Composition for forming a resist underlayer, method for manufacturing a semiconductor substrate, and method for forming a resist underlayer

Abstract

A composition for forming a resist underlayer film, comprising a metal compound, a polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2), and a solvent. (In formula (1), R1 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. R2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.) (In Formula (2), R3 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group obtained by substituting or unsubstituted reducing water 6 to 20 aromatic rings, excluding (n+1) hydrogen atoms. R4 is a monovalent hydroxyalkyl group or a hydroxyl group having 1 to 10 carbon atoms. n is an integer from 0 to 8. If n is 2 or more, multiple R4s may be identical or different.)

Description

Technology Field

[0001] The present invention relates to a composition for forming a resist underlayer, a method for manufacturing a semiconductor substrate, and a method for forming a resist underlayer. Background Technology

[0002] In the manufacture of semiconductor substrates, etc., a metal hard mask composition that serves as a resist underlayer has been proposed (see Japanese Patent Publication No. 2013-185155). When manufacturing semiconductor substrates, etc., a clean track is generally used. A clean track is a device capable of consistently performing processing steps such as spin coating, EBR (Edge Bead Removal), back rinsing, and firing. The EBR process is a process in which, after forming a film on a substrate (wafer) by spin coating, the film on the edge portion (periphery portion) of the substrate is removed using a removal solution. This prevents contamination of the substrate transport arm of the clean track. Contamination of the transport arm can cause defects and may reduce the yield of device manufacturing. As a removal solution used in the EBR process, a mixture of propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether (30:70, mass ratio) is used, and it is widely used in the EBR process of resist films or resist underlayer films (silicon-containing films, organic underlayer films, metal hard masks). Prior art literature

[0003] Japanese Patent Publication No. 2013-185155 The problem to be solved

[0004] A composition for forming a resist underlayer (metal hard mask composition) requires, along with uniform coating properties on the substrate surface, good wafer edge removal properties (smoothness of the boundary between the remaining and removed portions of the metal hard mask) and suppression of film thickness variation (hump) in the EBR process.

[0005] The present invention is made based on the above circumstances, and its purpose is to provide a composition for forming a resist underlayer film that has excellent coating properties, wafer edge removal properties and hump suppression properties during the EBR process, a method for manufacturing a semiconductor substrate using the same, and a method for forming a resist underlayer film. means of solving the problem

[0006] In one embodiment, the present invention,

[0007] A metal compound (hereinafter also referred to as “[A] compound”) and,

[0008] A polymer having a first structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (I)”) and a second structural unit represented by the following formula (2) (hereinafter also referred to as “structural unit (II)”) (hereinafter also referred to as “[B] polymer”), and

[0009] Solvent (hereinafter also referred to as "[C] solvent")

[0010] This relates to a composition for forming a resist underlayer film containing

[0011]

[0012] (In Equation (1), R 1 R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0013]

[0014] (In Equation (2), R 3 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group formed by removing (n+1) hydrogen atoms from a substituted or unsubstituted aromatic ring having 6 to 20 reduced water atoms. R 4is a monovalent hydroxyalkyl group or hydroxyl group having 1 to 10 carbon atoms. n is an integer from 0 to 8. If n is 2 or more, multiple R 4 is the same or different.)

[0015] In one embodiment, the present invention,

[0016] A process of coating a composition for forming a resist underlayer film on a substrate, either directly or indirectly, and

[0017] A process of forming a resist pattern directly or indirectly on a resist underlayer film formed by the above coating process, and

[0018] A process of forming a pattern on the resist underlayer film by etching using the resist pattern as a mask.

[0019] Includes,

[0020] The above composition for forming a resist underlayer film,

[0021] Metal compounds and,

[0022] A polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2), and

[0023] menstruum

[0024] This relates to a method for manufacturing a semiconductor substrate containing

[0025]

[0026] (In Equation (1), R 1 R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0027]

[0028] (In Equation (2), R 3is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group formed by removing (n+1) hydrogen atoms from a substituted or unsubstituted aromatic ring having 6 to 20 reduced water atoms. R 4 is a monovalent hydroxyalkyl group or hydroxyl group having 1 to 10 carbon atoms. n is an integer from 0 to 8. If n is 2 or more, multiple R 4 is the same or different.)

[0029] In addition, the present invention, in other embodiments,

[0030] A process of coating a composition for forming a resist underlayer film directly or indirectly onto a substrate.

[0031] Equipped with,

[0032] The above composition for forming a resist underlayer film,

[0033] Metal compounds and,

[0034] A polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2)

[0035] menstruum

[0036] This relates to a method for forming a resist underlayer film containing

[0037]

[0038] (In Equation (1), R 1 R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0039]

[0040] (In Equation (2), R 3is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group formed by removing (n+1) hydrogen atoms from a substituted or unsubstituted aromatic ring having 6 to 20 reduced water atoms. R 4 is a monovalent hydroxyalkyl group or hydroxyl group having 1 to 10 carbon atoms. n is an integer from 0 to 8. If n is 2 or more, multiple R 4 is the same or different.) Effects of the invention

[0041] The composition for forming the resist underlayer according to the present invention has excellent coating properties, wafer edge removal properties during the EBR process, and hump suppression properties. The method for manufacturing the semiconductor substrate according to the present invention forms the resist underlayer using the composition for forming the resist underlayer which has excellent coating properties, wafer edge removal properties during the EBR process, and hump suppression properties, thereby enabling the efficient manufacturing of a high-quality semiconductor substrate. According to the method for forming the resist underlayer according to the present invention, since the composition for forming the resist underlayer which has excellent coating properties, wafer edge removal properties during the EBR process, and hump suppression properties is used, the desired resist underlayer can be efficiently formed. Therefore, these can be suitably used for the manufacture of semiconductor devices, etc., for which further miniaturization is expected to proceed in the future. Brief explanation of the drawing

[0042] Figure 1a is an optical microscope image (magnification 10x) of a case where no removal non-uniformity was observed in the evaluation of wafer edge removalability. Figure 1b is an optical microscope image (magnification 10x) showing removal non-uniformity in the evaluation of wafer edge removalability. Specific details for implementing the invention

[0043] Hereinafter, a composition for forming a resist underlayer, a method for manufacturing a semiconductor substrate, and a method for forming a resist underlayer according to each embodiment of the present invention will be described in detail. The description of the composition for forming a resist underlayer will be appropriately developed during the description of the method for manufacturing a semiconductor substrate. A combination of suitable embodiments in the embodiments is also preferred.

[0044] Method for manufacturing a semiconductor substrate

[0045] The method for manufacturing the semiconductor substrate comprises a process of coating a substrate with a composition for forming a resist underlayer film (hereinafter also referred to as "composition") directly or indirectly (hereinafter also referred to as "coating process"), a process of forming a resist pattern directly or indirectly on the resist underlayer film formed by the coating process (hereinafter also referred to as "resist pattern forming process"), and a process of forming a pattern on the resist underlayer film by etching using the resist pattern as a mask (hereinafter also referred to as "etching process").

[0046] According to the method for manufacturing the semiconductor substrate, a resist underlayer is formed using a composition for forming a resist underlayer that has excellent coating properties, wafer edge removal properties during the EBR process, and hump suppression properties, thereby enabling the efficient manufacturing of a high-quality semiconductor substrate.

[0047] The method for manufacturing the semiconductor substrate may, if necessary, further include a process of forming an organic lower layer directly or indirectly on a substrate having the resist lower layer formed by the coating process, prior to the resist pattern forming process (hereinafter also referred to as the "organic lower layer forming process").

[0048] The method for manufacturing the semiconductor substrate may, if necessary, further include a process of forming a silicon-containing film directly or indirectly on a substrate having the resist underlayer formed by the coating process, prior to the resist pattern forming process (hereinafter also referred to as the "silicon-containing film forming process").

[0049] Hereinafter, a composition for forming a resist underlayer used in the method for manufacturing the semiconductor substrate, and each process in the case where optional processes such as an organic underlayer forming process and a silicon-containing film forming process are provided will be described.

[0050] Composition for forming a resist underlayer

[0051] The composition for forming a resist underlayer (hereinafter also simply referred to as the “Composition”) contains [A] a compound, [B] a polymer, and [C] a solvent. The composition may contain other optional components to the extent that it does not impair the effects of the present invention.

[0052] [[A] Compound]

[0053] [A] A compound refers to a compound containing a metal atom and an oxygen atom. Examples of metal atoms constituting [A] a compound include metal atoms of Group 3 to Group 16 of the periodic table (excluding silicon atoms). [A] A compound may have one or more types of metal atoms.

[0054] As Group 3 metal atoms, for example, scandium, yttrium, lanthanum, cerium, etc.,

[0055] As metal atoms of Group 4, for example, titanium, zirconium, hafnium, etc.

[0056] As metal atoms of Group 5, for example, vanadium, niobium, tantalum, etc.

[0057] As metal atoms of Group 6, for example, chromium, molybdenum, tungsten, etc.

[0058] As metal atoms of Group 7, manganese, rhenium, etc.

[0059] As metal atoms of Group 8, iron, ruthenium, osmium, etc.,

[0060] As metal atoms of Group 9, cobalt, rhodium, iridium, etc.,

[0061] As metal atoms of Group 10, nickel, palladium, platinum, etc.

[0062] As metal atoms of Group 11, copper, silver, gold, etc.,

[0063] As metal atoms of Group 12, zinc, cadmium, mercury, etc.

[0064] As metal atoms of Group 13, aluminum, gallium, indium, etc.

[0065] As metal atoms of Group 14, germanium, tin, lead, etc.

[0066] As metal atoms of Group 15, antimony, bismuth, etc.,

[0067] Examples of metal atoms in Group 16 include tellurium.

[0068] As for the metal atoms constituting the above [A] compound, metal atoms of Group 3 to Group 16 are preferred, metal atoms of Group 4 to Group 14 are more preferred, metal atoms of Group 4, Group 5 and Group 14 are even more preferred, and metal atoms of Group 4 are particularly preferred. Specifically, titanium, zirconium, hafnium, tantalum, tungsten, tin, or a combination thereof are more preferred.

[0069] As for the component other than the metal atom constituting the above [A] compound (hereinafter also referred to as the "[x] compound)," an organic acid (hereinafter also referred to as the "[a] organic acid), hydroxy acid ester, β-diketone, α,α-dicarboxylic acid ester, and amine compound are preferred. Here, "organic acid" refers to an organic compound that exhibits acidity, and "organic compound" refers to a compound having at least one carbon atom.

[0070] [a] Examples of organic acids include carboxylic acids, sulfonic acids, sulfinic acids, organic phosphinic acids, organic phosphonic acids, phenols, enols, thiols, acid imides, oximes, sulfonamides, etc.

[0071] Examples of the above carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentacarbonic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, oleic acid, acrylic acid, methacrylic acid, trans-2,3-dimethylacrylic acid, stearic acid, linoleic acid, linolenic acid, arachidonic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, gallic acid, and shikimic acid; dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, and tartaric acid; and carboxylic acids having three or more carboxyl groups such as citric acid. there is.

[0072] Examples of the above sulfonic acids include benzenesulfonic acid, p-toluenesulfonic acid, etc.

[0073] Examples of the above sulfinic acids include benzenesulfinic acid, p-toluenesulfinic acid, etc.

[0074] Examples of the above organic phosphinic acids include diethylphosphinic acid, methylphenylphosphinic acid, diphenylphosphinic acid, etc.

[0075] Examples of the above organic phosphonic acids include methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid, phenylphosphonic acid, etc.

[0076] The above phenols include, for example, monovalent phenols such as phenol, cresol, 2,6-xylenol, and naphthol;

[0077] Divalent phenols such as catechol, resorcinol, hydroquinone, and 1,2-naphthalenediol;

[0078] Examples include phenols of trivalent or higher hydride, such as pyrogallol and 2,3,6-naphthalene triol.

[0079] Examples of the above enols include 2-hydroxy-3-methyl-2-butene, 3-hydroxy-4-methyl-3-hexene, etc.

[0080] Examples of the above thiols include mercaptoethanol, mercaptopropanol, etc.

[0081] Examples of the above acid imides include carboxylic acid imides such as maleimide and succinate imide, and also sulfonic acid imides such as di(trifluoromethanesulfonic acid)imide and di(pentafluoroethanesulfonic acid)imide.

[0082] Examples of the above oximes include aldoximes such as benzaldoxime and salicylaldoxime, and ketoximes such as diethyl ketoxime, methyl ethyl ketoxime, and cyclohexanone oxime.

[0083] Examples of the above sulfonamides include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, toluenesulfonamide, etc.

[0084] [a] As for the organic acid, carboxylic acid is preferred, monocarboxylic acid is more preferred, and methacrylic acid and benzoic acid are more preferred.

[0085] Examples of the above hydroxy acid esters include glycolic acid esters, lactic acid esters, 2-hydroxycyclohexane-1-carboxylic acid esters, salicylic acid esters, etc.

[0086] Examples of the above β-diketones include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, etc.

[0087] Examples of the above β-keto esters include acetoacetic acid esters, α-alkyl-substituted acetoacetic acid esters, β-ketopentanoic acid esters, benzoylacetic acid esters, 1,3-acetone dicarboxylic acid esters, etc.

[0088] Examples of amine compounds include diethanolamine and triethanolamine.

[0089] As for the [A] compound, a metal compound composed of a metal atom and an [a] organic acid is preferred, a metal compound composed of a metal atom of Group 4, Group 5 and Group 14 and a carboxylic acid is more preferred, and a metal compound composed of titanium, zirconium, hafnium, tantalum, tungsten or tin and methacrylic acid or benzoic acid is even more preferred.

[0090] [A] The compound may contain one or more of the above metal compounds.

[0091] [A] The compound may contain one or more [a] organic acids.

[0092] As a lower limit for the content ratio of [A] compound in the total components contained in the composition, 2 mass% is preferred, 4 mass% is more preferred, and 6 mass% is even more preferred. As an upper limit for the content ratio, 30 mass% is preferred, 20 mass% is more preferred, and 15 mass% is even more preferred.

[0093] [[A] Method of synthesizing compounds]

[0094] [A] Compound can be synthesized by, for example, by a method of carrying out a hydrolysis condensation reaction using [b] metal-containing compound, or by a method of carrying out a ligand exchange reaction using [b] metal-containing compound. Here, “hydrolysis condensation reaction” refers to a reaction in which a hydrolyzable group of [b] metal-containing compound is hydrolyzed and converted to -OH, and the two obtained -OHs undergo dehydration condensation to form -O-.

[0095] ([b] metal-containing compounds)

[0096] [b] The metal-containing compound is a metal compound (b1) having a hydrolyzable group, a hydrolyzed product of a metal compound (b1) having a hydrolyzable group, a hydrolyzed condensed product of a metal compound (b1) having a hydrolyzable group, or a combination thereof. The metal compound (b1) may be used as a single type or in combination of two or more types.

[0097] Examples of the above hydrolytic groups include halogen atoms, alkoxy groups, acyloxy groups, etc.

[0098] Examples of the above halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0099] Examples of the above alkoxy groups include methoxy groups, ethoxy groups, n-propoxy groups, isopropoxy groups, n-butoxy groups, etc.

[0100] Examples of the above acyloxy groups include, for instance, acetoxy groups, ethyryloxy groups, propionyloxy groups, butyryloxy groups, t-butyryloxy groups, t-amyloxy groups, n-hexane carbonyloxy groups, n-octane carbonyloxy groups, etc.

[0101] As the above hydrolytic groups, alkoxy groups and acyloxy groups are preferred, and isopropoxy groups and acetoxy groups are more preferred.

[0102] [b] When the metal-containing compound is a hydrolysis condensate of a metal compound (b1), the hydrolysis condensate of the metal compound (b1) may be a hydrolysis condensate of a metal compound (b1) having hydrolyzable groups and a compound containing metal atoms, provided that the effects of the present invention are not impaired. That is, the hydrolysis condensate of the metal compound (b1) may contain metal atoms within a range that does not impair the effects of the present invention. Examples of the metal atoms include silicon, boron, germanium, antimony, tellurium, etc. The content of metal atoms in the hydrolysis condensate of the metal compound (b1) is typically less than 50 atomic% with respect to the total of metal atoms and metal atoms in the hydrolysis condensate. As an upper limit for the content of metal atoms, 30 atomic% is preferred and 10 atomic% is more preferred with respect to the total of metal atoms and metal atoms in the hydrolysis condensate.

[0103] Examples of metal compounds (b1) include compounds represented by the following formula (α) (hereinafter also referred to as “[m] compounds”).

[0104]

[0105] In the above formula (α), M is a metal atom. L is a ligand. a is an integer from 0 to 2. When a is 2, multiple Ls may be the same or different. Y is a hydrolytic group selected from halogen atoms, alkoxy groups, and acyloxy groups. b is an integer from 2 to 6. Multiple Ys may be the same or different. Additionally, L is a ligand that does not correspond to Y.

[0106] As metal atoms represented by M, examples include metal atoms such as those exemplified as metal atoms constituting the metal compound [A].

[0107] Examples of ligators represented by L include single-seat ligators and multi-seat ligators.

[0108] Examples of the above monodentate ligands include hydroxo ligands, carboxyl ligands, amide ligands, ammonia, etc.

[0109] Examples of the above amide ligands include, for instance, unsubstituted amide ligands (NH2), methylamide ligands (NHMe), dimethylamide ligands (NMe2), diethylamide ligands (NEt2), dipropylamide ligands (NPr2), etc.

[0110] Examples of the above polydentate ligands include hydroxy acid esters, β-diketones, β-keto esters, β-dicarboxylic acid esters, hydrocarbons having a π bond, diphosphine, etc.

[0111] Examples of the above hydroxy acid esters include glycolic acid esters, lactic acid esters, 2-hydroxycyclohexane-1-carboxylic acid esters, salicylic acid esters, etc.

[0112] Examples of the above β-diketones include 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, etc.

[0113] Examples of the above β-keto esters include acetoacetic acid esters, α-alkyl-substituted acetoacetic acid esters, β-ketopentanoic acid esters, benzoylacetic acid esters, 1,3-acetone dicarboxylic acid esters, etc.

[0114] Examples of the above β-dicarboxylic acid esters include malonic acid diesters, α-alkyl-substituted malonic acid diesters, α-cycloalkyl-substituted malonic acid diesters, α-aryl-substituted malonic acid diesters, etc.

[0115] As for the hydrocarbon having the above π bond, for example,

[0116] Chain olefins such as ethylene and propylene;

[0117] Cyclopentene, cyclohexene, norbornene, etc. cyclic olefins;

[0118] Chain dienes such as butadiene, isoprene, etc.;

[0119] Cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene, norbornadiene;

[0120] Examples include aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene, and indene.

[0121] Examples of the above-mentioned diphosphine include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-vinaphthyl, 1,1'-bis(diphenylphosphino)ferrocene, etc.

[0122] Examples of halogen atoms represented by Y include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0123] Examples of alkoxy groups represented by Y include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.

[0124] Examples of acyloxy groups represented by Y include acetoxy groups, ethyryloxy groups, butyryloxy groups, t-butyryloxy groups, t-amyloxy groups, n-hexane carbonyloxy groups, n-octane carbonyloxy groups, etc.

[0125] As for Y, alkoxy groups and acyloxy groups are preferred, and isopropoxy groups and acetoxy groups are more preferred.

[0126] As for b, 3 and 4 are preferable, and 4 is more preferable.

[0127] [b] As metal-containing compounds, metal alkoxides that do not undergo hydrolysis or hydrolytic condensation and metal acyloxides that do not undergo hydrolysis or hydrolytic condensation are preferred.

[0128] [b] As metal-containing compounds, zirconium tetran-butoxide, zirconium tetran-propoxide, zirconium tetraisopropoxide, hafnium tetraethoxide, indium triisopropoxide, hafnium tetraisopropoxide, hafnium tetran-propoxide, hafnium tetran-butoxide, tantalum pentaethoxide, tantalum penta-n-butoxide, tungsten pentamethoxide, tungsten penta-n-butoxide, tungsten hexaethoxide, tungsten hexa-n-butoxide, iron chloride, zinc diisopropoxide, zinc acetate dihydrate, tetrabutyl orthotitanate, titanium tetran-butoxide, titanium tetran-propoxide, zirconium din-butoxide bis(2,4-pentanedianate), titanium trin-butoxide stearate, Bis(cyclopentadienyl)hafnium dichloride, Bis(cyclopentadienyl)tungsten dichloride, Diacetato[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-vinaphyl]ruthenium, Dichloro[ethylenebis(diphenylphosphine)]cobalt, Titanium butoxide oligomer, Aminopropyltrimethoxytitanium, Aminopropyltriethoxyzirconium, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium, γ-glycidoxypropyltrimethoxyzirconium, 3-isocyanopropyltrimethoxyzirconium, 3-isocyanopropyltriethoxyzirconium, Triethoxymono(acetylacetonato)titanium, Tri-n-propoxymono(acetylacetonato)titanium, Examples include tri-isopropoxymono(acetylacetonato)titanium, triethoxymono(acetylacetonato)zirconium, tri-n-propoxymono(acetylacetonato)zirconium, tri-isopropoxymono(acetylacetonato)zirconium, diisopropoxybis(acetylacetonato)titanium, din-butoxybis(acetylacetonato)titanium, din-butoxybis(acetylacetonato)zirconium, tri(3-methacryloxypropyl)methoxyzirconium, tri(3-acryloxypropyl)methoxyzirconium, tin-tetraisopropoxide, tin-tetran-butoxide, lanthanum oxide, yttrium oxide, etc.

[0129] Among these, metal alkoxides and metal acyloxides are preferred, metal alkoxides are more preferred, and alkoxides of titanium, zirconium, hafnium, tantalum, tungsten, and tin are even more preferred.

[0130] [A] When using an organic acid in the synthesis of a compound, the lower limit of the amount of the organic acid used is preferably 1 mole per 1 mole of [b] metal-containing compound, and more preferably 2 moles. Meanwhile, the upper limit of the amount of the organic acid used is preferably 6 moles per 1 mole of [b] metal-containing compound, and more preferably 5 moles.

[0131] [A] In the synthesis reaction of the compound, in addition to the metal compound (b1) and [a] organic acid, a compound that can be a polydentate ligand represented by L in the compound of formula (α) or a compound that can be a crosslinking ligand may be added. Examples of compounds that can be crosslinking ligands include compounds having multiple hydroxyl groups, isocyanate groups, amino groups, ester groups, and amide groups.

[0132] [b] As a method for carrying out a hydrolysis condensation reaction using a metal-containing compound, for example, a method of carrying out a hydrolysis condensation reaction of the [b] metal-containing compound in a solvent containing water may be used. In this case, other compounds having hydrolyzable groups may be added as needed. As a lower limit for the amount of water used in this hydrolysis condensation reaction, 0.2 times mole is preferred, 1 times mole is more preferred, and 3 times mole is even more preferred with respect to the hydrolyzable groups of the [b] metal-containing compound, etc. As an upper limit for the amount of water, 20 times mole is preferred, 15 times mole is more preferred, and 10 times mole is even more preferred.

[0133] [b] As a method for carrying out a ligand exchange reaction using a metal-containing compound, for example, [b] a metal-containing compound and [a] an organic acid can be mixed. In this case, the mixture may be mixed in a solvent or without using a solvent. In addition, a base such as triethylamine may be added to the mixture as needed. The amount of the base added is, for example, 1 part by mass or more and 200 parts by mass or less, with respect to 100 parts by mass of the total amount of [b] metal-containing compound and [a] organic acid.

[0134] [A] The solvent used for the synthesis reaction of the compound (hereinafter also referred to as the [d] solvent) is not particularly limited, and, for example, any solvent similar to the [C] solvent described below may be used. Among these, alcohol-based solvents, ether-based solvents, ester-based solvents, and hydrocarbon-based solvents are preferred, alcohol-based solvents, ether-based solvents, and ester-based solvents are more preferred, monoalcohol-based solvents, polyalcohol partial ether-based solvents, and polyalcohol partial ether carboxylate-based solvents are even more preferred, and ethanol, n-propanol, isopropanol, 1-butanol, propylene glycol monoethyl ether, and propylene glycol monoethyl ether acetate are particularly preferred.

[0135] [A] When [d] solvent is used in the synthesis reaction of the compound, the used solvent may be removed after the reaction, but it may also be used as the [C] solvent of the resist underlayer forming composition without being removed after the reaction.

[0136] [[B] Polymer]

[0137] [B] The polymer has structural unit (I) and structural unit (II) (except for structural unit (I) which corresponds to structural unit (II)). [B] The polymer may contain other structural units other than structural unit (I) and structural unit (II) (hereinafter simply referred to as “other structural units”). [B] The polymer may have one or more of each structural unit.

[0138] (Structural Unit (I))

[0139] The structural unit (I) is a structural unit represented by the following formula (1). [B] By having the polymer having the structural unit (I), the fluidity of the composition can be improved, and as a result, the wafer edge removal and hump suppression properties during the EBR process of the resist underlayer film formed by the composition can be improved.

[0140]

[0141] In the above equation (1), R 1 R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0142] In this specification, "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Additionally, "hydrocarbon group" includes saturated hydrocarbon groups and unsaturated hydrocarbon groups. "Chain hydrocarbon group" refers to a hydrocarbon group that does not include a ring structure and is composed solely of a chain structure, and includes both straight-chain hydrocarbon groups and branched-chain hydrocarbon groups. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that includes only an alicyclic structure as a ring structure and does not include an aromatic ring structure, and includes both single-ring alicyclic hydrocarbon groups and multi-ring alicyclic hydrocarbon groups. However, an alicyclic hydrocarbon group does not necessarily have to be composed solely of an alicyclic structure and may include a chain structure in part. "Aromatic hydrocarbon group" refers to a hydrocarbon group that includes an aromatic ring structure as a ring structure. However, the aromatic hydrocarbon group does not need to be composed solely of an aromatic ring structure, and may include a chain structure or a ring structure in part.

[0143] R 1 or R 2 Examples of unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms include unsubstituted monovalent chain hydrocarbon groups having 1 to 20 carbon atoms, unsubstituted monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, unsubstituted monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, etc.

[0144] Examples of unsubstituted monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; and alkynyl groups such as ethinyl, propynyl, and butynyl groups.

[0145] Examples of unsubstituted monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, cycloalkenyl groups such as cyclopropenyl groups, cyclopentenyl groups and cyclohexenyl groups, and exchanged hydrocarbon groups such as norbornyl groups and adamantyl groups.

[0146] Examples of unsubstituted monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl groups and naphthyl groups, aralkyl groups such as benzyl groups, phenethyl groups, and naphthylmethyl groups.

[0147] R 1 or R 2 Examples of substituents in this include monovalent chain hydrocarbon groups having 1 to 10 carbon atoms, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, alkoxy groups such as methoxy groups, ethoxy groups, and propoxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups, ethoxycarbonyl groups, alkoxycarbonyloxy groups such as methoxycarbonyloxy groups, ethoxycarbonyloxy groups, and alkoxycarbonyloxy groups, acyl groups such as formyl groups, acetyl groups, propionyl groups, and butyryl groups, cyano groups, nitro groups, and hydroxyl groups.

[0148] R 1 As such, a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms is preferred, a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms is more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0149] R 2As such, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms substituted is preferred, a monovalent chain hydrocarbon group having 1 to 20 carbon atoms substituted with fluorine atoms is more preferred, and a hexafluoroisopropyl group, a 2,2,2-trifluoroethyl group, or a 3,3,4,4,5,5,6,6-octafluorohexyl group is even more preferred. In this case, the wafer edge removal performance and hump suppression performance during the EBR process of the resist underlayer film formed by the composition can be further improved. In this specification, "a monovalent chain hydrocarbon group having 1 to 20 carbon atoms substituted with fluorine atoms" means a group in which some or all of the hydrogen atoms of the chain hydrocarbon are substituted with fluorine atoms.

[0150] [B] The lower limit of the content ratio of structural unit (I) in the total structural unit constituting the polymer is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%. The upper limit of the content ratio is preferably 90 mol%, more preferably 80 mol%, and even more preferably 70 mol%. When the content ratio of structural unit (I) is within the above range, the wafer edge removal and hump suppression properties during the EBR process of the resist underlayer film formed by the composition can be further improved.

[0151] (Structural Unit (II))

[0152] The structural unit (II) is a structural unit represented by the following formula (2). [B] By having the polymer with the structural unit (II), compatibility with the [A] compound and affinity with the substrate can be improved, and as a result, the coating properties of the composition can be improved.

[0153]

[0154] In the above equation (2), R 3is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group formed by removing (n+1) hydrogen atoms from a substituted or unsubstituted aromatic ring having 6 to 20 reduced water atoms. R 4 is a monovalent hydroxyalkyl group or hydroxyl group having 1 to 10 carbon atoms. n is an integer from 0 to 8. If n is 2 or more, multiple R 4 is the same or different.

[0155] R 3 As for the unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms in the above, for example, R of the above formula (1). 1 Examples of unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, such as those exemplified above, may be given.

[0156] R 3 As a substituent in , for example, R of the above formula (1) 1 Examples of substituents in this include groups similar to those exemplified.

[0157] R 3 As such, a hydrogen atom or a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms is preferred, a hydrogen atom or an unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms is more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0158] Examples of divalent linkers in L include divalent hydrocarbon groups having 1 to 10 carbon atoms, -COO-, -CO-, -O-, -CONH-, etc.

[0159] As for L, a single bond is preferred.

[0160] Examples of aromatic rings of 6 to 20 unsubstituted reduced water in Ar include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, anthracene rings, indene rings, and pyrene rings; aromatic heterocyclic rings such as furan rings, pyrrole rings, thiophene rings, phosphol rings, pyrazol rings, oxazole rings, isooxazole rings, thiazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, and triazine rings. Among these, aromatic hydrocarbon rings are preferred. In this specification, "reduced water" refers to the number of atoms constituting a ring, and in the case of a polycyclic ring, it refers to the number of atoms constituting the polycyclic ring.

[0161] As a substituent in Ar, for example, R of the above formula (1). 1 Groups similar to those exemplified as substituents in can be cited. However, R described later 4 is not considered a substituent in Ar.

[0162] As for Ar, a group excluding (n+1) hydrogen atoms from an unsubstituted aromatic ring of 6 to 20 reduced water is preferred, a group excluding (n+1) hydrogen atoms from an unsubstituted aromatic hydrocarbon ring of 6 to 20 reduced water is more preferred, and a group excluding (n+1) hydrogen atoms from an unsubstituted benzene ring is even more preferred.

[0163] R 4 The monovalent hydroxyalkyl group having 1 to 10 carbon atoms in the above is a group in which some or all of the hydrogen atoms of the monovalent alkyl group having 1 to 10 carbon atoms are substituted with a hydroxyl group.

[0164] R 4 As for, a monovalent hydroxyalkyl group having 1 to 10 carbon atoms is preferred, a monovalent monohydroxyalkyl group having 1 to 10 carbon atoms is more preferred, and a monohydroxymethyl group is even more preferred. R 4 Due to the above-mentioned cause, the flatness of the resist underlayer film formed by the said composition can be further improved.

[0165] As for n, 1 to 5 is preferred, 1 to 3 is more preferred, 1 or 2 is even more preferred, and 1 is particularly preferred.

[0166] [B] The lower limit of the content ratio of structural unit (II) in the total structural units constituting the polymer is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%. The upper limit of the content ratio is preferably 90 mol%, more preferably 80 mol%, and even more preferably 70 mol%. When the content ratio of structural unit (II) is within the above range, the coating properties of the composition can be further improved.

[0167] (Other structural units)

[0168] Other structural units include, for example, structural units derived from (meth)acrylic acid esters, structural units derived from (meth)acrylic acid, and structural units derived from acenaphthylene compounds.

[0169] [B] When the polymer has other structural units, the upper limit of the content ratio of other structural units in the total structural units constituting the [B] polymer is preferably 20 mol%, and more preferably 5 mol%.

[0170] [B] As a lower limit of the polymer Mw, 1,000 is preferred, 2,000 is more preferred, 3,000 is even more preferred, and 3,500 is particularly preferred. As an upper limit of the polymer Mw, 100,000 is preferred, 50,000 is more preferred, 30,000 is even more preferred, and 20,000 is particularly preferred. [B] By setting the polymer Mw to the above range, in addition to the coating properties of the composition, wafer edge removal properties and hump suppression properties during the EBR process of the resist underlayer film formed by the composition can be improved.

[0171] [B] The upper limit of the polymer's Mw / Mn is preferably 5, more preferably 3, and even more preferably 2.5. The lower limit of the Mw / Mn is typically 1, and 1.2 is preferred.

[0172] As a lower limit for the content of [B] polymer in the composition, 0.00001 parts by mass is preferred, 0.00005 parts by mass is more preferred, 0.0001 parts by mass is even more preferred, and 0.001 parts by mass is particularly preferred with respect to 10 parts by mass of [A] compound. As an upper limit for the content, 2 parts by mass is preferred, 1.5 parts by mass is more preferred, 1 part by mass is even more preferred, and 0.8 parts by mass is particularly preferred. By having the content of [B] polymer within the above range, the coating properties of the composition, along with the wafer edge removal properties and hump suppression properties during the EBR process of the resist underlayer film formed by the composition, can be improved.

[0173] ([B] Method of polymer synthesis)

[0174] [B] A polymer can be synthesized by polymerizing, for example, a monomer that provides a structural unit (I), a monomer that provides a structural unit (II), and, if necessary, a monomer that provides other structural units, using amounts of each in a predetermined content ratio, by a known method.

[0175] [[C] Solvent]

[0176] [C] As a solvent, it is not particularly limited as long as it is a solvent capable of dissolving or dispersing at least [A] a compound, [B] a polymer, and any other optional components. The composition may contain one or more [C] solvents.

[0177] [C] Organic solvents can be used as solvents. Examples of organic solvents include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, nitrogen-containing solvents, etc.

[0178] Examples of alcohol-based solvents include monoalcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, and 1-butanol, and polyalcohol-based solvents such as ethylene glycol, 1,2-propylene glycol, triethylene glycol, and tripropylene glycol.

[0179] Examples of ketone-based solvents include chain-based ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone, and cyclic ketone solvents such as cyclohexanone.

[0180] Examples of ether-based solvents include chain ether-based solvents such as n-butyl ether, polyhydric alcohol ether-based solvents such as tetrahydrofuran and 1,4-dioxane, polyhydric alcohol partial ether-based solvents such as propylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and tetraethylene glycol monomethyl ether.

[0181] Examples of ester-based solvents include carbonate-based solvents such as diethyl carbonate, acetic acid monoester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate, lactone-based solvents such as γ-butyrolactone, polyhydric alcohol moiety ether carboxylate-based solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and lactic acid ester-based solvents such as methyl lactate and ethyl lactate.

[0182] Examples of nitrogen-containing solvents include chain nitrogen-containing solvents such as N,N-dimethylacetamide and cyclic nitrogen-containing solvents such as N-methylpyrrolidone.

[0183] Other examples include aromatic solvents such as toluene, xylene, and mesitylene.

[0184] [C] As a solvent, ether-based solvents and / or ester-based solvents are preferred, polyhydric alcohol partial ether-based solvents and / or polyhydric alcohol partial ether carboxylate-based solvents are more preferred, and propylene glycol monoethyl ether and / or propylene glycol monomethyl ether acetate are even more preferred.

[0185] [A] As a lower limit for the content of [C] solvent in the total amount of compound and [C] solvent, 50 mass% is more preferable, 60 mass% is more preferable, and 70 mass% is more preferable. As an upper limit for the above content, 99 mass% is more preferable, 95 mass% is more preferable, and 90 mass% is more preferable. By setting the content of [C] solvent to the above range, the preparation of the composition can be facilitated, and the coating properties can be improved.

[0186] [Other optional components]

[0187] The composition may contain other components other than those mentioned above, such as acid generators, polymer additives, polymerization inhibitors, surfactants, etc.

[0188] If the composition contains other optional components, the content of the other optional components in the composition can be appropriately determined according to the type or function of the other optional components used.

[0189] An acid-generating agent is a compound that generates acid upon irradiation and / or heating. The composition may contain one or more acid-generating agents.

[0190] Examples of acid-generating agents include onium salt compounds and N-sulfonylmide compounds.

[0191] The composition can further enhance the coating properties or film continuity on a substrate or an organic underlayer film by containing a polymer additive. The composition may contain one or more polymer additives.

[0192] Examples of polymer additives include (poly)oxyalkylene-based polymer compounds, fluorine-containing polymer compounds, and non-fluorine-based polymer compounds.

[0193] (Poly)oxyalkylene-based polymer compounds include, for example, polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether; (poly)oxyalkyl ethers such as oxyethylene oxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly)oxyalkylene (alkyl)aryl ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether; acetylene ethers obtained by addition polymerization of alkylene oxides to acetylene alcohols such as 2,4,7,9-tetramethyl-5-decine-4,7-diol, 2,5-dimethyl-3-hexine-2,5-diol, and 3-methyl-1-butyn-3-ol; diethylene glycol oleic acid esters; and diethylene glycol lauric acid esters. Examples include (poly)oxyalkylene fatty acid esters such as ethylene glycol distearic acid ester, (poly)oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolauric acid ester and polyoxyethylene sorbitan trioleic acid ester, (poly)oxyalkylene alkyl(aryl) ether sulfate salts such as polyoxypropylene methyl ether sodium sulfate and polyoxyethylene dodecylphenol ether sodium sulfate, (poly)oxyalkylene alkyl phosphate esters such as (poly)oxyethylene stearyl phosphate ester, and (poly)oxyalkylene alkylamines such as polyoxyethylene laurylamine.

[0194] Examples of fluorine-containing polymer compounds include, for instance, the compound described in Japanese Patent Publication No. 2011-89090. Examples of fluorine-containing polymer compounds include, for instance, a compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom, and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups).

[0195] As non-fluorinated polymer compounds, for example, straight-chain or branched alkyl (meth)acrylates such as lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, isostearyl (meth)acrylate, isononyl (meth)acrylate, alkoxyethyl (meth)acrylates such as methoxyethyl (meth)acrylate, alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, Hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (-(CH2CH2O) n Examples include compounds having a structure, n=1 to 17) (meth)acrylate, containing one or more repeating units derived from (meth)acrylate monomers, etc.

[0196] The composition may increase the storage stability of the composition by containing a polymerization inhibitor. The composition may contain one or more polymerization inhibitors.

[0197] Examples of polymerization inhibitors include hydroquinone compounds such as 4-methoxyphenol and 2,5-di-tert-butylhydroquinone, and nitroso compounds such as N-nitrosophenylhydroxylamine and its aluminum salt.

[0198] The composition can further enhance the coating properties on a substrate or an organic underlayer film or the continuity of the film by containing a surfactant. The composition may contain one or more types of surfactants.

[0199] As commercially available surfactants, for example, “Newcol 2320”, “Newcol 714-F”, “Newcol 723”, “Newcol 2307”, “Newcol 2303” (all from Nippon New Kazai Co., Ltd.), “Pionin D-1107-S”, “Pionin D-1007”, “Pionin D-1106-DIR”, “New Calgen TG310”, “New Calgen TG310”, “Pionin D-6105-W”, “Pionin D-6112”, “Pionin D-6512” (all from Takemoto Yushi Co., Ltd.), “Surfinol 420”, “Surfinol 440”, “Surfinol 465”, “Surfinol 2502” (all from Nippon Air Products Co., Ltd.), “Megapac” F171", "F172", "F173", "F176", "F177", "F141", "F142", "F143", "F144", "R30", "F437", "F475", "F479", "F482", "F562", "F563", "F780", "R-40", "DS-21", "RS-56", "RS-90", "RS-72-K" (all from DIC Corporation), "Fluorad FC430", "FC431" (all from Sumitomo 3M Corporation), "Asahi Guard AG710", "Suplon S-382", "all Examples include "SC-101", "SC-102", "SC-103", "SC-104", "SC-105", "SC-106" (all from AGC Inc.), "FTX-218", "NBX-15" (NEOS Inc.), etc.

[0200] [Method for preparing a composition for forming a resist underlayer]

[0201] The composition for forming the resist underlayer can be prepared by mixing [A] a compound, [B] a polymer, [C] a solvent, and optionally any component in a predetermined ratio, and preferably by filtering the obtained mixture through a membrane filter with a hole diameter of 0.5 μm or less.

[0202] [Painting Process]

[0203] In the coating process, the composition for forming the resist underlayer is coated onto the substrate directly or indirectly. The method of coating the composition for forming the resist underlayer is not particularly limited, and, for example, rotary coating, flexible coating, roll coating, etc., can be carried out by suitable methods. By doing so, a coating film is formed, and the resist underlayer is formed as the volatilization of the [C] solvent occurs.

[0204] Examples of substrates include metal or semimetal substrates such as silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, and titanium substrates, and among these, a silicon substrate is preferred. The substrate may be a substrate on which a silicon nitride film, an alumina film, a silicon dioxide film, a tantalum nitride film, a titanium nitride film, etc. are formed.

[0205] As a lower limit for the average thickness of the formed resist underlayer film, 3 nm is preferred, 5 nm is more preferred, and 10 nm is even more preferred. As an upper limit for the average thickness, 500 nm is preferred, 200 nm is more preferred, and 50 nm is even more preferred. In addition, the method for measuring the average thickness is as described in the examples.

[0206] The method for manufacturing the semiconductor substrate preferably further includes a process of heating the coating film formed by the above coating process (hereinafter also referred to as a "heating process"). The heating of the coating film promotes the formation of a resist underlayer. More specifically, the heating of the coating film promotes the volatilization of the [C] solvent, etc.

[0207] The heating of the above coating film is typically performed under ambient air, but may also be performed under a nitrogen atmosphere. The lower limit of the temperature for heating is preferably 150°C, and more preferably 200°C. The upper limit of the temperature is preferably 600°C, and more preferably 400°C. The lower limit of the heating time is preferably 15 seconds, and more preferably 30 seconds. The upper limit of the time is preferably 1,200 seconds, and more preferably 600 seconds.

[0208] [Organic Sublayer Formation Process]

[0209] In this process, prior to the resist pattern formation process, an organic underlayer is formed directly or indirectly on a substrate having the resist underlayer formed by the coating process.

[0210] An organic underlayer can be formed by coating with a composition for forming an organic underlayer. As a method for forming an organic underlayer by coating with a composition for forming an organic underlayer, examples include a method of curing, etc., by heating or exposing the coated film formed by directly or indirectly coating the composition for forming an organic underlayer onto a substrate having the said resist underlayer. As the above composition for forming an organic underlayer, for example, JSR Corporation’s “HM8006” can be used. Various conditions for heating or exposure can be appropriately determined depending on the type of composition for forming an organic underlayer used.

[0211] [Silicon-containing film formation process]

[0212] In this process, prior to the resist pattern forming process, a silicon-containing film is formed directly or indirectly on a substrate having the resist underlayer film formed by the coating process.

[0213] Examples of cases in which a silicon-containing film is formed indirectly on a substrate having the said resist underlayer include, for instance, a case in which a surface modification film of the said resist underlayer is formed on the said resist underlayer.

[0214] Silicon-containing films can be formed by coating with a composition for forming silicon-containing films, chemical vapor deposition (CVD), atomic layer deposition (ALD), etc. As a method for forming a silicon-containing film by coating with a composition for forming silicon-containing films, examples include a method of curing, etc., by exposing and / or heating the coated film formed by coating the composition for forming silicon-containing films directly or indirectly onto the resist underlayer film. As commercially available products for the composition for forming silicon-containing films, examples include "NFC SOG01," "NFC SOG04," and "NFC SOG080" (all manufactured by JSR Corporation). Silicon oxide films, silicon nitride films, silicon oxynitride films, and amorphous silicon films can be formed by chemical vapor deposition (CVD) or atomic layer deposition (ALD).

[0215] [Resist Pattern Formation Process]

[0216] In this process, a resist pattern is formed directly or indirectly on the resist underlayer. Methods for performing this process include, for example, using a resist composition, using a nanoimprint method, or using a self-organizing composition. As for the case where a resist pattern is formed indirectly on the resist underlayer, for example, when the method for manufacturing the semiconductor substrate includes the silicon-containing film formation process, a resist pattern is formed on the silicon-containing film.

[0217] Specifically, the method of using the above resist composition involves forming a resist film by coating the resist composition so that the resist film to be formed has a predetermined thickness, and then volatilizing the solvent in the coated film by pre-baking.

[0218] Examples of the above resist compositions include, for instance, a positive or negative type chemically amplified resist composition containing a radioactive acid-reducing agent, a positive type resist composition containing an alkali-soluble resin and a quinone diazide-based photosensitive agent, and a negative type resist composition containing an alkali-soluble resin and a crosslinking agent. In addition, in this process, a commercially available resist composition may be used as is.

[0219] Next, the resist film formed above is exposed by selective radiation. The radiation used for exposure can be appropriately selected according to the type of radioactive acid generator used in the resist composition, and examples include visible light, ultraviolet light, far ultraviolet light, electromagnetic waves such as X-rays and γ-rays, and particle beams such as electron beams, molecular beams, and ion beams. Among these, far ultraviolet light is preferred, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 excimer laser light (wavelength 157 nm), Kr2 excimer laser light (wavelength 147 nm), ArKr excimer laser light (wavelength 134 nm), or extreme ultraviolet light (wavelength 13.5 nm, etc., hereinafter also referred to as "EUV") is more preferred, and KrF excimer laser light, ArF excimer laser light, or EUV is even more preferred.

[0220] After the above exposure, a post-bake may be performed to improve resolution, pattern profile, developability, etc. The temperature and time of this post-bake can be appropriately determined depending on the type of resist composition used, etc.

[0221] Next, the exposed resist film is developed with a developer to form a resist pattern. This development may be an alkaline development or an organic solvent development. As for the developer, in the case of alkaline development, basic aqueous solutions such as ammonia, triethanolamine, tetramethylammonium hydroxide (TMAH), and tetraethylammonium hydroxide may be used. To these basic aqueous solutions, an appropriate amount of water-soluble organic solvents, such as alcohols like methanol and ethanol, and surfactants may be added. Furthermore, in the case of organic solvent development, the developer may be various organic solvents exemplified as the [C] solvent of the composition described above.

[0222] After developing with the above developer, a predetermined resist pattern is formed by washing and drying.

[0223] [Etching Process]

[0224] In this process, a pattern is formed on the resist underlayer film by etching using the resist pattern as a mask. Regarding the number of etching steps, it may be performed once or multiple times, that is, sequential etching may be performed using the pattern obtained by etching as a mask; however, from the perspective of obtaining a pattern with a better shape, multiple steps are preferred. When performing multiple etching steps, sequential etching is performed in the order of the silicon-containing film, the organic underlayer film, the resist underlayer film, and the substrate. Examples of etching methods include dry etching and wet etching. Among these, dry etching is preferred from the perspective of obtaining a better pattern shape on the substrate. For this dry etching, a gas plasma, such as oxygen plasma, is used. By the above etching, a semiconductor substrate having a predetermined pattern is obtained.

[0225] Dry etching can be performed, for example, using a known dry etching apparatus. The etching gas used for dry etching can be appropriately selected based on the mask pattern, the elemental composition of the film to be etched, etc. Examples include fluorine-based gases such as CHF3, CF4, C2F6, C3F8, SF6, chlorine-based gases such as Cl2, BCl3, oxygen-based gases such as O2, O3, H2O, reducing gases such as H2, NH3, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H4, C3H6, C3H8, HF, HI, HBr, HCl, NO, NH3, BCl3, and inert gases such as He, N2, and Ar. These gases may also be used in combination. When etching a substrate using the pattern of the resist underlayer as a mask, fluorine-based gases are typically used.

[0226] Method for Forming a Resist Sublayer

[0227] The method for forming the resist underlayer comprises a process of coating a composition for forming the resist underlayer directly or indirectly onto a substrate. As the composition for forming the resist underlayer, the composition for forming the resist underlayer used in the method for manufacturing the semiconductor substrate can be suitably employed. As the coating process, the coating process in the method for manufacturing the semiconductor substrate can be suitably employed.

[0228] Examples

[0229] Examples are described below. Furthermore, the examples described below represent representative embodiments of the present invention, and the scope of the present invention should not be interpreted narrowly by such examples.

[0230] In this embodiment, the concentration of components other than the solvent in the mixture containing [A] compound, the weight average molecular weight (Mw) of the hydrolysis condensate in the mixture containing [A] compound, the weight average molecular weight (Mw) of the [B] polymer, and the average thickness of the film were measured by the following method.

[0231] [[A] Concentration of components other than the solvent in a mixture containing a compound]

[0232] [A] The mass of the residue was measured after calcining 0.5 g of a mixture containing [A] compound at 250°C for 30 minutes, and the concentration (mass%) of components other than the solvent in the mixture containing [A] compound was calculated by dividing the mass of the residue by the mass of the mixture containing [A] compound.

[0233] [[A] Weight average molecular weight (Mw) of hydrolysis condensate in a mixture containing a compound]

[0234] GPC columns (two “AWM-H” columns, one “AW-H” column, and two “AW2500” columns from Toso Co., Ltd.) were used, and under analysis conditions of flow rate: 0.3 mL / min, elution solvent: N,N-dimethylacetamide with added LiBr (30 mM) and citric acid (30 mM), and column temperature: 40℃, measurements were taken by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard.

[0235] [[B] Weight average molecular weight (Mw) of the polymer]

[0236] The Mw of the polymer was measured by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard, under analysis conditions of: flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40°C, using GPC columns (two “G2000HXL” columns, one “G3000HXL” column, and one “G4000HXL” column from Toso Co., Ltd.).

[0237] [Average thickness of the resist sublayer]

[0238] The average thickness of the resist underlayer was determined by using a spectroscopic ellipsometer (JAWOOLLAM “M2000D”) to measure the film thickness at 9 randomly spaced points 5 cm apart, including the center of the resist underlayer, and calculating the average value of their film thicknesses.

[0239] <[A] Synthesis of Compounds>

[0240] [A] The [m] compound, [x] compound, [d] solvent, and [C] solvent used in the synthesis of the compound are shown below. In the following synthesis examples, unless otherwise specified, "parts by mass" refers to the value when the mass of the [m] compound used is 100 parts by mass. Also, "molar ratio" refers to the value when the amount of the [m] compound used is 1. The concentration (mass%) of components other than the solvent in the mixture containing the [A] compound is shown in Table 1.

[0241] [m] As a compound, the following compounds were used.

[0242] m-1: Tetra-n-propoxyzirconium(IV)

[0243] m-2: Tetra-n-butoxyzirconium(IV)

[0244] m-3: Tetra-n-propoxyhafnium(IV)

[0245] m-4: Tetraisopropoxytitanium(IV)

[0246] m-5: Pentaethoxytantal(V)

[0247] [x] As a compound, the following compounds were used.

[0248] x-1: Propionic acid

[0249] x-2: Butyric acid

[0250] x-3: Isobutyric acid

[0251] x-4: Methacryl acid

[0252] x-5: 2-ethylhexanoic acid

[0253] x-6: Acetylacetone

[0254] x-7: Diethanolamine

[0255] [d] As a solvent, the following compounds were used.

[0256] d-1: n-propanol

[0257] d-2: Ethanol

[0258] d-3: 1-butanol

[0259] d-4: Isopropanol

[0260] [C] As a solvent, the following compounds were used.

[0261] C-1: Propylene glycol monomethyl ether acetate

[0262] C-2: Propylene glycol monoethyl ether

[0263] [Synthesization Example 1-1] ([A] Synthesis of Compound (A-1))

[0264] Under a nitrogen atmosphere, compound (m-1) and solvent (d-1) (40 parts by mass) were introduced into a reaction vessel. In the reaction vessel, compound (x-1) (molar ratio 5) was added dropwise over 20 minutes while stirring at 50°C. Subsequently, the reaction was carried out at 80°C for 3 hours. After the reaction was finished, the reaction vessel was cooled to 30°C or lower. The precipitate obtained by cooling was filtered and separated, washed with n-hexane (100 parts by mass), and vacuum dried to obtain compound (A-1).

[0265] [Synthesization Example 1-2] (Synthesization of [A] Compound (A-2))

[0266] Under a nitrogen atmosphere, compound (m-1) and solvent (d-1) (200 parts by mass) were introduced into a reaction vessel. In the reaction vessel, compound (x-2) (molar ratio 5) was added dropwise over 20 minutes while stirring at 50°C. Subsequently, the reaction was carried out at 80°C for 3 hours. After the reaction was finished, the reaction vessel was cooled to 30°C or lower. 900 parts by mass of solvent (C-1) were added to the cooled reaction solution, and then, using an evaporator, solvent (d-1), the alcohol produced by the reaction, and excess solvent (C-1) were removed to obtain a mixture containing compound (A-2). [A] The concentration of components other than the solvent in the mixture containing compound (A-2) was 14% by mass.

[0267] [Synthesization Examples 1-10, 1-14] ([A] Synthesis of compounds (A-10), (A-14))

[0268] Compounds [A] (A-10) and (A-14) were obtained in the same manner as Synthesis Example 1-1, except that [m] compound, [x] compound, and [d] solvent were used in the types and amounts shown in Table 1 below.

[0269] [Synthesized Examples 1-3 to 1-9 and 1-11 to 1-13] ([A] Synthesis of Compounds (A-3) to (A-9) and (A-11) to (A-13))

[0270] A mixture containing [A] compounds (A-3) to (A-9) and (A-11) to (A-13) was obtained in the same manner as Synthesis Example 1-2, except that [m] compound, [x] compound, [d] solvent, and [C] solvent were used in the types and amounts shown in Table 1 below.

[0271] [Synthesization Example 1-15] (Synthesization of [A] Compound (A-15))

[0272] Under a nitrogen atmosphere, compound (m-4) was introduced into a reaction vessel. In the reaction vessel, compound (x-6) (molar ratio 2) was added dropwise over 30 minutes while stirring at room temperature (25°C to 30°C). Subsequently, the reaction was carried out at 60°C for 2 hours. After the reaction was finished, the reaction vessel was cooled to 30°C or lower. The cooled reaction solution was diluted with solvent (d-4) (900 parts by mass). In the reaction vessel, water (molar ratio 2) was added dropwise over 10 minutes while stirring at room temperature (25°C to 30°C). Subsequently, a hydrolysis condensation reaction was carried out at 60°C for 2 hours. After the hydrolysis condensation reaction was finished, the reaction vessel was cooled to 30°C or lower. [A] After adding 1,000 parts by mass of solvent (C-2) to the cooled reaction solution, water, isopropanol, alcohol produced by the reaction, water, and excess solvent (C-2) were removed using an evaporator to obtain a mixture containing compound (A-15). The concentration of components other than the solvent in the mixture containing compound (A-15) was 13 mass%. The Mw of compound (A-15) was 2,800.

[0273] [Synthesization Example 1-16] (Synthesization of [A] Compound (A-16))

[0274] A mixture containing [A] compound (A-16) was obtained in the same manner as Synthesis Example 1-15, except that [m] compound, [x] compound, [d] solvent, and [C] solvent of the types and amounts shown in Table 1 below were used. The Mw of compound (A-16) was 1,600.

[0275]

[0276] <[B] Synthesis of Polymers>

[0277] [B] As a polymer, a polymer represented by the following formulas (B-1) to (B-10) and (b-1) (hereinafter referred to as “polymers (B-1) to (B-10) and (b-1)”) was synthesized by the following procedure.

[0278]

[0279] In the above formulas (B-1) to (B-10) and (b-1), the number attached to each structural unit indicates the content ratio (mol%) of that structural unit.

[0280] [Synthesization Example 2-1] (Synthesization of Polymer (B-1))

[0281] 43.0 g of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate and 57.0 g of vinylbenzyl alcohol were dissolved in 130 g of methyl isobutyl ketone, and 19.6 g of 2,2'-azobis(2-methylpropionic acid)dimethyl was added to prepare a monomer solution. 70 g of methyl isobutyl ketone was placed in a reaction vessel under a nitrogen atmosphere, heated to 80°C, and the monomer solution was added dropwise over 3 hours while stirring. The start of the dropwise addition was set as the start time of the polymerization reaction, and after carrying out the polymerization reaction for 6 hours, it was cooled to 30°C or below. 300 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the methyl isobutyl ketone was removed by reduced pressure concentration to obtain a propylene glycol monomethyl ether acetate solution of polymer (B-1). The Mw of the polymer (B-1) was 4,200.

[0282] [Synthesization Examples 2-2 to 2-11] (Synthesization of polymers (B-2) to (B-10) and (b-1)

[0283] Solutions of propylene glycol monomethyl ether of polymers (B-2) to (B-10) and (b-1) were obtained in the same manner as in Synthesis Example 2-1, except that each monomer was used to impart each structural unit shown in the above formulas (B-2) to (B-10) and (b-1) in each content ratio (mol%). The Mw of polymer (B-2) was 3,800, the Mw of polymer (B-3) was 4,000, the Mw of polymer (B-4) was 4,300, the Mw of polymer (B-5) was 4,500, the Mw of polymer (B-6) was 4,100, the Mw of polymer (B-7) was 4,100, the Mw of polymer (B-8) was 4,200, the Mw of polymer (B-9) was 4,200, the Mw of polymer (B-10) was 4,300, and the Mw of polymer (b-1) was 4,100.

[0284] <Preparation of Composition>

[0285] [A] Compound, [B] Polymer, [C] Solvent, and [F] Other Optional Components used in the preparation of the composition are shown below.

[0286] [A] As a compound, the above-described synthesized compounds (A-1) to (A-16) were used.

[0287] [B] As a polymer, the above-described synthesized polymers (B-1) to (B-10) and (b-1) were used.

[0288] [C] As a solvent, in addition to (C-1) and (C-2) used in the synthesis of [A] compound, the following compounds were used.

[0289] C-3: Cyclohexanone

[0290] C-4: 2-heptanone

[0291] C-5: Mesitylene

[0292] C-6: Butyl acetate

[0293] [F] As other optional components, the following compounds were used.

[0294] F-1: 4-Methoxyphenol

[0295] F-2: Surfactant (NEOS Corp.'s "NBX-15")

[0296] F-3: Surfactant (DIC Corporation’s “F563”)

[0297] [Example 1-1] Preparation of Composition (J-1)

[0298] As shown in Table 2 below, [A] a polymer (B-1) was mixed with 0.05 parts by mass and [C] (C-3) as a solvent with 90 parts by mass for every 10 parts by mass of [A] compound (A-1). The resulting solution was filtered through a polytetrafluoroethylene (PTFE) filter with a pore diameter of 0.2 μm to prepare composition (J-1). In Table 2 below, the “-” in [B] polymer and [F] other optional components indicates that [B] polymer and [F] other optional components were not used. The same applies below.

[0299] [Example 1-2] Preparation of Composition (J-2)

[0300] As shown in Table 2 below, a mixture containing [A] compound (A-2) and [C] solvent (C-1) were mixed such that for every 10 parts by mass of the component other than the solvent in [A] compound (A-2), [B] polymer (B-1) was 0.05 parts by mass and [C] solvent was 90 parts by mass (including [C] solvent included in the mixture containing [A] compound). The obtained solution was filtered through a polytetrafluoroethylene (PTFE) filter with a pore diameter of 0.2 μm to prepare composition (J-2).

[0301] [Examples 1-3 to 1-38] Preparation of compositions (J-3) to (J-38)

[0302] Compositions (J-3) to (J-38) were prepared by operating in the same manner as Example 1-1 or Example 1-2, except that the type and content of each component were as shown in Table 2 below.

[0303] [Comparative Examples 1-1 to 1-4] Preparation of compositions (j-1) to (j-4)

[0304] Compositions (j-1) to (j-4) were prepared by operating in the same manner as in Examples 1-2, except that the type and content of each component were as shown in Table 2 below.

[0305]

[0306] <Evaluation>

[0307] Using each of the compositions prepared above, coating properties, wafer edge removal properties, and hump suppression properties were evaluated according to the following methods. The evaluation results are shown in Table 3 below.

[0308] [Formation of a substrate equipped with an EBR-treated resist underlayer]

[0309] After coating the composition immediately after preparation using a spin coater (Tokyo Electron Inc.’s “CLEAN TRACK ACT8”) on a silicon wafer (substrate) by a rotational coating method, the composition was rotated at 1,500 rpm, and the removal liquid discharge nozzle was moved at a speed of 1 mm per second to a position where the length from the outer edge of the substrate to the center of the substrate was 2 mm, and the removal liquid (propylene glycol monomethyl ether acetate / propylene glycol monoethyl ether = 30 / 70, mass ratio) was discharged at a discharge rate of 2 ml per second. After discharging the removal liquid at a discharge rate of 2 ml per second for 10 seconds at a position where the length from the outer edge of the substrate to the center of the substrate was 2 mm, the discharge of the removal liquid was stopped, and the substrate was rotated under conditions of 1,500 rpm and 30 seconds. Next, by heating this substrate at 450°C for 60 seconds, a substrate having a resist underlayer film with an average thickness of 30 nm was obtained.

[0310] [Potter's Fortress]

[0311] Regarding coating performance, the substrate equipped with the above-mentioned resist lower layer was visually observed, and if no circular coating defects were visible, it was evaluated as “A” (good), and if there was one or more circular coating defects, it was evaluated as “B” (poor).

[0312] [Wafer Edge Removability]

[0313] Regarding wafer edge removal performance, the wafer periphery portion extending from the outer edge of the substrate equipped with the resist underlayer film to the center of the substrate by 5 mm was observed using an optical microscope (magnification 10x), and if no removal non-uniformity was observed, it was evaluated as “A” (good), and if removal non-uniformity was observed, it was evaluated as “B” (poor). FIG. 1a is an optical microscope image showing the case where no removal non-uniformity was observed in the evaluation of wafer edge removal performance, and FIG. 1b is an optical microscope image showing the case where removal non-uniformity was observed in the evaluation of wafer edge removal performance.

[0314] [Hump deterrence]

[0315] Regarding hump suppression performance, the change in height at a position from the outer edge of the substrate equipped with the above-mentioned resist underlayer film to the center of the substrate up to a length of 10 mm was measured using a stylus-type step meter (KLA Alpha-Step D-600, stylus pressure 5 mg). When the height of the substrate without the resist underlayer film was set to 0, it was evaluated as “A” (good) if the height was less than 40 nm, “B” (slightly good but poor) if the height was 40 nm or more and less than 50 nm, and “C” (poor) if the height was 50 nm or more.

[0316]

[0317] As can be seen from the results in Table 3, the composition of the example and the resist underlayer film formed from the composition had excellent coating properties, wafer edge removal properties, and hump suppression properties compared to the comparative example. Industrial applicability

[0318] The composition for forming a resist underlayer of the present invention has excellent coating properties, wafer edge removal properties during the EBR process, and hump suppression properties. The method for manufacturing a semiconductor substrate of the present invention forms a resist underlayer using a composition for forming a resist underlayer that has excellent coating properties, wafer edge removal properties during the EBR process, and hump suppression properties, thereby enabling the efficient manufacturing of a high-quality semiconductor substrate. According to the method for forming a resist underlayer of the present invention, since a composition for forming a resist underlayer that has excellent coating properties, wafer edge removal properties during the EBR process, and hump suppression properties is used, a desired resist underlayer can be efficiently formed. Therefore, these can be suitably used for the manufacture of semiconductor devices, for which further miniaturization is expected to proceed in the future.

Claims

Claim 1 A composition for forming a resist sublayer, comprising a metal compound, a polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2), and a solvent, wherein the metal compound is a [A] compound containing at least one [X] compound selected from the group consisting of a metal atom, an organic acid, a hydroxy acid ester, a β-diketone, an α,α-dicarboxylic acid ester, and an amine compound. (In Equation (1), R 1 R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. (In Equation (2), R 3 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group formed by removing (n+1) hydrogen atoms from a substituted or unsubstituted aromatic ring having 6 to 20 reduced water atoms. R 4 is a monovalent hydroxyalkyl group or hydroxyl group having 1 to 10 carbon atoms. n is an integer from 1 to 8. If n is 2 or more, multiple R 4 is the same or different.) Claim 2 A composition for forming a resist underlayer according to claim 1, wherein the content of the polymer relative to 10 parts by mass of the metal compound is 0.00001 parts by mass or more and 2 parts by mass or less. Claim 3 In paragraph 1 or 2, R 2 A composition for forming a resist underlayer, wherein the group is a monovalent chain hydrocarbon group having 1 to 20 carbon atoms that is substituted or unsubstituted. Claim 4 In paragraph 1 or 2, R 2 A composition for forming a resist underlayer, wherein the group is a monovalent chain hydrocarbon group having 1 to 20 carbon atoms substituted, and some or all of the hydrogen atoms of the chain hydrocarbon group are substituted with fluorine atoms. Claim 5 In paragraph 1 or 2, at least one R in formula (2) 4 A composition for forming a resist underlayer, wherein a is a monohydroxyalkyl group. Claim 6 A composition for forming a resist underlayer, wherein, in claim 5, the monohydroxyalkyl group is a monohydroxymethyl group. Claim 7 A composition for forming a resist underlayer according to claim 1 or 2, wherein the content ratio of the first structural unit in the total structural unit constituting the polymer is 10 mol% or more and 90 mol% or less. Claim 8 A composition for forming a resist underlayer according to claim 1 or 2, wherein the content ratio of the second structural unit in the total structural unit constituting the polymer is 10 mol% or more and 90 mol% or less. Claim 9 A composition for forming a resist underlayer according to claim 1 or 2, wherein the metal atom included in the metal compound belongs to groups 3 to 16 of the periodic table. Claim 10 A composition for forming a resist underlayer according to claim 1 or 2, wherein the metal atom included in the metal compound belongs to Group 4 of the periodic table. Claim 11 A composition for forming a resist sublayer according to claim 1 or 2, wherein the content ratio of the metal compound in the total components contained in the composition for forming a resist sublayer is 2 mass% or more and 30 mass% or less. Claim 12 A method for manufacturing a semiconductor substrate comprising the steps of: coating a composition for forming a resist sublayer film directly or indirectly on a substrate; forming a resist pattern directly or indirectly on the resist sublayer film formed by the coating process; and forming a pattern on the resist sublayer film by etching using the resist pattern as a mask, wherein the composition for forming a resist sublayer film comprises a metal compound, a polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2), and a solvent, wherein the metal compound is a [A] compound containing at least one [X] compound selected from the group consisting of a metal atom, an organic acid, a hydroxy acid ester, a β-diketone, an α,α-dicarboxylic acid ester, and an amine compound. (In Equation (1), R 1 R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. (In Equation (2), R 3 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group formed by removing (n+1) hydrogen atoms from a substituted or unsubstituted aromatic ring having 6 to 20 reduced water atoms. R 4 is a monovalent hydroxyalkyl group or hydroxyl group having 1 to 10 carbon atoms. n is an integer from 1 to 8. If n is 2 or more, multiple R 4 is the same or different.) Claim 13 A method for manufacturing a semiconductor substrate according to claim 12, further comprising a process of forming an organic lower layer directly or indirectly on a resist lower layer formed by the coating process prior to the resist pattern forming process. Claim 14 A method for manufacturing a semiconductor substrate according to claim 12 or 13, further comprising a process of forming a silicon-containing film directly or indirectly on a resist underlayer film formed by the coating process prior to the resist pattern forming process. Claim 15 A method for forming a resist sublayer, comprising a process of applying a composition for forming a resist sublayer directly or indirectly to a substrate, wherein the composition for forming a resist sublayer comprises a metal compound, a polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2), and a solvent, wherein the metal compound is a [A] compound containing at least one [X] compound selected from the group consisting of a metal atom, an organic acid, a hydroxy acid ester, a β-diketone, an α,α-dicarboxylic acid ester, and an amine compound. (In Equation (1), R 1 R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. 2 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. (In Equation (2), R 3 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent linker. Ar is a group formed by removing (n+1) hydrogen atoms from a substituted or unsubstituted aromatic ring having 6 to 20 reduced water atoms. R 4 is a monovalent hydroxyalkyl group or hydroxyl group having 1 to 10 carbon atoms. n is an integer from 1 to 8. If n is 2 or more, multiple R 4 is the same or different.)

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