a case of directly coating on a substrate formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom; or a case of coating on a substrate having a film containing a nitrogen atom formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, and the film containing a nitrogen atom constitutes the outermost layer of the substrate.

[0165] (II-2) Unit structure A having a carbazole skeleton or a phenol / phenoxy skeleton

[0166] (II-2-1)

[0167] As a repeating unit structure having a carbazole skeleton or a phenol / phenoxy skeleton as at least a part of the structure, which is a repeating unit structure of a novolak resin, any unit structure containing a carbazole skeleton, or a phenol skeleton or a phenoxy skeleton in a part of the structure is exemplified. As preferred unit structures, the following structural formulas (A-1) to (A-7) and (A-8) to (A-9) can be respectively exemplified. Here, the carbazole skeleton refers to a skeleton formed by 12 carbon atoms and 1 nitrogen atom constituting an unsubstituted carbazole ring, and the phenol / phenoxy skeleton refers to a skeleton formed by 6 carbon atoms constituting an unsubstituted phenol ring or an unsubstituted phenoxy group (a residue obtained by removing the hydrogen atom of the phenolic hydroxyl group from the phenol ring).

[0168] The expression "at least as part of the structure" means that it includes not only the case where the carbon skeleton is composed solely of a carbazole skeleton or a phenol / phenoxy skeleton, but also the case where a condensed ring is further formed with other carbon rings, the case where multiple carbazole skeletons or phenol / phenoxy skeletons are bonded via a linking group, etc., and a skeleton considered to be a carbazole skeleton or a phenol / phenoxy skeleton is included in a part of the carbon skeleton.

[0169]

[0170] (II-2-2)

[0171] Here, R in formulas (A-1) to (A-7) N and R in formulas (A-8) to (A-9) O each independently represent

[0172] (i) a hydrogen atom or a hydroxymethyl group,

[0173] (ii) an aryl group having 6 to 30 carbon atoms, or

[0174] (iii) a linear, branched or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms.

[0175] In addition, R N is bonded to the nitrogen atom on the carbazole skeleton, and R O is bonded to the oxygen atom of the aryloxy group of the Ar B ring.

[0176] Among them, regarding the above (ii) and (iii), the hydrogen atom in the substituent may be further substituted by a substituent containing an oxygen atom (hydroxyl group, alkoxy group, aryloxy group, carboxyl group, carbonyl group, etc.), a substituent containing a sulfur atom (sulfonic acid group, a group containing a thioether, a group containing a sulfonyl, etc.), a substituent containing a nitrogen atom (amino group, substituted amino group (monoalkylamine, dialkylamine, etc., mono-substituted or di-substituted amino), amide group, nitro group, cyano group, etc.), an aryl group (preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, etc.) or a halogen-containing group, and the hydrocarbon chain part of the above (iii) may be further interrupted by a substituent containing an oxygen atom (-O-, -C(O)-, -C(O)O-, -OC(O)-, etc.), a substituent containing a sulfur atom (-S-, etc.), a substituent containing a nitrogen atom (-N(R)C(O)-, -C(O)N(R)-, -OC(O)N(R)-, -N(R)C(O)O-, -N(R)C(O)N(R)-, -NR-, etc.) or an arylene group (phenylene group, etc.). Here, among the substituents used for the above interruption, R are each independently the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

[0177] R N and R O At least a part of is preferably an alkynyl group from the viewpoint of self-crosslinkability. As such an alkynyl group, the following alkynyl substituents can be mentioned.

[0178] *-R 3 -C≡C-R 4

[0179] Here, * represents a bonding site, and R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms, preferably an alkylene group, more preferably a methylene group; R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. Here, the so-called organic group refers to a residue of an organic compound. In addition, as at least a part of R N preferably 5 to 100% of the number of R N is an alkynyl group. Such a percentage can be determined, for example, by 1 H-NMR measurement, 13 C-NMR to calculate the incorporation rate. The percentage can be calculated using an internal standard or the like as needed.

[0180] As specific examples of R N and R O the following substituents can be exemplified. Here, * in R N refers to the bond to the nitrogen atom on the carbazole skeleton, and in R O refers to the bond to the oxygen atom of the phenolic hydroxyl group of the phenol skeleton (the oxygen atom of the aryloxy group of the Ar B ring) (thereby forming a phenoxy skeleton).

[0181]

[0182]

[0183] (II-2-3)

[0184] In formulas (A-8) to (A-9), Ar B each independently represents a benzene ring, a naphthalene ring, or a condensed ring containing one or more benzene rings.

[0185] When Ar B is a condensed ring, it preferably contains 1 to 8 benzene rings in the condensed ring. In addition, as such a condensed ring, a naphthalene ring, an anthracene ring, a pyrene ring, etc. can be exemplified. Further, Ar BOptionally, it may form a fused ring with an aliphatic ring other than the benzene ring (which may be a saturated aliphatic ring and may contain an unsaturated bond as long as it does not belong to an aromatic ring. It also includes an aliphatic heterocycle). This aliphatic ring may be sandwiched by multiple benzene rings to form a fused ring. Examples include 5,6,7,8-tetrahydro-1-naphthol ring, 9,10-dihydroanthracen-1-ol ring, 9,10-dihydroanthracen-2-ol ring, etc.

[0186] (II-2-4)

[0187] In formula (A-7), n1 is the number of carbazole skeletons bonded to L through the carbon atoms on the aromatic ring of the carbazole skeleton; n2 is the number of carbazole skeletons bonded to L through the nitrogen atoms on the carbazole skeleton. n1 and n2 are each an integer of 0 or more, but n, which is the sum of n1 and n2, is an integer of 2 to 8. When L is a single bond, the sum of n1 and n2 is 2.

[0188] In formula (A-8), m represents the number of OR O groups of 1 or more. Preferably, m is 1 to 3.

[0189] In formula (A-9), m11 and m12 each independently represent the number of R B O groups on the aromatic ring of Ar O . Preferably, m11 and m12 are each independently 1 to 3. In addition, m21 is the number of (R B O) O Ar m11 groups in which the carbon atom on the Ar B ring is bonded to L, and m22 represents the number of OAr B groups in which the oxygen atom of the aryloxy group of the Ar B (OR O ) m12 groups is bonded to L. Here, the oxygen atom of the aryloxy group refers to the ether oxygen atom that is a substituent on any benzene ring constituting the Ar B ring. Furthermore, m11, m21, m12, and m22 in formula (A-9) are each independently 0 or more, but the sum of m21 and m11 and m22 is 1 or more, and the sum of m21 and m22 is 2 to 8. When L is a single bond, the sum of m21 and m22 is 2.

[0190] (II-2-5)

[0191] In addition, L in formula (A-7) and formula (A-9) represents a single bond or a polyvalent linking group (n-valent, n is an integer of 2 to 8),

[0192] In formula (A-7), L connects each carbon atom on the aromatic ring of n1 carbazole skeletons and the nitrogen atoms on n2 carbazole skeletons,

[0193] In formula (A-9), L connects each carbon atom on the aromatic ring of m21 (R O O) m11 Ar B group and the oxygen atom of the aryloxy group on the m22 OAr B (OR O ) m12 group.

[0194] As the preferred linking group L, it is selected from a single bond, -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, -NH-, -(CR 1 R 2 ) m1 -, -(Ar) m2 -, -CH2-(Ar) m2 -CH2- and -(cyclo-R)-.

[0195] Here, R 1 and R 2 are the same or different and each independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m1 represents an integer of 1 to 10. Ar represents an arylene group having 6 to 30 carbon atoms; m2 represents an integer of 1 to 3 which is the number of aromatic rings bonded to each other by a single bond. As such Ar, a divalent benzene ring, naphthalene ring, anthracene ring, pyrene ring, biphenyl ring, terphenyl ring, etc. can be exemplified. The hydrocarbon group having 1 to 5 carbon atoms is preferably a linear, branched or cyclic aliphatic hydrocarbon group.

[0196] cyclo-R represents a divalent alicyclic hydrocarbon group having 5 to 8 members, preferably 6 to 8 members, which can form a fused ring with one or two benzene rings or naphthalene rings. In addition, the two bonding sites of cyclo-R refer to the bonding sites extending from the carbon atoms of the ring constituting the alicyclic hydrocarbon group (preferably the same carbon atom, excluding the carbon atoms belonging to any included fused benzene ring or fused naphthalene ring). As the above alicyclic hydrocarbon group, it can be a divalent monocyclic hydrocarbon group derived from cyclohexane, cyclopentane, etc., or a divalent polycyclic hydrocarbon group derived from dicyclopentadiene, etc. In addition, as the alicyclic hydrocarbon group forming a fused ring with a benzene ring or naphthalene ring, a divalent hydrocarbon group derived from tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, indane, fluorene, benzocyclobutene, benzofluorene, dibenzofluorene, acenaphthene, etc. can be exemplified. However, when the alicyclic hydrocarbon group is a divalent hydrocarbon group derived from a 5-membered ring, i.e., cyclopentane, the number of benzene rings or naphthalene rings to form a fused ring is preferably 0 to 2.

[0197] (II-2-6)

[0198] Among formula (A-7), the following formula (A-7-1) corresponding to n2 = 0 is more preferred.

[0199]

[0200] Here, R N and L are the same as defined in formula (A-7), where L is connected to each respective carbon atom on the aromatic ring of n (n is an integer from 2 to 6) carbazole skeletons. When L is a single bond, n is 2.

[0201] In addition, among formula (A-9), the following formula (A-9-1) corresponding to m22 = 0 is more preferred.

[0202] [(R O O) m1 Ar B m2 L

[0203] (A-9-1)

[0204] Here, R O and L are the same as defined in formula (A-9), where L is connected to each respective carbon atom on the m2 (m2 is an integer from 2 to 8) Ar B rings. When L is a single bond, n is 2.

[0205] In addition, m2 is the number of (R B O) O O m1 Ar B groups in which the carbon atoms on the Ar O ring are bonded to L, and each m1 independently represents the number of R

[0206] O groups of 0 or more. Preferably, each m1 is independently 1 to 3.

[0207] (II-2-7)

[0208] ​On the aromatic rings contained in each carbazole skeleton in formulas (A-1) to (A-7) or on the aromatic rings contained in formulas (A-8) to (A-9), further substituents may optionally be present. Examples of such substituents include substituents containing an oxygen atom (hydroxyl group, alkoxy group, aryloxy group, carboxyl group, carbonyl group, formyl group, ether group, ester group, etc.), substituents containing a sulfur atom (sulfonic acid group, sulfur ether-containing group, sulfonyl-containing group, etc.), substituents containing a nitrogen atom (amino group, substituted amino group (monosubstituted or disubstituted amino such as monoalkylamine, dialkylamine, etc.), amide group, nitro group, cyano group, etc.), a hydrocarbon group having 1 to 20 carbon atoms (alkyl group, alkenyl group, alkynyl group, aryl group (preferably an aryl group having 6 to 20 carbon atoms such as a phenyl group, etc.)) or a halogen-containing group (fluoro group, chloro group, bromo group, iodo group, trifluoromethyl group). In addition, adjacent substituents may condense to form a ring. For example, adjacent substituents or a hydroxyl group and a carboxyl group in the substituents may form a lactone ring and cyclize, and similarly an amino group and a carboxyl group may form an amide and form an internal amide ring.

[0209] (II-2-8)

[0210] As a specific example of the repeating unit structure A having a carbazole skeleton as at least a partial structure, for example, unit structures derived from the following compounds can be exemplified.

[0211]

[0212]

[0213]

[0214]

[0215] In addition, hereinafter, as the repeating unit structure A having a carbazole skeleton as at least a partial structure, typical unit structures are also shown with bonding lines marked.

[0216]

[0217] (II-2-9)

[0218] As the repeating unit structure A having a phenol skeleton as at least a partial structure, for example, unit structures derived from the following compounds can be exemplified. Unit structures derived from compounds in which the phenolic hydroxyl group (the hydroxyl group on the benzene ring contained as at least a partial skeleton) on the exemplified phenol skeletons is replaced with an R O O group (provided that R O is other than a hydrogen atom) to form a phenoxy skeleton can also be exemplified.

[0219]

[0220]

[0221]

[0222]

[0223] In addition, the following typical unit structures are also shown with bonding bonds, where the repeating unit structure A has a phenol / phenoxy skeleton as at least part of the structure.

[0224]

[0225]

[0226]

[0227] (II-3) Other unit structure A

[0228] The unit structure A is a repeating unit structure of a novolak resin derived from a compound having an aromatic ring. Within the range that does not impair the effect of the coating agent composition for a substrate containing a nitrogen atom as one aspect of the present invention, the novolak resin may contain a unit structure A other than a unit structure having a carbazole skeleton and a phenol / phenoxy skeleton as at least part of the structure (hereinafter, sometimes referred to as "other unit structure A").

[0229] Preferably, the aromatic ring in the other unit structure A has 6 to 30 carbon atoms, more preferably 6 to 24 carbon atoms.

[0230] Preferably, such an aromatic ring is one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings; or a condensed ring of a benzene ring, naphthalene ring, anthracene ring, pyrene ring, biphenyl ring and a heterocyclic ring or an aliphatic ring (fluorene ring, benzofluorene ring, dibenzofluorene ring, indole ring, etc.).

[0231] The aromatic ring may optionally have a substituent, but preferably the substituent contains a heteroatom. In addition, two or more aromatic rings may be connected by a linking group, and preferably the linking group contains a heteroatom. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0232] Preferably, the "aromatic ring" is an organic group having 6 to 30 or 6 to 24 carbon atoms containing at least one heteroatom selected from N, S, and O in the ring, within the ring, or between the rings.

[0233] As the heteroatom contained in the ring, as long as it does not correspond to a unit structure having at least a carbazole skeleton or a phenol / phenoxy skeleton as part of the structure, the description of the above (II-2-7) can be cited. For example, the nitrogen atom contained in an amino group (e.g., propargylamino group), a cyano group, etc.; the oxygen atom contained in a formyl group, a carboxyl group, etc. as an oxygen-containing substituent; the nitrogen atom and oxygen atom contained in a nitro group as an oxygen-containing substituent and a nitrogen-containing substituent, etc. As the heteroatom contained in the ring, for example, the oxygen atom contained in xanthene can be cited.

[0234] As the heteroatom contained in the linking group of two or more aromatic rings, the nitrogen atom, oxygen atom, and sulfur atom contained in -NH- bond, -NHCO- bond, -O- bond, -COO- bond, -CO- bond, -S- bond, -SS- bond, -SO2- bond, etc. can be cited. It is preferred that the other unit structure A is a unit structure having an aromatic ring with the above oxygen-containing substituent, a unit structure having two or more aromatic rings linked by -NH-, or a unit structure having a fused ring of one or more aromatic hydrocarbon rings and one or more heterocycles.

[0235] For example, as the skeleton used for the other unit structure A, the following skeletons can be exemplified.

[0236] (Examples of other unit structures A derived from heterocycles)

[0237] In addition, -NH- can also take a structure in which the hydrogen atom on N is substituted.

[0238]

[0239] (Examples of other unit structures A of aromatic hydrocarbons linked by -NH-)

[0240] In addition, -NH- can also take a structure in which the hydrogen atom on N is substituted.

[0241]

[0242] (Others)

[0243] The H of NH in the examples of other unit structures A derived from the above heterocycles and the H of NH in the examples of other unit structures A of aromatic hydrocarbons linked by the above -NH- can be replaced with other substituents, such as the substituents exemplified in the above (II-2-2).

[0244] (II-4) Novolak resin

[0245] The novolak resin preferably contains a composite unit structure A-B represented by the following formula (AB).

[0246]

[0247] In formula (AB), n represents the number of composite unit structures A-B. The unit structure A is a repeating unit structure that has at least a carbazole skeleton or a phenol / phenoxy skeleton as part of its structure, which was described in (II-2) to (II-3) above.

[0248] (II-4-1) Unit structure B

[0249] The unit structure B is one or more unit structures containing a connecting carbon atom bonded to the aromatic ring in the unit structure A [refer to (I-1) above], and preferably contains the structures represented by formula (B1), (B2), or (B3) described in (II-4-2) to (II-4-4) below. The unit structure B can connect two unit structures A by forming a covalent bond with a carbon atom on the aromatic ring of the unit structure A.

[0250] In addition, at least one composite unit structure A-B can be replaced with one or more unit structures C containing the structures represented by formula (C1), (C2), and (C3) described in (II-4-2-3), (II-4-3-2), and (II-4-4-3) respectively, which are equivalent to one unit structure.

[0251] (II-4-2) Formula (B1)

[0252]

[0253] In formula (B1),

[0254] R and R' each independently represent a hydrogen atom, an aromatic ring residue having 6 to 30 carbon atoms that may have a substituent; a heterocyclic residue having 3 to 30 carbon atoms that may have a substituent; a linear, branched, or cyclic alkyl group having 10 or fewer carbon atoms that may have a substituent; or a formyl group.

[0255] In addition, the two bonding sites of formula (B1) can form a covalent bond with the aromatic ring in the unit structure A.

[0256] (II-4-2-1)

[0257] In the definitions of R and R' in formula (B1), for "aromatic ring" and "heterocyclic ring", reference can be made to (I-3) and (I-4) above.

[0258] In the definitions of R and R' in formula (B1), examples of the "alkyl group" include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and the like.

[0259] Preferably, R and R' are each independently phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, or pyrenyl.

[0260] (II-4-2-2)

[0261] In addition, in the unit structure containing the structure represented by formula (B1), for example, a structure in which two or three of the above-mentioned structures of formula (B1), which may be the same or different from each other, are combined with a divalent or trivalent linking group to form a dimer or trimer structure may be included. In this case, as shown in the following formula (B11), one of the two bonding bonds in each structure of the above formula (B1) is combined with the above linking group.

[0262]

[0263] As such a linking group, for example, a linking group having two or three aromatic rings (corresponding to the unit structure A) can be cited. As examples of specific divalent or trivalent linking groups, in addition to the following divalent linking group (L1) exemplified in the above formula (B11), divalent or trivalent linking groups of the following formulas (L2) and (L3) can also be exemplified.

[0264]

[0265] [X 1 represents a single bond, a methylene group, an oxygen atom, a sulfur atom, -N(R 5 )-, and R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (including a chain hydrocarbon and a cyclic hydrocarbon (which may be aromatic or non-aromatic)).]

[0266]

[0267] [X 2 represents a methylene group, an oxygen atom or -N(R 6 )-, and R 6 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 5 to 20 carbon atoms.]

[0268]

[0269] Divalent linking groups such as the following formula (L4) that can form a covalent bond with a linking carbon atom through an addition reaction of an acetylide and a ketone can also be exemplified.

[0270]

[0271] (II-4-2-3)

[0272] Further, when at least one of R and R' in the formula (B1) is an aromatic ring residue, the aromatic ring [for example, Ar in the following formula (B12)] can be further bonded to another unit structure B.

[0273]

[0274] In this case, when one bonding bond connecting carbon atoms is bonded to the polymer terminal T (a hydrogen atom; various functional groups such as a hydroxyl group, an unsaturated aliphatic hydrocarbon group, a terminal unit structure A, a unit structure A in other polymer chains, etc.) as in the following formula (C1), as a unit structure C equivalent to the composite unit structure A-B, it can also be replaced with at least 1 composite unit structure A-B. That is, by bonding the above aromatic ring [Ar in formula (C1)] in formula (C1) to other unit structures B and using the remaining bonding bond connecting carbon atoms shown in formula (C1) to bond to the aromatic ring of unit structure A, the polymer chain can be extended.

[0275]

[0276] (II-4-2-4)

[0277] If several specific examples of the unit structure B containing the structure shown in formula (B1) are given, they are as follows. *Basically represents the bonding site with the unit structure A. Needless to say, it can be a structure containing the exemplified structure in a part of the whole.

[0278]

[0279]

[0280] (II-4-3) Formula (B2)

[0281] *-J 1 -Z 0 -J 2 -*(B2)

[0282] In formula (B2),

[0283] Z 0 represents an aromatic ring residue or an aliphatic ring residue having 6 to 30 carbon atoms which may have substituents, or an organic group in which two aromatic ring residues or aliphatic ring residues are connected by a single bond. As the organic group in which two aromatic ring residues or aliphatic ring residues are connected by a single bond, divalent residues such as biphenyl, cyclohexylphenyl, and dicyclohexyl can be cited.

[0284] J 1 and J 2 each independently represents a direct bond or a divalent organic group which may have substituents. As this divalent organic group, a linear or branched alkylene having 1 to 6 carbon atoms which can be substituted with a hydroxyl group, an aryl group (phenyl, substituted phenyl, etc.) or a halogen-containing group (for example, fluorine) as a substituent is preferred. As the linear alkylene, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. can be cited.

[0285] (II-4-3-1)

[0286] In addition, in the unit structure including the structure shown in formula (B2), similar to the above (II-4-2-2) regarding formula (B1), a structure in which two or three of the above structures of formula (B2), which may be the same as or different from each other, are combined with a divalent or trivalent linking group to form a dimer or trimer structure may be included.

[0287] (II-4-3-2)

[0288] In addition, since the embodiment including an aromatic ring is included in formula (B2) [Z in formula (B2)] 0 , similar to (II-4-2-3) of the above formula (B1), this aromatic ring [for example, Z in the following formula (B21)] 0 Ar (the aromatic ring in ) can be further combined with another unit structure B [the vertical bonding bond in formula (B21)].

[0289]

[0290] [In formula (B21),

[0291] Z 0 Ar is an aromatic ring residue having 6 to 30 carbon atoms which may have substituents, or an organic group in which two aromatic ring residues or aliphatic ring residues are connected by a single bond, and has at least one aromatic ring. The bonding bond extending downward from Z 0 Ar extends from the aromatic ring in Z 0 Ar ,

[0292] J 1 and J 2 are the same as the definitions in formula (B2).]

[0293] In this case, when one bonding bond connecting carbon atoms is combined with a polymer terminal T (a hydrogen atom; various functional groups such as a hydroxyl group, an unsaturated aliphatic hydrocarbon group, a terminal unit structure A, an unit structure A in other polymer chains, etc.) as shown in the following formula (C2), as a unit structure C equivalent to the composite unit structure A-B, it can also be replaced with at least one composite unit structure A-B. That is, through the above aromatic ring in formula (C2) [the aromatic ring in Z in formula (C2)] 0 Ar being combined with another unit structure B, and using the remaining bonding bond connecting carbon atoms shown in formula (C2) to be combined with the aromatic ring of the unit structure A, the polymer chain can be extended.

[0294]

[0295] [In formula (C2),

[0296] Z 0 Ar 、J 1 and J 2 are the same as defined in formula (B21),

[0297] T represents the polymer end.]

[0298] (II-4-3-3)

[0299] If several specific examples of the unit structure containing the structure shown in formula (B2) are given, they are as follows. * represents the bonding site with the unit structure A. Needless to say, it can be a unit structure containing the exemplified structure in a part of the whole.

[0300]

[0301]

[0302] (II-4-4) Formula (B3)

[0303]

[0304] In formula (B3),

[0305] Z is a monocyclic, bicyclic, tricyclic or tetracyclic condensed ring having 4 to 25 carbon atoms which may have substituents. Further, the number of carbon atoms here means the number of only carbon atoms constituting the ring skeleton of the monocyclic, bicyclic, tricyclic or tetracyclic condensed ring excluding substituents, and does not include the number of heteroatoms constituting the heterocycle in the case where the above monocyclic or condensed ring is a heterocycle.

[0306] The above monocyclic ring is a non-aromatic monocyclic ring; at least one of the monocyclic rings constituting the above bicyclic, tricyclic and tetracyclic rings is a non-aromatic monocyclic ring, and the remaining monocyclic rings may be aromatic monocyclic rings or non-aromatic monocyclic rings.

[0307] The above monocyclic, bicyclic, tricyclic or tetracyclic condensed ring may further form a condensed ring with one or more aromatic rings to become a condensed ring of five rings or more, and the number of carbon atoms of the condensed ring of five rings or more is preferably 40 or less. The number of carbon atoms here means the number of only carbon atoms constituting the ring skeleton of the above condensed ring of five rings or more excluding substituents, and does not include the number of heteroatoms constituting the heterocycle in the case where the above condensed ring of five rings or more is a heterocycle.

[0308] X and Y are the same or different and represent -CR 31 R 32 - group, R 31 and R32 Each is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The above hydrocarbon group is preferably a linear, branched or cyclic aliphatic hydrocarbon group.

[0309] x and y each represent the number of X and Y, and each independently represents 0 or 1.

[0310] *——X x Is bonded to any carbon atom (referred to as "carbon atom 1") constituting the above non-aromatic monocyclic ring of Z (when x = 1) or extends from carbon atom 1 (when x = 0),

[0311] Y y ——* is bonded to any carbon atom (referred to as "carbon atom 2") constituting the above non-aromatic monocyclic ring of Z (when y = 1) or extends from carbon atom 2 (when y = 0). Carbon atom 1 and carbon atom 2 may be the same or different. In the case of being different, they may belong to the same non-aromatic monocyclic ring or different non-aromatic monocyclic rings.

[0312] In addition, in formula (B3), connecting carbon atoms other than carbon atom 1 and carbon atom 2 can be optionally included [refer to (II-4-4-2) described later]

[0313] Further, in the case where Z is a polycyclic ring of tricyclic or higher, the positional relationship of arrangement in the polycyclic ring of one or two non-aromatic monocyclic rings to which carbon atoms 1 and 2 in formula (B3) each belong and the remaining monocyclic rings is arbitrary. In the case where carbon atoms 1 and 2 belong to different non-aromatic monocyclic rings (referred to as "non-aromatic monocyclic ring 1" and "non-aromatic monocyclic ring 2" respectively), the positional relationship of arrangement of the non-aromatic monocyclic ring 1 and the non-aromatic monocyclic ring 2 in the polycyclic ring is also arbitrary.

[0314] (II-4-4-1)

[0315] Similar to the above (II-4-2-2) regarding formula (B1), two or three structures of the above formula (B3) that are the same or different from each other can be combined with a divalent or trivalent linking group to form a dimer or trimer structure.

[0316] (II-4-4-2)

[0317] If several specific examples of organic groups containing the structure shown in formula (B3) are given, they are as follows. The binding site to the unit structure A is not particularly limited. Needless to say, it can be a structure containing the exemplified structure in a part of the whole.

[0318] In addition, examples in which the number of bonding bonds (*) exceeds 2 are also included, and the remaining bonding bonds can be used for bonding, crosslinking, etc. with aromatic rings in other polymer chains.

[0319]

[0320]

[0321] (II-4-4-3)

[0322] In addition, when Z in formula (B3) contains an aromatic ring, this aromatic ring [for example, refer to Ar in the following formula (B32) 1 may further combine with other unit structures B.

[0323]

[0324] In formula (B32),

[0325] Z 1 represents at least one non-aromatic monocyclic ring, and Ar 1 represents at least one aromatic monocyclic ring that forms a fused ring with the non-aromatic monocyclic ring of Z 1 . Z 1 and Ar 1 as a whole constitute a bicyclic, tricyclic, tetracyclic or pentacyclic fused ring having 8 to 25 carbon atoms that may have substituents. Furthermore, the number of carbon atoms here refers to the number of only carbon atoms that make up the ring skeleton of the bicyclic, tricyclic, tetracyclic or pentacyclic fused ring excluding substituents, and does not include the number of heteroatoms that make up the heterocyclic ring when the above bicyclic, tricyclic, tetracyclic or pentacyclic fused ring is a heterocyclic ring.

[0326] The above bicyclic, tricyclic, tetracyclic or pentacyclic fused ring may further form a fused ring with one or more aromatic rings to become hexacyclic or higher, and the number of carbon atoms of the hexacyclic or higher fused ring is preferably 40 or less. The number of carbon atoms here refers to the number of only carbon atoms that make up the ring skeleton of the above hexacyclic or higher fused ring excluding substituents, and does not include the number of heteroatoms that make up the heterocyclic ring when the above hexacyclic or higher fused ring is a heterocyclic ring.

[0327] In addition, the sequential positional relationship of one or more non-aromatic monocyclic rings belonging to Z 1 and one or more aromatic monocyclic rings belonging to Ar 1 includes any relationship. For example, when there are two or more non-aromatic monocyclic rings belonging to Z 1 and two or more aromatic monocyclic rings belonging to Ar 1 , the non-aromatic monocyclic rings belonging to Z 1 and the aromatic monocyclic rings belonging to Ar 1 can be alternately arranged to form a fused ring.

[0328] In addition, X, Y, x and y have the same definitions as in formula (B3).

[0329] In this case, when one bonding bond connecting carbon atoms is bonded to the polymer terminal T (a hydrogen atom; various functional groups such as a hydroxyl group, an unsaturated aliphatic hydrocarbon group, a terminal unit structure A, a unit structure A in other polymer chains, etc.) as in the following formula (C3), as a unit structure C equivalent to the composite unit structure A-B, it can also be replaced with at least 1 composite unit structure A-B. That is, through the above aromatic ring [Ar in formula (C3) 1 in formula (C3) is bonded to other unit structure B, and the remaining bonding bond connecting carbon atoms shown in formula (C3) is used to bond to the aromatic ring of unit structure A, thereby the polymer chain can be extended.

[0330]

[0331] [In formula (C3),

[0332] Z 1 、Ar 1 、X, Y, x and y are the same as the definitions in formula (B32),

[0333] T represents the polymer terminal.]

[0334] (II-4-4-4)

[0335] As a more specific structure of formula (C3), for example, in the following formula (C31), T in formula (C3) is a hydrogen atom as the terminal group, and through p and k1, or p and k2 among p, k1 and k2 that can form a bonding bond, one unit structure C equivalent to the composite unit structure A-B can be formed.

[0336] In addition, unit structure A can also be formed and function through k1 and k2.

[0337]

[0338] Furthermore, in the following formula (C32), an example where T in formula (C3) is a phenyl group is shown. In this example, through p and k1, p and k2, or p and m among p, k1, k2 and m that can form a bonding bond, one unit structure C equivalent to the composite unit structure A-B can be formed.

[0339] In addition, unit structure A can also be formed and function through k1 and k2, k1 and m, or k2 and m.

[0340]

[0341] If several more specific examples of the unit structure C of formula (C3) (one unit structure equivalent to the composite unit structure A-B) are given, they are as follows. * indicates the binding site to the unit structure A.

[0342] In the unit structure C, the binding bond to the unit structure B extends separately from the aromatic ring in these structures, but in the following specific examples, such a binding bond is omitted. It goes without saying that it can be a unit structure including the exemplified structure in a part of the whole.

[0343]

[0344] In addition, in the above specific examples, in the case of no binding bond from the aromatic ring, it can be a specific example of the polymer end.

[0345] (II-4-5)

[0346] The novolak resin having the structure represented by formula (AB) can be prepared by a known method. For example, it can be prepared by condensing a ring-containing compound represented by H-A-H with an oxygen-containing compound represented by OHC-B, O=C-B, HO-B-OH, RO-B-OR, RO-CH2-B-CH2-OR, etc. Here, in the formula, A and B have the same meanings as above. R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0347] Both the ring-containing compound and the oxygen-containing compound can be used singly or in combination of two or more. In this condensation reaction, the oxygen-containing compound can be used in a proportion of 0.1 to 10 moles, preferably 0.1 to 2 moles, per 1 mole of the ring-containing compound.

[0348] As the catalyst used in the condensation reaction, for example, inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid, carboxylic acids such as formic acid and oxalic acid, and mercaptopropionic acid can be used. The amount of the catalyst used varies depending on the type of the catalyst used, but it is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass, relative to 100 parts by mass of the ring-containing compound (in the case of a plurality, their total).

[0349] The condensation reaction can proceed even without a solvent, but it is usually carried out using a solvent. As the solvent, there is no particular limitation as long as it can dissolve the reaction substrate and does not hinder the reaction. Examples include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, dioxane, dichloromethane, 1,2-dichloroethane, toluene, N-methylpyrrolidone, dimethylformamide, etc. 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.

[0350] The weight-average molecular weight of the novolak 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.

[0351] (II-5) Solvent

[0352] The coating agent composition for a substrate containing a nitrogen atom according to one embodiment of the present invention contains a solvent.

[0353] There is no particular limitation on the solvent as long as it can dissolve the specific novolak resin and any other components added as needed.

[0354] (II-5-1)

[0355] Examples of the solvent include 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 monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl acetate, ethyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl glycolate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more kinds.

[0356] (II-5-2)

[0357] In addition, a solvent having a boiling point of 160 °C or higher can be combined with a solvent having a boiling point of less than 160 °C.

[0358] As such a high-boiling solvent, for example, the following compounds described in International Publication No. 2018 / 131562 (A1) can be preferably used.

[0359]

[0360] [R in formula (i) 1 , R 2 and R 3 each represents a hydrogen atom; an alkyl group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom or an amide bond, and which may be the same or different from each other and may combine with each other to form a ring structure.]

[0361] Alternatively, 1,6-diacetoxyhexane (boiling point 260 °C), tripropylene glycol monomethyl ether (boiling point 242 °C), and various high-boiling solvents described in paragraph 0082 of the same published gazette can be preferably used.

[0362] Alternatively, 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 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), γ-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 (boiling point 260 °C), dipropylene glycol (boiling point 230 °C), 1,3-butanediol diacetate (boiling point 232 °C), and various high-boiling solvents described in paragraphs 0023 to 0031 of the same published gazette can be preferably used.

[0363] (II-6) Acid and / or its salt and / or acid generator

[0364] The coating agent composition for a substrate containing a nitrogen atom according to one aspect of the invention of the present application may contain an acid and / or its salt and / or an acid generator.

[0365] (II-6-1)

[0366] Examples of the acid include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthoic acid, and the like.

[0367] As the salt, salts of the above acids can also be used. There is no limitation as the salt, but ammonium derivative salts such as trimethylamine salt and triethylamine salt, pyridine derivative salts, morpholine derivative salts, etc. can be suitably used.

[0368] The acid and / or its salt may be used alone, or two or more thereof may be used in combination. The blending amount is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass with respect to all solid components.

[0369] (II-6-2)

[0370] Examples of the acid generator include a thermal acid generator and a photoacid generator.

[0371] (II-6-2-1)

[0372] Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE [registered trademark] CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other organic sulfonic acid alkyl esters.

[0373] (II-6-2-2)

[0374] The photoacid generator generates an acid when the resist is exposed. Therefore, the acidity of the resist underlayer film as a coating film can be adjusted. This is one method for making the acidity of the resist underlayer film consistent with that of the upper-layer resist. In addition, by adjusting the acidity of the resist underlayer film, the pattern shape of the resist formed on the upper layer can be adjusted.

[0375] Examples of the photoacid generator contained in the coating agent composition for a substrate containing a nitrogen atom as one aspect of the present invention include onium salt compounds, sulfimide compounds, and disulfonyldiazomethane compounds.

[0376] Examples of the onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0377] Examples of the sulfimide compounds include, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenedicarboximide.

[0378] Examples of the disulfonyldiazomethane compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0379] (II-6-2-3)

[0380] The acid generator may be used alone or two or more thereof may be used in combination.

[0381] When the acid generator is used, as its ratio, it is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the coating composition for a substrate containing a nitrogen atom.

[0382] (II-7) Other optional components

[0383] The coating composition for a substrate containing a nitrogen atom according to one embodiment of the present invention may further contain a crosslinking agent, a surfactant, a light absorber, a rheology modifier, an adhesion aid, etc. as needed in addition to the above.

[0384] (II-7-1) Crosslinking agent

[0385] As representative crosslinking agents, aminoplast crosslinking agents and phenolic plastic crosslinking agents can be exemplified.

[0386] As the above crosslinking agent, a crosslinking agent with high heat resistance can be used. As the crosslinking agent with high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (for example, a benzene ring, a naphthalene ring) in the molecule can be preferably used.

[0387] (II-7-1-1)

[0388] As amino plastic crosslinking agents, there may be mentioned highly alkylated, alkoxylated or alkoxyalkylated melamine, benzoguanamine, glycoluril, urea, their polymers, etc. Crosslinking agents having at least 2 crosslinking-forming substituents are preferred, and examples thereof are compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea or butoxymethylated thiourea. In addition, condensates of these compounds may also be used.

[0389] The amino plastic crosslinking agent is preferably at least one selected from tetramethoxymethyl glycoluril and hexamethoxymethyl melamine.

[0390] If several specific examples are given, they are as follows.

[0391]

[0392] As phenolic plastic crosslinking agents, there may be mentioned highly alkylated, alkoxylated or alkoxyalkylated aromatic compounds, their polymers, etc. Crosslinking agents having at least 2 crosslinking-forming substituents in one molecule are preferred, and examples thereof are compounds 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, α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. In addition, condensates of these compounds may also be used.

[0393] Examples of such compounds include, in addition to the above, compounds having a partial structure of the following formula (4), polymers or oligomers having a repeating unit of the following formula (5).

[0394]

[0395] The above R 11 , R 12 , R 13 and R 14 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and these alkyl groups may be those exemplified above. n1 is an integer of 1 to 4, n2 is an integer of 1 to (5 - n1), and (n1 + n2) represents an integer of 2 to 5. n3 is an integer of 1 to 4, n4 is 0 to (4 - n3), and (n3 + n4) represents an integer of 1 to 4. The oligomers and polymers may be used in the range where the number of repeating unit structures is 2 to 100 or 2 to 50.

[0396] If several specific examples are given, they are as follows.

[0397]

[0398] (II-7-1-3)

[0399] Crosslinking agents such as amino plastic crosslinking agents and phenolic plastic crosslinking agents can be used alone, or two or more of them can be used in combination. Amino plastic crosslinking agents and phenolic plastic crosslinking agents can be produced by known methods or according to known methods, and in addition, commercially available products can be used.

[0400] In addition, the amount of use of crosslinking agents such as amino plastic crosslinking agents and phenolic plastic crosslinking agents varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but is 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 relative to all solid components of the coating agent composition or the resist underlayer film forming agent composition for a substrate containing a nitrogen atom according to the present invention.

[0401] (II-7-2) Surfactant

[0402] In the coating agent composition for a substrate containing a nitrogen atom according to the present invention, in order not to generate pinholes, streaks, etc. and to further improve the coatability on an uneven surface, a surfactant can be blended.

[0403] Examples of the surfactant include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; nonionic surfactants,

[0404] Eftop EF301, EF303, EF352 (manufactured by Tokem Products Co., Ltd., trade name), Megafac (registered trademark) F171, F173, R-30, R-40 (manufactured by DIC Corporation, trade name), Fluorard FC430, FC431 (manufactured by Sumitomo 3M Limited, trade name), Asahi Guard (registered trademark) AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., trade name), etc. fluorosurfactants,

[0405] Siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

[0406] The mixing amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, relative to all solid components of the coating agent composition for a substrate containing a nitrogen atom, which is one aspect of the present invention. These surfactants can be added individually, and in addition, they can also be added in combinations of two or more.

[0407] (II-7-3) Other additives

[0408] As the light absorbent, for example, commercially available light absorbents described in "Technology and Market of Industrial Dyes" (published by CMC) and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry), such as C.I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C.I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; C.I. Disperse Violet 43; C.I. Disperse Blue 96; C.I. Fluorescent Brightener 112, 135 and 163; C.I. Solvent Orange 2 and 45; C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; C.I. Pigment Green 10; C.I. Pigment Brown 2, etc. The above light absorbents are usually mixed in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to all solid components of the coating agent composition for a substrate containing a nitrogen atom or the resist underlayer film forming agent composition related to the present invention.

[0409] The rheology modifier is mainly added for the purpose of improving the fluidity of the coating composition used for a substrate containing nitrogen atoms, particularly for improving the film thickness uniformity of the coating film in the baking process and the filling property of the coating composition for a substrate containing nitrogen atoms into the interior of the pores. As specific examples, phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate, adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyl decyl adipate, maleic acid derivatives such as di(n-butyl) maleate, diethyl maleate, and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate, or stearic acid derivatives such as n-butyl stearate and glycerol stearate can be cited. These rheology modifiers are generally blended in a proportion of less than 30% by mass relative to all the solid components of the coating composition for a substrate containing nitrogen atoms according to one aspect of the present invention.

[0410] The adhesion promoter is mainly added for the purpose of improving the adhesion between the substrate or the resist and the coating film formed by the coating composition for a substrate containing nitrogen atoms, particularly for preventing the resist from peeling off during development. As specific examples, chlorosilanes such as trimethylchlorosilane, dimethylethenylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylethenylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane, silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole, silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea can be cited. These adhesion promoters are generally blended in a proportion of less than 5% by mass, preferably less than 2% by mass, relative to all the solid components of the coating composition for a substrate containing nitrogen atoms according to one aspect of the present invention.

[0411] The solid component of the coating composition for a substrate containing nitrogen atoms according to one aspect of the present invention is 0.1 to 70% by mass or 0.1 to 60% by mass. The solid component is the content ratio of all the components obtained by removing the solvent from the coating composition for a substrate containing nitrogen atoms. A crosslinkable resin can be contained in the solid component in a proportion of 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, or 50 to 90% by mass.

[0412] [III. Underlying Resist Film]

[0413] A coating agent composition for a substrate containing a nitrogen atom, which is an aspect of the present invention, can be used to form an underlying resist film on a substrate containing a nitrogen atom. That is, as a fired product of a coating film formed from the coating agent composition for a substrate containing a nitrogen atom, an underlying resist film can be formed on a substrate containing a nitrogen atom. Another aspect of the present invention is a method for manufacturing the following laminate, which is a method for manufacturing a laminate having two or more layers including a substrate containing a nitrogen atom and an underlying resist film, and includes the following steps: a step of coating at least one surface of a substrate containing a nitrogen atom with the coating agent composition for a substrate containing a nitrogen atom; and a step of firing the obtained coating film to form an underlying resist film. The above laminate can laminate a resist film on the surface of the underlying resist film opposite to the substrate containing a nitrogen atom (laminated in the order of substrate / underlying resist film / resist film). In addition, another aspect of the present invention is the use of the coating agent composition for a substrate containing a nitrogen atom for forming an underlying resist film on a substrate containing a nitrogen atom.

[0414] Another aspect of the present invention is a laminate having two or more layers including a substrate containing a nitrogen atom and an underlying resist film. Further other aspects of the present invention are laminates in which the above underlying resist film and resist film are laminated in this order on at least one surface of a substrate containing a nitrogen atom. Further other aspects of the present invention are the use of the coating agent composition for a substrate containing a nitrogen atom in the manufacture of these laminates or semiconductor devices.

[0415] More specifically, on a substrate containing a nitrogen atom (for example, a silicon nitride substrate (SiN substrate), a silicon oxynitride substrate (SiON substrate), a titanium nitride substrate (TiN substrate), or a titanium oxynitride substrate (TiON), etc.) among the substrates used in the manufacture of semiconductor devices, the coating agent composition for a substrate containing a nitrogen atom, which is an aspect of the present invention, is coated by an appropriate coating method such as a spinner or a coater, and then fired using a heating means such as a hot plate, thereby forming an underlying resist film on the substrate containing a nitrogen atom. As the firing conditions, they are appropriately selected from a firing temperature of 80°C to 800°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 500°C (more preferably 150°C to 400°C), and the firing time is 0.5 to 2 minutes. As the atmosphere gas during firing, air can be used, or inert gases such as nitrogen and argon can be used. In one aspect, an oxygen concentration of 1% or less is particularly preferred.

[0416] Here, as the film thickness of the formed lower resist film, for example, it is 10 to 1000 nm, or 20 to 500 nm, or 30 to 400 nm, or it may also be 50 to 300 nm. However, from the viewpoints of cost and manufacturing, an ultra-thin film with a film thickness less than 10 nm is preferred. The film thickness is preferably 1 to less than 10 nm, more preferably 3 to less than 10 nm. Even for such an ultra-thin film, the coating agent composition for a substrate containing nitrogen atoms according to one aspect of the present invention has good coatability by blending a specific novolak resin, and can maintain the resolution of the resist not inferior to that of the resist immediately after the formation of the resist film even when exposure is performed after a long time has passed since the formation of the resist film.

[0417] In addition, a conformal layer and / or a silicon-containing layer containing 99% by mass or less or 50% by mass or less of Si can be formed on the lower resist film on the substrate containing nitrogen atoms according to one aspect of the present invention by coating or vapor deposition. For example, in addition to the conformal layer described in JP-A-2013-202982 and JP No. 5827180, and the method of forming a silicon-containing lower resist film (inorganic lower resist film) composition described in WO 2009 / 104552 (A1) by spin coating, a Si-based inorganic material film can also be formed by a CVD method or the like.

[0418] In addition, by coating the coating agent composition for a substrate containing nitrogen atoms according to one aspect of the present invention on a semiconductor substrate (so-called stepped substrate) having a stepped portion and a non-stepped portion, and firing, the step difference between the stepped portion and the non-stepped portion can be reduced.

[0419] [IV. Method for manufacturing a semiconductor device]

[0420] (IV-1)

[0421] The method for manufacturing a semiconductor device according to one aspect of the present invention includes the following steps:

[0422] A step of forming a lower resist film on a semiconductor substrate containing nitrogen atoms by the coating agent composition for a substrate containing nitrogen atoms according to one aspect of the present invention;

[0423] A step of forming a resist film on the lower resist film; and

[0424] A step of forming a resist pattern on the resist film by irradiation with light or an electron beam and development.

[0425] In addition, a method for forming a resist pattern for manufacturing a semiconductor according to an aspect of the present invention includes a step of coating a coating composition for a substrate containing a nitrogen atom on a semiconductor substrate containing a nitrogen atom, and then performing firing to form a resist underlayer film.

[0426] Furthermore, another aspect of the present invention is a semiconductor device having a resist underlayer film, which is a fired product of a coating film of a coating composition for a substrate containing a nitrogen atom, on at least one surface of a semiconductor substrate containing a nitrogen atom. The above resist underlayer film can be patterned according to circuit wiring.

[0427] Furthermore, it may include a step of etching the resist underlayer film via a resist pattern, and further may include a step of processing the semiconductor substrate through the patterned resist underlayer film.

[0428] (IV-2)

[0429] The step of forming a resist underlayer film on a semiconductor substrate containing a nitrogen atom using a coating composition for a substrate containing a nitrogen atom according to an aspect of the present invention is as described in the above [III. Resist Underlayer Film].

[0430] Furthermore, a hard mask such as a silicon-containing film can be formed on the resist underlayer film formed through the above steps as a second resist underlayer film, and a resist pattern can be formed thereon. The hard mask can be a coating film formed from a composition containing an inorganic substance or the like, and can be a vapor deposition film of an inorganic substance or the like formed by a vapor deposition method such as CVD or PVD. Examples thereof include a SiON film, a SiN film, or a SiO2 film. Further, an anti-reflection film (BARC) can be formed on the hard mask, and a resist shape correction film having no anti-reflection ability can be formed.

[0431] (IV-3)

[0432] In the step of forming a resist pattern after forming a resist film on the resist underlayer film, a resist pattern can be formed on the resist film by irradiation with light or an electron beam and development.

[0433] Exposure is performed through a mask (reticle) for forming a predetermined pattern or by direct writing. In the exposure source, for example, g-ray, i-ray, KrF excimer laser, ArF excimer laser, EUV, or electron beam can be used. After exposure, post-exposure bake is performed as needed. Then, development is performed using a developer (for example, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, butyl acetate, etc.), and further washed with a rinsing solution or pure water to remove the used developer. Then, post-baking is performed for drying the resist pattern and improving the adhesion to the substrate.

[0434] The etching process performed after the formation of the resist pattern is carried out, for example, by dry etching.

[0435] In addition, the following gases, namely CF4, CHF3, CH2F2, CH3F, C4F6, C4F8, O2, N2O, NO2, H2 or He, can be used in the processing of the hard mask (silicon-containing layer) / under-resist film / substrate. These gases can be used alone or in combination of two or more gases. Furthermore, argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon or nitrogen trifluoride can be mixed in these gases.

[0436] (IV-4)

[0437] The above resist film can be patterned by nanoimprint lithography or self-assembled monolayer method. That is, the process of forming a resist pattern on the above resist film can be carried out by nanoimprint lithography or self-assembled monolayer method.

[0438] In nanoimprint lithography, the resist composition is molded using a mold (die) that is transparent to the irradiation light and has been patterned. In addition, in the self-assembled monolayer method, a self-assembled monolayer that naturally forms a nano-scale regular structure, such as a diblock polymer (polystyrene-polymethyl methacrylate, etc.), is used for patterning.

[0439] In nanoimprint lithography, before applying the curable composition that becomes the resist film, a silicon-containing layer (hard mask layer) can be optionally formed on the under-resist film by coating or evaporation, and further, a bonding layer can be formed on the under-resist film or the silicon-containing layer (hard mask layer) by coating or evaporation, and the curable composition that becomes the resist film is applied on this bonding layer.

[0440] (IV-5)

[0441] In addition, sometimes wet etching treatment is carried out for the purpose of simplifying the process steps and reducing the damage to the processed substrate. Thereby, fluctuations in the processing dimensions and pattern roughness can be suppressed, and the substrate can be processed with a good yield. Therefore, when a hard mask is used, the hard mask can be removed by either etching or an alkaline solution. Especially when using an alkaline solution, there is no limitation on the composition, but as the alkaline component, the following are preferably included.

[0442] Examples of the basic component include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, cetyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, 1,5-diazabicyclo[4,3,0]non-5-ene, etc. Further, from the viewpoint of operation, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, and an inorganic base can be used in combination with a quaternary ammonium hydroxide. As the inorganic base, hydroxides of alkali metals such as potassium hydroxide, sodium hydroxide, rubidium hydroxide, etc. are preferred, and potassium hydroxide is more preferred.

[0443] Examples

[0444] ○ Synthesis of polymer

[0445] For the synthesis of the polymers having the structural formulas (S1) to (S20) used as the underlayer film of the resist, and for the synthesis of the structural formulas (SS1) to (SS2) as comparative examples, the following compound groups A to D, catalyst group E, solvent group F, and reprecipitation solvent group G were used.

[0446] ○ Compound groups A to D

[0447]

[0448] ○ Catalyst group E, solvent group F, reprecipitation solvent group G

[0449] Methanesulfonic acid: E1

[0450] p-Toluenesulfonic acid monohydrate: E2

[0451] Tetrabutylammonium iodide: E3

[0452] Benzyltriethylammonium chloride: E4

[0453] Mercaptopropionic acid: E5

[0454] Propylene glycol monomethyl ether acetate (=PGMEA): F1

[0455] Propylene glycol monomethyl ether (=PGME): F2

[0456] Tetrahydrofuran (=THF): F3

[0457] 25% aqueous sodium hydroxide solution: F4

[0458] Methanol: G1

[0459] Methanol / water: G2

[0460] [Synthesis Example 1]

[0461] 12.0 g of A1, 7.9 g of C1, 3.2 g of C2, 0.7 g of E1, and 71.3 g of PGMEA were placed in a flask. Then, it was heated to 120°C under nitrogen and reacted for about 14 hours. After the reaction stopped, it was reprecipitated with methanol and the resin was dried to obtain (S1). The weight-average molecular weight Mw measured by GPC in terms of polystyrene was about 1,700. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target compound solution. In addition, the polymer insoluble in PGMEA was dissolved in PGME or cyclohexanone, and ion exchange was carried out in the same manner.

[0462] [Synthesis Examples 2 to 17, 22]

[0463] Resins (S2) to (S17) and (SS2) were synthesized by the same operation as in Synthesis Example 1 (see Table 1 for the compounds used in the reaction). In addition, the polymer insoluble in PGMEA was dissolved in PGME or cyclohexanone, and ion exchange was carried out in the same manner.

[0464] [Synthesis Example 18]

[0465] 7.0 g of the resin (S17) synthesized in Synthesis Example 17, 9.0 g of D3, 0.5 g of E3, 18.8 g of THF, and 15.7 g of 25% aqueous sodium hydroxide solution were placed in a flask. It was heated to 55°C under nitrogen and reacted for about 24 hours. After the reaction stopped, liquid separation operation was repeatedly carried out with butyl acetate and water, the organic layer was concentrated, reprecipitated with methanol and water, and dried to obtain resin (S18). The weight-average molecular weight Mw measured by GPC in terms of polystyrene was about 2,900. The obtained resin was dissolved in PGMEA, and ion exchange was carried out for 4 hours using a cation exchange resin and an anion exchange resin to obtain a target compound solution.

[0466] [Synthesis Examples 19 to 20]

[0467] (S19) to (S20) were obtained in the same manner as in Synthesis Example 18 (see Table 1 for the compounds used in the reaction).

[0468] [Synthesis Example 21]

[0469] In a flask, 100.0 g of D1, 66.4 g of D2, 4.1 g of E4, and 682.0 g of propylene glycol monomethyl ether were dissolved, and the mixture was reacted at 130 °C for 24 hours. The solution was subjected to ion exchange for 4 hours using a cation exchange resin and an anion exchange resin to obtain the target resin (SS1). The weight average molecular weight Mw measured by GPC in terms of polystyrene was approximately 6,800.

[0470] Table 1

[0471]

[0472]

[0473]

[0474] 〇 Preparation of resist underlayer film material

[0475] Resins (S1) to (S20) and (SS1) to (SS2), crosslinking agents (CL1 to CL4), acid generators (Ad1 to Ad2), solvents (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CYH)), and Megafac (registered trademark) R-40 (manufactured by DIC Corporation, H1) as a surfactant were mixed in the ratios shown in Table 2 below (parts by mass relative to 100 parts by mass of the resin for the crosslinking agent, acid generator, and surfactant; parts by mass relative to 100 of the total mass of the solvent for the solvent), and filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare resist underlayer film materials (M1 to M21, Comparative M1 to Comparative M2) as substrate coating agent compositions.

[0476]

[0477] Table 2

[0478]

[0479]

[0480] [Dissolution test in resist solvent]

[0481] The resist underlayer film materials of Comparative Examples 1 to 2 and Examples 1 to 21 were applied to a substrate containing nitrogen atoms on which SiON or TiN was vapor-deposited using a spin coater, and fired at a specified temperature and a specified time in the atmosphere as described in Table 3 to form a resist underlayer film with a film thickness of 5 nm. The formed resist underlayer film was immersed in a mixed solvent of PGME / PGMEA=7 / 3 as a general diluent for 60 seconds, then spin dried, and fired at 100°C for 30 seconds to evaporate the solvent, and the film thickness at this time was measured. The resistance to solvents was confirmed by comparing the film thickness before and after immersion. The case where the change rate of the film thickness before and after immersion in the diluent was 10% or more was judged as ×, the case where it was 5% or more and less than 10% was judged as △, the case where it was 2% or more and less than 5% was judged as ○, and the case where it was less than 2% was judged as ◎ (Table 3). The evaluation samples above ○ were judged to be at a level that can be used. The solvent resistance in a nitrogen atmosphere was evaluated by the same method as described above using ACT-8 manufactured by Tokyo Electron Co., Ltd.

[0482] Table 3

[0483]

[0484] Since 5nm is an ultra-thin film, even if the film thickness reduction rate is extremely small, it greatly affects the characteristics compared to the case of thick films. The embodiments show very good curing properties on substrates containing nitrogen atoms in both oxygen atmospheres and nitrogen atmospheres. On the other hand, in Comparative Example 1, good curing properties are shown in low-temperature firing, but in high-temperature firing, the film disappears to an area where the film thickness cannot be measured due to insufficient heat resistance of the resin. In addition, Comparative Example 2 is not limited to nitrogen atmospheres, and even under firing conditions in an atmospheric atmosphere, which is a general firing condition, sufficient solvent resistance cannot be obtained, so it cannot be used as a resist lower film. Therefore, in subsequent evaluations, with respect to the comparative examples, only the samples in which Comparative Example 1 was fired at 240°C were evaluated.

[0485] [Applicability Evaluation 1]

[0486] The resist underlayer film materials of Comparative Example 1 and Examples 1 to 21 were coated on various substrates without height differences using a spin coater, and fired at the specified temperature and for the specified time described in Table 4 in an atmospheric atmosphere to form a resist underlayer film with a film thickness of 5 nm. By visual confirmation, the case where coating could be performed without pinholes, unevenness, or depressions was judged as ○. In addition, the resist underlayer film materials of Comparative Example 1 and Examples 1 to 21 were coated on various substrates with height differences (SiO2 substrates, SiN substrates, and TiN substrates with a film thickness of 200 nm) using a spin coater, and fired at the specified temperature and for the specified time described in Table 4 in an atmospheric atmosphere to form a resist underlayer film with a film thickness of 100 nm. In addition, with respect to the depth of the substrate with height differences, for a film thickness of 5 nm, it was difficult to ensure a sufficient amount of resin to embed the substrate, and it was difficult to appropriately evaluate the coatability. Therefore, the evaluation was carried out with a film thickness of 100 nm. By visual confirmation, the case where coating could be performed without pinholes, unevenness, or depressions was judged as ○ (Table 4).

[0487] In addition, in order to show that it has the same coatability as the existing materials even for Si substrates and SiO2 substrates that do not contain nitrogen atoms, the results are shown for reference.

[0488] Table 4

[0489]

[0490] [Coatability Evaluation 2]

[0491] The resist underlayer film materials of Comparative Example 1 and Examples 1 to 21 were coated using ACT-8 or Lithius Pro manufactured by Tokyo Electron Limited, and fired at the specified temperature and for the specified time described in Table 5 in an atmospheric atmosphere to form a 5-nm resist underlayer film. In addition, for the substrate containing nitrogen atoms on which SiON was evaporated, ACT-8 was used, and for the silicon wafer, Lithius Pro was used for coating. The uniformity of the film thickness in the plane of the wafer of the formed resist underlayer film was evaluated by measuring 49 points on the circumference of the entire wafer for the film thickness. The case where the ratio of the fluctuation range of the film thickness (maximum film thickness - minimum film thickness) with respect to the average film thickness was less than that of Comparative Example 1 was judged as ○. In addition, a small ratio of the fluctuation range of the film thickness means higher uniformity of the film thickness in the plane of the wafer (Table 5).

[0492] In addition, in order to show that it has the same coatability as the existing materials even for Si substrates that do not contain nitrogen atoms, the results are shown for reference.

[0493] [Coatability Evaluation 3]

[0494] The resist underlayer film materials of Comparative Example 1 and Examples 1 to 21 were coated on a nitrogen atom-containing substrate on which SiON was vapor-deposited using ACT-8 manufactured by Tokyo Electron Limited, and fired at the specified temperature and for the specified time described in Table 5 in an atmospheric atmosphere to form a 5-nm resist underlayer film. Then, the surface roughness was evaluated using AFM, and the coatability was evaluated. As a result of AFM observation, the cases where the coatability was not problematic were evaluated as ○ (Table 5).

[0495] Table 5

[0496]

[0497]

[0498] According to Table 4 and Table 5, the coating agent composition for a nitrogen atom-containing substrate of the present invention shows excellent coatability regardless of the presence or absence of height differences on the nitrogen atom-containing substrate, similar to a silicon wafer, in the same manner as the existing material composition.

[0499] [Lithography evaluation]

[0500] Using ACT-8 manufactured by Tokyo Electron Limited, the coating agent compositions of Comparative Example 1 and Examples 1 to 21 were respectively coated on a nitrogen atom-containing substrate on which a SiON film was formed to a film thickness of 5 nm, and fired at the specified temperature and for the specified time described in Table 6 to form a resist underlayer film. In addition, as comparative examples, Comparative Examples 2 to 4 in which no resist underlayer film was formed were also tested except for Comparative Example 1. A commercially available ArF resist solution (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SAIL X-206) was coated on these resist underlayer films or the substrates on which no resist underlayer film was formed, fired at 85°C for 60 seconds, and a photoresist film with a film thickness of 100 nm was formed. Exposure and development treatments were performed on two types of substrates immediately after the formation of the resist film and 48 hours after the formation of the resist film. Using an NSR (registered trademark)-S307E scanner manufactured by Nikon Corporation (wavelength 193 nm, NA = 0.85, σ = 0.93 / 0.85), exposure was performed after development through a mask set in such a way that the line width of the photoresist and the width between its lines were each 0.1 μm, that is, a dense line with a line and space (L / S) = 1 / 1 of 0.1 μm. Then, it was baked on a hot plate at 95°C for 60 seconds, and after cooling, developed with butyl acetate for 60 seconds to form a negative pattern on the resist underlayer film.

[0501] The pattern size immediately after forming the resist pattern was observed using a CD-SEM (manufactured by Hitachi High-Tech Corporation). The sizes of the resist patterns that were exposed and developed immediately after forming the resist film were compared with those of the resist patterns that were exposed and developed after 48 hours. A case where the change in the pattern size was less than that of all Comparative Examples 1 to 4 was judged as ○. Subsequently, the sheet material capable of forming the target pattern size was cut, and observation was performed using a scanning electron microscope (S-4800) manufactured by Hitachi High-Tech Corporation. A case where the resist shape was a vertical shape without being affected by poisoning of the substrate containing nitrogen atoms was judged as ○, and a case where it was affected and was a non-vertical shape was judged as × (Table 6).

[0502] Table 6

[0503]

[0504] As described above, novolak resins containing a unit structure derived from phenol and novolak resins containing a unit structure derived from carbazole can exhibit very good curability both in an air atmosphere and in a nitrogen atmosphere at a film thickness of less than 10 nm, and can be used as an underlayer film for a resist in an ultra-thin film state. In addition, even when a triple bond is introduced into the OH group in the phenol / phenoxy skeleton or the NH group in the carbazole skeleton, the effect is not impaired. Furthermore, even at a film thickness of less than 10 nm, good coatability is exhibited with respect to various types of vapor deposition films, and both substrates with height differences and substrates without height differences show high in-plane uniformity of the film thickness. In addition, the structure of this embodiment can block amine components diffusing from amine-containing base substrates such as SiON, SiN, and TiN. Thus, even when exposure and development processes are performed after a long time has elapsed after forming the resist film, the size and shape of the resist can be maintained in the same manner as when exposure and development are performed immediately after forming the resist film. Therefore, it is expected that the coating agent composition for a substrate containing nitrogen atoms will become a material that can be widely applied to diverse semiconductor manufacturing processes for coating substrates containing nitrogen atoms.

Claims

1. A coating agent composition for a substrate containing a nitrogen atom, which is a coating agent composition for a substrate containing a nitrogen atom comprising a novolak resin and a solvent, wherein, the novolak resin contains a unit structure A having at least a carbazole skeleton or a phenol / phenoxy skeleton as a partial structure, the substrate containing a nitrogen atom is a substrate formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing a nitrogen atom, the film containing a nitrogen atom is formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom.

2. The coating agent composition for a substrate containing a nitrogen atom according to claim 1, which is a composition for forming an underlayer film of a resist.

3. The coating agent composition for a substrate containing a nitrogen atom according to claim 2, wherein the underlayer film of the resist is an underlayer thin film of the resist having a film thickness of less than 10 nm.

4. The coating agent composition for a substrate containing a nitrogen atom according to claim 1, wherein the film containing a nitrogen atom constitutes the outermost layer of the substrate containing a nitrogen atom.

5. The coating agent composition for a substrate containing a nitrogen atom according to claim 1, wherein the metal atom or the metalloid atom is (i) silicon, (ii) titanium, or (iii) tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or an alloy thereof.

6. The coating agent composition for a substrate containing a nitrogen atom according to claim 5, wherein the compound having a bond between a metal atom or a metalloid atom and a nitrogen atom is SiON, SiN, TiON or TiN.

7. The coating agent composition for a substrate containing a nitrogen atom according to claim 1, wherein the unit structure A having at least a carbazole skeleton or a phenol / phenoxy skeleton as a partial structure is a structural unit derived from one or more compounds selected from the following structural formulas (A-1) to (A-9), wherein, in formulas (A-1) to (A-9), R N and R O each independently represents (i) a hydrogen atom or a hydroxymethyl group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, Among them, R N is combined with the nitrogen atom on the carbazole skeleton, and R O is combined with the oxygen atom of the aryloxy group of the Ar B ring. furthermore, regarding the above (ii) and (iii), a hydrogen atom in these groups may be further substituted with a substituent containing an oxygen atom, a substituent containing a sulfur atom, a substituent containing a nitrogen atom, an aryl group or a halogen-containing group, and a hydrocarbon chain portion of the above (iii) may be further interrupted with a substituent containing an oxygen atom, a substituent containing a sulfur atom, a substituent containing a nitrogen atom or an arylene group, in formulas (A-8) to (A-9), Ar B each independently represents a benzene ring, a naphthalene ring or a condensed ring containing one or more benzene rings In formula (A-8), m represents the number of R O O groups of 1 or more, O and, in formulas (A-7) and (A-9), L represents a single bond or a polyvalent linking group having a valence of 2 to 8, in formula (A-7), n1 represents the number of carbazole skeletons in which a carbon atom on the aromatic ring of the carbazole skeleton is bonded to L, n2 represents the number of carbazole skeletons in which a nitrogen atom on the carbazole skeleton is bonded to L, n1 and n2 are each 0 or more, but the sum of n1 and n2 is an integer of 2 to 8. When L is a single bond, the sum of n1 and n2 is 2. In formula (A-9), m21 is Ar B The carbon atoms on the ring are combined with L in the (R O O) m11 Ar B The number of groups, m11 each independently represents R O The number of O groups, m22 represents Ar B The oxygen atom of the aryloxy group of the ring is combined with L to form OAr B (OR O ) m12 The number of groups, m12 each independently represents R O The number of O groups, m11, m21, m12, and m22 are each 0 or more, but the sum of m21 of m11 and m22 is 1 or more, the sum of m21 and m22 is 2 to 8, and when L is a single bond, the sum of m21 and m22 is 2 In each of these aromatic rings in formulas (A-1) to (A-9), further substituents may optionally be present.

8. The coating agent composition for a nitrogen atom-containing substrate according to claim 7, L is selected from a single bond, -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, -NH-, -(CR 1 R 2 ) m1 -, -(Ar) m2 -, -CH2-(Ar) m2 -CH2- and -(cyclo-R)-, R 1 and R 2 which are the same as or different from each other, each independently represents a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms or an aryl group having 6 to 30 carbon atoms, and m1 represents an integer of 1 to 10 Ar represents an arylene group having 6 to 30 carbon atoms, and m2 represents an integer of 1 to 3 which is the number of aromatic rings bonded to each other by a single bond. cyclo-R represents a divalent alicyclic hydrocarbon group having 5 to 8 members which can form a condensed ring with one or two benzene rings or naphthalene rings.

9. The coating agent composition for a substrate containing a nitrogen atom according to claim 7, wherein at least a part of R N or R O contains the following substituents, *-R 3 -C≡C-R 4 Wherein, * represents a bonding site, R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms, R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

10. The coating agent composition for a nitrogen atom-containing substrate according to claim 1, The novolak resin contains a composite unit structure A-B represented by the following formula (AB), In the formula (AB), n represents the number of the composite unit structure A-B, The unit structure A is the unit structure A described in claim 1, The unit structure B represents one or more unit structures including the structures represented by the following formulas (B1), (B2) or (B3), * represents a bonding site, In formula (B1), R and R’ each independently represent a hydrogen atom, an aromatic ring residue having 6 to 30 carbon atoms which may have a substituent; a heterocyclic residue having 3 to 30 carbon atoms which may have a substituent; a linear, branched or cyclic alkyl group having 10 or less carbon atoms which may have a substituent; or a formyl group, * represents a bonding site, *-J 1 -Z 0 -J 2 -* (B2) In formula (B2), Z 0 represents an aromatic ring residue or an aliphatic ring residue having 6 to 30 carbon atoms which may have substituents, or an organic group in which two aromatic ring residues or aliphatic ring residues are connected by a single bond J 1 and J 2 each independently represents a divalent organic group that is directly bonded or may have substituents, * represents a bonding site, In formula (B3), Z is a monocyclic or bicyclic, tricyclic or tetracyclic condensed ring having 4 to 25 carbon atoms which may have a substituent, the monocyclic ring is a non-aromatic monocyclic ring; at least one of the monocyclic rings constituting the bicyclic, tricyclic and tetracyclic rings is a non-aromatic monocyclic ring, and the remaining monocyclic rings may be aromatic monocyclic rings or non-aromatic monocyclic rings. The monocyclic or bicyclic, tricyclic or tetracyclic condensed ring may further form a condensed ring with one or more aromatic rings to form a condensed ring having five or more members. X and Y are the same or different and represent -CR 31 R 32 -group, R 31 and R 32 each of which is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, x and y each represent the number of X and Y, and each independently represents 0 or 1. *-X x In the case of x = 1, it binds to any carbon atom of the non-aromatic monocyclic ring constituting Z, i.e., carbon atom 1, and in the case of x = 0, it extends from carbon atom 1. Y y - *When y = 1, it binds to any carbon atom of the non-aromatic monocyclic ring that constitutes Z, namely carbon atom 2, and when y = 0, it extends from carbon atom 2 The carbon atom 1 and the carbon atom 2 may be the same or different. In the case of being different, they may belong to the same non-aromatic monocyclic ring or different non-aromatic monocyclic rings. * represents a bonding site.

11. The coating agent composition for a nitrogen atom-containing substrate according to claim 1, wherein the solvent contains a solvent having a boiling point of 160 °C or higher.

12. The coating agent composition for a nitrogen atom-containing substrate according to claim 1, further comprising an acid and / or its salt and / or an acid generator.

13. The coating agent composition for a nitrogen atom-containing substrate according to claim 1, further comprising a crosslinking agent.

14. The coating agent composition for a nitrogen atom-containing substrate according to claim 13, wherein the crosslinking agent is an amino plastic crosslinking agent or a phenolic plastic crosslinking agent.

15. The coating agent composition for a substrate containing a nitrogen atom according to claim 1, further comprising a surfactant.

16. An underlayer film of a resist on a substrate containing a nitrogen atom, which is a fired product of a coating film formed from the coating agent composition for a substrate containing a nitrogen atom according to any one of claims 1 to 15.

17. The underlayer film of a resist on a substrate containing a nitrogen atom according to claim 16, having a film thickness of less than 10 nm.

18. A method for forming a resist pattern for manufacturing a semiconductor, comprising the step of coating the coating agent composition for a substrate containing a nitrogen atom according to any one of claims 1 to 15 on a semiconductor substrate containing a nitrogen atom, and then performing firing to form an underlayer film of a resist.

19. A method for manufacturing a semiconductor device, comprising the following steps: a step of forming an underlayer film of a resist on a semiconductor substrate containing a nitrogen atom by the coating agent composition for a substrate containing a nitrogen atom according to any one of claims 1 to 15; a step of forming a resist film on the underlayer film of a resist; and a step of forming a resist pattern on the resist film by irradiation with light or an electron beam and development.

20. The method for manufacturing a semiconductor device according to claim 19, further comprising a step of etching the underlayer film of a resist via the resist pattern.

21. The method for manufacturing a semiconductor device according to claim 20, further comprising a step of processing the semiconductor substrate through the patterned underlayer film of a resist.

22. The method for manufacturing a semiconductor device according to claim 19, wherein the step of forming a resist pattern on the resist film is performed by a nanoimprint method or a self-assembled monolayer method.

23. An underlayer film forming agent composition for a resist, which is an underlayer film forming agent composition containing a novolak resin and a solvent, the novolak resin contains a repeating unit structure A having at least a carbazole skeleton or a phenol / phenoxy skeleton as a partial structure, the underlayer film of a resist has a film thickness of less than 10 nm.

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