Method for manufacturing semiconductor substrate and composition for forming film

Abstract

The invention provides a method for manufacturing a semiconductor substrate and a composition for forming a film, which can form a film with excellent etching resistance and embedding property. A method for producing a semiconductor substrate, the method including a step for applying, on a substrate, a film-forming composition containing a metal compound, an aromatic compound having an aromatic hydrocarbon ring structure having 6 or more carbon atoms and a partial structure represented by formula (1), and a solvent. [Formula 1] (In formula (1), X is a group represented by formula (i), formula (ii), formula (iii), or formula (iv); and * represents a bonding site to each of two adjacent carbon atoms constituting the aromatic hydrocarbon ring structure. ) (In formula (i), R1 represents a hydrogen atom or a monovalent organic group having 1-20 carbon atoms; r2 is a monovalent organic group with the carbon number of 1-20; in formula (ii), R3 represents a hydrogen atom or a monovalent organic group having 1-20 carbon atoms; r4 is a monovalent organic group having 1 to 20 carbon atoms; in formula (iii), R5 represents a monovalent organic group having 1-20 carbon atoms; in formula (iv), R6 represents a monovalent organic group having 1-20 carbon atoms. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a semiconductor substrate and a film-forming composition. Background Art

[0002] In the manufacture of semiconductor elements, for example, a multilayer resist process is used, wherein a resist film laminated on a substrate with an organic base film, a silicon-containing film, or the like interposed therebetween is exposed and developed to form a resist pattern. In the process, the resist base film is etched using the resist pattern as a mask, and the substrate is further etched using the obtained resist base film pattern as a mask, thereby forming a desired pattern on the substrate, and thus a patterned substrate can be obtained (see Japanese Patent Laid-Open No. 2004-177668).

[0003] In recent years, a metal hard mask composition has been proposed as a resist underlayer film (see Japanese Patent Application Laid-Open No. 2013-185155).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2004-177668

[0007] Patent Document 2: Japanese Patent Application Publication No. 2013-185155 Summary of the invention

[0008] Problems to be solved by the invention

[0009] Recently, substrates with patterns such as trenches and holes are often used, and metal hard mask compositions are required to have excellent etching resistance and to be able to form a pattern that can fully embed into the substrate. However, conventional metal hard mask compositions cannot meet these requirements.

[0010] The present invention has been made based on the above circumstances, and an object of the present invention is to provide a method for producing a semiconductor substrate and a film-forming composition capable of forming a film having excellent etching resistance and embedding properties.

[0011] Technical means of solving problems

[0012] In one embodiment, the present invention relates to a method for manufacturing a semiconductor substrate, comprising the steps of applying a film-forming composition on a substrate,

[0013] The film-forming composition comprises:

[0014] A metal compound (hereinafter, also referred to as “[A] compound”);

[0015] An aromatic compound having an aromatic hydrocarbon ring structure and a partial structure represented by the following formula (1) (hereinafter also referred to as "[B] compound"); and

[0016] a solvent (hereinafter also referred to as "[C] solvent"),

[0017] The aromatic hydrocarbon ring structure has 6 or more carbon atoms.

[0018]

[0019] (In formula (1), X is a group represented by the following formula (i), formula (ii), formula (iii) or formula (iv); * is a bonding site to two adjacent carbon atoms constituting the aromatic hydrocarbon ring structure.)

[0020] [Chemistry 2]

[0021]

[0022] (In formula (i), R 1 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 2 It is a monovalent organic group having 1 to 20 carbon atoms.

[0023] In formula (ii), R 3 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 4 It is a monovalent organic group having 1 to 20 carbon atoms.

[0024] In formula (iii), R 5 It is a monovalent organic group having 1 to 20 carbon atoms.

[0025] In formula (iv), R 6 It is a monovalent organic group having 1 to 20 carbon atoms.

[0026] In another embodiment, the present invention relates to a film-forming composition comprising:

[0027] Metal compounds;

[0028] An aromatic compound having an aromatic hydrocarbon ring structure and a partial structure represented by the following formula (1); and

[0029] solvent,

[0030] The aromatic hydrocarbon ring structure has 6 or more carbon atoms.

[0031] [Chemistry 3]

[0032]

[0033] (In formula (1), X is a group represented by the following formula (i), formula (ii), formula (iii) or formula (iv); * is a bonding site to two adjacent carbon atoms constituting the aromatic hydrocarbon ring structure.)

[0034] [Chemistry 4]

[0035]

[0036] (In formula (i), R 1 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 2 It is a monovalent organic group having 1 to 20 carbon atoms.

[0037] In formula (ii), R 3 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 4 It is a monovalent organic group having 1 to 20 carbon atoms.

[0038] In formula (iii), R 5 It is a monovalent organic group having 1 to 20 carbon atoms.

[0039] In formula (iv), R 6 It is a monovalent organic group having 1 to 20 carbon atoms.

[0040] Effects of the Invention

[0041] By the method for manufacturing a semiconductor substrate, a well-patterned semiconductor substrate can be obtained because a resist base film having excellent etching resistance and embedding properties is formed. By the film-forming composition, a film having excellent etching resistance and embedding properties can be formed. Therefore, these can be suitably used for the manufacture of semiconductor elements that are expected to be further miniaturized in the future. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] [ Figure 1 ] is an electron microscope photograph of a groove pattern embedded using the composition of Example 1-1.

[0043] [ Figure 2 ] is an electron microscope photograph of a groove pattern embedded using the composition of Comparative Example 1-1. DETAILED DESCRIPTION

[0044] 《Method for manufacturing semiconductor substrate》

[0045] The method for manufacturing the semiconductor substrate includes a step of coating a film-forming composition on a substrate (hereinafter, also referred to as a "coating step"). The method for manufacturing the semiconductor substrate preferably also includes: a step of directly or indirectly forming a resist pattern on the resist base film formed by the coating step (hereinafter, also referred to as a "resist pattern forming step"); and a step of forming a pattern on the film by etching using the resist pattern as a mask (hereinafter, also referred to as an "etching step").

[0046] The method for manufacturing the semiconductor substrate may, if necessary, also include the following step before the resist pattern forming step: a step of directly or indirectly forming an organic base film on the substrate having the resist base film formed by the coating step (hereinafter also referred to as "organic base film forming step").

[0047] The method for manufacturing the semiconductor substrate may, if necessary, further include the following step before the resist pattern forming step: a step of directly or indirectly forming a silicon-containing film on the substrate having the resist underlying film formed by the coating step (hereinafter also referred to as a "silicon-containing film forming step").

[0048] First, the film-forming composition used in the method for manufacturing the semiconductor substrate is described, and then each step including the resist pattern forming step and the etching step as appropriate steps, and the organic base film forming step and the silicon-containing film forming step as optional steps is described.

[0049] <Film-forming composition>

[0050] The film-forming composition (hereinafter also referred to as "composition") contains [A] compound, [B] compound and [C] solvent. The composition may also contain any other components within the range that does not impair the effect of the present invention. As a metal hard mask composition, if it is only a metal compound and a solvent, it is sometimes impossible to fully bury a groove or hole of tens of nanometers. In the composition, by using the [B] compound together with the [A] compound, excellent embedding property and etching resistance can be exerted.

[0051] [[A] Compound]

[0052] The [A] compound refers to a compound containing a metal atom and an oxygen atom. Examples of the metal atom constituting the [A] compound include metal atoms of Groups 3 to 16 of the periodic table (except silicon atoms). The [A] compound may have one or more metal atoms.

[0053] Examples of the metal atom of Group 3 include scandium, yttrium, lanthanum, and cerium.

[0054] Examples of the metal atom of Group 4 include titanium, zirconium, and hafnium.

[0055] Examples of the metal atom of Group 5 include vanadium, niobium, and tantalum.

[0056] Examples of the metal atom of Group 6 include chromium, molybdenum, and tungsten.

[0057] Examples of the metal atom of Group 7 include manganese and rhenium.

[0058] Examples of the metal atom of Group 8 include iron, ruthenium, and osmium.

[0059] Examples of the metal atom of Group 9 include cobalt, rhodium, iridium, and the like.

[0060] Examples of the metal atom of Group 10 include nickel, palladium, platinum, and the like.

[0061] Examples of the metal atom of Group 11 include copper, silver, gold, and the like.

[0062] Examples of the metal atom of Group 12 include zinc, cadmium, mercury, and the like.

[0063] Examples of the metal atom of Group 13 include aluminum, gallium, and indium.

[0064] Examples of the metal atom of Group 14 include germanium, tin, and lead.

[0065] Examples of the metal atom of Group 15 include antimony and bismuth.

[0066] Examples of the metal atom of Group 16 include tellurium and the like.

[0067] The metal atom constituting the compound [A] is preferably a metal atom of Group 3 to Group 16, more preferably a metal atom of Group 4 to Group 14, further preferably a metal atom of Group 4, Group 5 and Group 14, and particularly preferably a metal atom of Group 4. Specifically, titanium, zirconium, hafnium, tantalum, tungsten, tin or a combination thereof is further preferred.

[0068] As components other than the metal atom constituting the compound [A] (hereinafter also referred to as "compound [x]"), preferably an organic acid (hereinafter also referred to as "organic acid [a]"), a hydroxy acid ester, a β-diketone, an α,α-dicarboxylic acid ester, or an amine compound. Here, the term "organic acid" refers to an organic compound showing acidity, and the term "organic compound" refers to a compound having at least one carbon atom.

[0069] [a] Examples of the organic acid include carboxylic acid, sulfonic acid, sulfinic acid, organic phosphinic acid, organic phosphonic acid, phenols, enols, thiols, acid imides, oximes, and sulfonamides.

[0070] Examples of the carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, 2-ethylhexanoic acid, oleic acid, acrylic acid, methacrylic acid, trans-2,3-dimethylacrylic acid, stearic acid, linoleic acid, linolenic acid, arachidic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, gallic acid, and shikimic acid; examples of dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, and tartaric acid; and examples of carboxylic acids having three or more carboxyl groups such as citric acid.

[0071] Examples of the sulfonic acid include benzenesulfonic acid and p-toluenesulfonic acid.

[0072] Examples of the sulfinic acid include benzenesulfinic acid and p-toluenesulfinic acid.

[0073] Examples of the organic phosphinic acid include diethylphosphinic acid, methylphenylphosphinic acid, and diphenylphosphinic acid.

[0074] Examples of the organic phosphonic acid include methylphosphonic acid, ethylphosphonic acid, tert-butylphosphonic acid, cyclohexylphosphonic acid, and phenylphosphonic acid.

[0075] Examples of the phenols include monohydric phenols such as phenol, cresol, 2,6-dimethylphenol, and naphthol;

[0076] Diphenols such as catechol, resorcinol, hydroquinone, 1,2-naphthalenediol, etc.

[0077] Gallic acid, 2,3,6-naphthalenetriol and other trivalent or higher phenols, etc.

[0078] Examples of the enol include 2-hydroxy-3-methyl-2-butene and 3-hydroxy-4-methyl-3-hexene.

[0079] Examples of the mercaptan include mercaptoethanol and mercaptopropanol.

[0080] Examples of the acid imide include carboxylic acid imides such as maleimide and succinimide, and sulfonic acid imides such as bis(trifluoromethanesulfonic acid)imide and bis(pentafluoroethanesulfonic acid)imide.

[0081] Examples of the oxime include aldoximes such as benzaldehyde oxime and salicylaldehyde oxime, and ketoximes such as diethylketoxime, methylethylketoxime and cyclohexanone oxime.

[0082] Examples of the sulfonamide include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, and toluenesulfonamide.

[0083] [a] The organic acid is preferably a carboxylic acid, more preferably a monocarboxylic acid, and still more preferably methacrylic acid and benzoic acid.

[0084] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, and salicylic acid ester.

[0085] Examples of the β-diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione.

[0086] Examples of the β-keto acid ester include acetoacetate, α-alkyl-substituted acetoacetate, β-ketovalerate, benzoyl acetate, and 1,3-acetone dicarboxylate.

[0087] Examples of the amine compound include diethanolamine and triethanolamine.

[0088] The [A] compound is preferably a metal compound comprising a metal atom and [a] an organic acid, more preferably a metal compound comprising a metal atom of Group 4, Group 5 or Group 14 and a carboxylic acid, and still more preferably a metal compound comprising titanium, zirconium, hafnium, tantalum, tungsten or tin and methacrylic acid or benzoic acid.

[0089] The compound [A] may contain one or two or more of the above metal compounds.

[0090] The [A] compound may contain one or two or more [a] organic acids.

[0091] The lower limit of the content of the compound [A] in all the components contained in the composition is preferably 2 mass %, more preferably 4 mass %, and further preferably 6 mass %. The upper limit of the content is preferably 30 mass %, more preferably 20 mass %, and further preferably 15 mass %.

[0092] [[A] Method for synthesizing compound]

[0093] The [A] compound can be synthesized, for example, by a method of performing a hydrolysis-condensation reaction using the [b] metal-containing compound, a method of performing a ligand exchange reaction using the [b] metal-containing compound, etc. Here, the so-called "hydrolysis-condensation reaction" refers to a reaction in which the hydrolyzable group of the [b] metal-containing compound is hydrolyzed and converted into -OH, and the two obtained -OH groups are dehydrated and condensed to form -O-.

[0094] ([b] Metal-containing compounds)

[0095] [b] The metal-containing compound is a metal compound (b1) having a hydrolyzable group, a hydrolyzate of a metal compound (b1) having a hydrolyzable group, a hydrolysis-condensation product of a metal compound (b1) having a hydrolyzable group, or a combination thereof. The metal compound (b1) may be used alone or in combination of two or more.

[0096] Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group.

[0097] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0098] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group.

[0099] Examples of the acyloxy group include an acetyloxy group, an ethylcarbonyloxy group, a propionyloxy group, a butyryloxy group, a tert-butyryloxy group, a tert-amylcarbonyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.

[0100] The hydrolyzable group is preferably an alkoxy group and an acyloxy group, and more preferably an isopropoxy group and an acetoxy group.

[0101] In the case where the metal-containing compound [b] is a hydrolysis condensate of a metal compound (b1), as long as the effect of the present invention is not impaired, the hydrolysis condensate of the metal compound (b1) may also be a hydrolysis condensate of a metal compound (b1) having a hydrolyzable group and a compound containing a metalloid atom. That is, the hydrolysis condensate of the metal compound (b1) may also contain a metalloid atom within the range that does not impair the effect of the present invention. As the metalloid atom, for example, silicon, boron, germanium, antimony, tellurium, etc. may be cited. The content of the metalloid atom in the hydrolysis condensate of the metal compound (b1) is generally less than 50 atomic % relative to the total of the metal atoms and metalloid atoms in the hydrolysis condensate. As the upper limit of the content of the metalloid atom, it is preferably 30 atomic %, more preferably 10 atomic % relative to the total of the metal atoms and metalloid atoms in the hydrolysis condensate.

[0102] Examples of the metal compound (b1) include compounds represented by the following formula (α) (hereinafter also referred to as “[m] compounds”).

[0103] [Chemistry 5]

[0104] L a MY b (α)

[0105] In the formula (α), M is a metal atom. L is a ligand. a is an integer of 0 to 6. When a is 2, multiple L groups may be the same or different. Y is a halogen atom, a hydrolyzable group selected from an alkoxy group and an acyloxy group. b is an integer of 2 to 6. Multiple Y groups may be the same or different. In addition, L is a ligand that is not compatible with Y.

[0106] Examples of the metal atom represented by M include the same metal atoms as exemplified as the metal atom constituting the metal compound contained in the compound [A].

[0107] Examples of the ligand represented by L include monodentate ligands and polydentate ligands.

[0108] Examples of the monodentate ligand include hydroxide ligands, carboxyl ligands, amide ligands, and ammonia.

[0109] Examples of the amide ligand include unsubstituted amide ligand (NH2), methylamide ligand (NHMe), dimethylamide ligand (NMe2), diethylamide ligand (NEt2), and dipropylamide ligand (NPr2).

[0110] Examples of the polydentate ligand include hydroxy acid esters, β-diketones, β-keto acid esters, β-dicarboxylates, hydrocarbons having a π bond, and diphosphines.

[0111] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, and salicylic acid ester.

[0112] Examples of the β-diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione.

[0113] Examples of the β-keto acid ester include acetoacetate, α-alkyl-substituted acetoacetate, β-ketovalerate, benzoyl acetate, and 1,3-acetone dicarboxylate.

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

[0115] Examples of the hydrocarbon having a π bond include:

[0116] Chain olefins such as ethylene and propylene;

[0117] Cyclic olefins such as cyclopentene, cyclohexene, and norbornene;

[0118] Chain dienes such as butadiene and isoprene;

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

[0120] Aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene, indene, etc.

[0121] Examples of the diphosphine include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and 1,1′-bis(diphenylphosphino)ferrocene.

[0122] Examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0123] Examples of the alkoxy group represented by Y include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0124] Examples of the acyloxy group represented by Y include an acetyloxy group, an ethylcarbonyloxy group, a butyryloxy group, a tert-butyryloxy group, a tert-amylcarbonyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.

[0125] Y is preferably an alkoxy group and an acyloxy group, and more preferably an isopropoxy group and an acetoxy group.

[0126] b is preferably 3 or 4, and more preferably 4.

[0127] [b] The metal-containing compound is preferably a metal alkoxide that has not undergone hydrolysis or hydrolytic condensation, and a metal acyl oxide that has not undergone hydrolysis or hydrolytic condensation.

[0128] Examples of the metal-containing compound [b] include zirconium tetra-n-butyl oxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, hafnium tetraethoxide, indium triisopropoxide, hafnium tetraisopropoxide, hafnium tetra-n-propoxide, hafnium tetra-n-butyl oxide, tantalum pentaethoxide, tungsten pentamethoxide, tungsten penta-n-butyl oxide, tungsten hexaethoxide, tungsten hexa-n-butyl oxide, ferric chloride, zinc diisopropoxide, zinc acetate dihydrate, tetrabutyl orthotitanate, titanium tetra-n-butyl oxide, titanium tetra-n-propoxide, bis(2,4-pentanedione)di-n-butyl oxide, titanium tri-n-butyl oxide stearate, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)tungsten dichloride, diacetyl[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium, [ethylenebis(diphenylphosphine)]cobalt dichloride, titanium butoxide oligomers , aminopropyl trimethoxytitanium, aminopropyl triethoxyzirconium, 2-(3,4-epoxycyclohexyl)ethyl trimethoxyzirconium, γ-glycidyloxypropyl trimethoxyzirconium, 3-isocyanopropyl trimethoxyzirconium, 3-isocyanopropyl triethoxyzirconium, triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-isopropoxy mono(acetylacetonate)titanium, triethoxy mono(acetylacetonate)zirconium, tri-n-propoxy mono(acetylacetonate)zirconium, tri-isopropoxy mono(acetylacetonate)zirconium, diisopropoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)zirconium, tri(3-methacryloxypropyl) methoxy zirconium, tri(3-acryloxypropyl) methoxy zirconium, tetraisopropoxy tin oxide, tetra-n-butoxy tin oxide, lanthanum oxide, yttrium oxide, etc.

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

[0130] When an organic acid is used in the synthesis of the compound [A], the lower limit of the amount of the organic acid used is preferably 1 mol, more preferably 2 mol, per mol of the metal-containing compound [b]. On the other hand, the upper limit of the amount of the organic acid used is preferably 6 mol, more preferably 5 mol, per mol of the metal-containing compound [b].

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

[0132] As a method for hydrolysis-condensation reaction using a metal-containing compound [b], for example, a method for hydrolysis-condensation reaction of a metal-containing compound [b] in a solvent containing water can be cited. In the case, other compounds with hydrolyzable groups can also be added as needed. As the lower limit of the amount of water used in the hydrolysis-condensation reaction, relative to the hydrolyzable groups possessed by the metal-containing compound [b], it is preferably 0.2 times mole, more preferably 1 times mole, and further preferably 3 times mole. As the upper limit of the amount of water, it is preferably 20 times mole, more preferably 15 times mole, and further preferably 10 times mole.

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

[0134] The solvent used in the synthesis reaction of the [A] compound (hereinafter also referred to as "[d] solvent") is not particularly limited, and for example, the same solvents as those exemplified as the [C] solvent described later can be used. Among these, alcohol solvents, ether solvents, ester solvents, and hydrocarbon solvents are preferred, alcohol solvents, ether solvents, and ester solvents are more preferred, monoalcohol solvents, polyol partial ether solvents, and polyol partial ether carboxylate solvents are further preferred, and ethanol, n-propanol, isopropanol, 1-butanol, propylene glycol monoethyl ether, and propylene glycol monoethyl ether acetate are particularly preferred.

[0135] When the solvent [d] is used in the synthesis reaction of the compound [A], the used solvent may be removed after the reaction, or may be used as the solvent [C] of the film-forming composition without being removed after the reaction.

[0136] [[B] Compound]

[0137] The [B] compound is a compound having an aromatic hydrocarbon ring structure (hereinafter also referred to as "aromatic hydrocarbon ring structure (I)") and a partial structure represented by the following formula (1) described later (hereinafter also referred to as "partial structure (II)").

[0138] [Aromatic hydrocarbon ring structure (I)]

[0139] The aromatic hydrocarbon ring structure (I) is an aromatic hydrocarbon ring structure having a carbon number of 6 or more. In the present specification, the "carbon number of the aromatic hydrocarbon ring structure (I)" refers to the number of carbon atoms constituting the ring structure of the aromatic hydrocarbon ring structure (I). The "carbon number of the aromatic hydrocarbon ring structure (I)" does not include the number of carbon atoms constituting the partial structure (II).

[0140] The lower limit of the number of carbon atoms in the aromatic hydrocarbon ring structure (I) is 6, preferably 8, and more preferably 10. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, 100 or 80. When the number of carbon atoms in the aromatic hydrocarbon ring structure (I) is 6 or more, a film having excellent etching resistance can be formed.

[0141] As the aromatic hydrocarbon ring structure (I), there can be listed: a monocyclic structure (i.e., a benzene structure), a structure including a condensed polycyclic structure, a structure including a ring aggregate structure, or a structure composed of these. In the present specification, the so-called "condensed polycyclic structure" refers to a ring structure in which a certain aromatic hydrocarbon ring in a polycyclic structure having two or more aromatic hydrocarbon rings is bonded to other aromatic hydrocarbon rings in a manner of sharing two carbon atoms. The so-called "ring aggregate structure" refers to a ring structure in which a certain aromatic hydrocarbon ring in a polycyclic structure having two or more aromatic hydrocarbon rings is not bonded to other aromatic hydrocarbon rings in a manner of sharing carbon atoms, but is bonded via a single bond.

[0142] The condensed polycyclic structure is not particularly limited as long as it has 6 or more carbon atoms, and examples thereof include a naphthalene structure, anthracene structure, phenanthrene structure, pyrene structure, fluorene structure, perylene structure, coronene structure, trinaphthylene structure, heptaphene structure, heptacene structure, pyranthrene structure, ovalene structure, and hexabenzocoronene structure.

[0143] The ring aggregate structure is not particularly limited as long as it has 6 or more carbon atoms, and examples thereof include a biphenyl structure, a terphenyl structure, a tetraphenylbenzene structure, a pentaphenylbenzene structure, and a hexaphenylbenzene structure.

[0144] The aromatic hydrocarbon ring structure (I) is preferably a structure including a condensed polycyclic structure. When the aromatic hydrocarbon ring structure (I) is a structure including a condensed polycyclic structure, the etching resistance of the film formed from the composition can be further improved.

[0145] [Partial structure (II)]

[0146] The partial structure (II) is a partial structure represented by the following formula (1).

[0147] [Chemistry 6]

[0148]

[0149] In the formula (1), X is a group represented by the following formula (i), formula (ii), formula (iii) or formula (iv) (hereinafter also referred to as "group (X)"). * is a bonding site to two adjacent carbon atoms constituting the aromatic hydrocarbon ring structure (aromatic hydrocarbon ring structure (I)).

[0150] In the compound [B], the partial structure (II) is bonded to the aromatic hydrocarbon ring structure (I). More specifically, the partial structure (II) is bonded to two adjacent carbon atoms constituting the aromatic hydrocarbon ring structure (I).

[0151] The lower limit of the number of partial structures (II) in the compound [B] is 1, preferably 2. The upper limit of the number of partial structures (II) is not particularly limited, but is preferably 10, more preferably 6. When the compound [B] has two or more partial structures (II), X in the formula (1) may be the same or different.

[0152] (Base(X))

[0153] The group (X) is a group represented by the following formula (i), formula (ii), formula (iii) or formula (iv) (hereinafter also referred to as "group (Xi) to group (X-iv)").

[0154] [Chemistry 7]

[0155]

[0156] In the formula (i), R 1 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 2 It is a monovalent organic group having 1 to 20 carbon atoms.

[0157] In the formula (ii), R 3 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 4 It is a monovalent organic group having 1 to 20 carbon atoms.

[0158] In the formula (iii), R 5 It is a monovalent organic group having 1 to 20 carbon atoms.

[0159] In the formula (iv), R 6 It is a monovalent organic group having 1 to 20 carbon atoms.

[0160] In the present specification, the "organic group" refers to a group containing at least one carbon atom.

[0161] As R 1, R 2 , R 3 , R 4 , R 5 and R 6 The monovalent organic group having 1 to 20 carbon atoms represented may include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group having a divalent heteroatom-containing group between carbon atoms of the hydrocarbon group (hereinafter, also referred to as "group (α)"), a group in which a part or all of the hydrogen atoms possessed by the hydrocarbon group are substituted with a monovalent heteroatom-containing group (hereinafter, also referred to as "group (β)"), a group in which a part or all of the hydrogen atoms possessed by the group (α) are substituted with a monovalent heteroatom-containing group (hereinafter, also referred to as "group (γ)"), and the like.

[0162] In the present specification, the "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The "hydrocarbon group" includes saturated hydrocarbon groups and unsaturated hydrocarbon groups. The so-called "chain hydrocarbon group" refers to a hydrocarbon group that does not contain a ring structure but only contains a chain structure, including both straight-chain hydrocarbon groups and branched-chain hydrocarbon groups. The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains an alicyclic structure and does not contain an aromatic ring structure as a ring structure, including both a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic hydrocarbon group (wherein it is not necessary to contain only an alicyclic structure, and a part of it may also contain a chain structure). The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure (wherein it is not necessary to contain only an aromatic ring structure, and a part of it may also contain an alicyclic structure or a chain structure).

[0163] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and combinations thereof.

[0164] Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl; alkenyl groups such as vinyl, propenyl and butenyl; and alkynyl groups such as ethynyl, propynyl and butynyl.

[0165] Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopentyl and cyclohexyl; cycloalkenyl groups such as cyclopropenyl, cyclopentenyl and cyclohexenyl; bridged ring saturated hydrocarbon groups such as norbornyl, adamantyl and tricyclodecanyl; and bridged ring unsaturated hydrocarbon groups such as norbornyl and tricyclodecanyl.

[0166] Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, tolyl, naphthyl, anthracenyl, and pyrenyl.

[0167] Examples of the hetero atom constituting the divalent or monovalent hetero atom-containing group include oxygen, nitrogen, sulfur, phosphorus, silicon, and halogen atoms. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms.

[0168] Examples of the divalent heteroatom-containing group include -CO-, -CS-, -NH-, -O-, -S-, and groups obtained by combining these.

[0169] Examples of the monovalent heteroatom-containing group include a hydroxyl group, a sulfonyl group, a cyano group, a nitro group, and a halogen atom.

[0170] The compound [B] preferably has at least one group selected from the group consisting of a group represented by the following formula (2-1) and a group represented by the following formula (2-2).

[0171] [Chemistry 8]

[0172]

[0173] (In the above formula (2-1) and formula (2-2), R 7 are each independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms or a single bond; * is a bond to a carbon atom in the compound [B])

[0174] In the above formula (2-1) and formula (2-2), R 7 The divalent hydrocarbon group having 1 to 20 carbon atoms represented by can be suitably selected from the above R 1 A group formed by removing one hydrogen atom from a monovalent hydrocarbon group having 1 to 20 carbon atoms. 7 The divalent hydrocarbon group having 1 to 20 carbon atoms represented is preferably a divalent chain hydrocarbon group having 1 to 10 carbon atoms, more preferably a divalent chain saturated hydrocarbon group having 1 to 5 carbon atoms, and further preferably a methanediyl group.

[0175] [B] In addition to the aromatic hydrocarbon ring structure (I) and the partial structure (II), the compound may also contain an aromatic heterocyclic structure such as a furan structure, a pyrrole structure, a thiophene structure, a phosphole structure, a pyrazole structure, an oxazole structure, an isoxazole structure, a thiazole structure, an imidazole structure, a pyridine structure, a pyrazine structure, a pyrimidine structure, a pyridazine structure, a triazine structure, a quinoline structure, an isoquinoline structure, a quinoxaline structure, a quinazoline structure, a cinnoline structure, a benzofuran structure, an isobenzofuran structure, an indole structure, an isoindole structure, a benzothiophene structure, a benzimidazole structure, an indazole structure, a benzoxazole structure, a benzisoxazole structure, a benzothiazole structure, and an acridine structure.

[0176] Examples of the compound [B] include compounds represented by the following formulae (1-1) to (1-20) (hereinafter also referred to as “compounds (1-1) to (1-20)”).

[0177] [Chemistry 9]

[0178]

[0179] [Chemistry 10]

[0180]

[0181] [Chemistry 11]

[0182]

[0183] [Chemistry 12]

[0184]

[0185] As the [B] compound, compounds (1-1) to (1-13) are preferred.

[0186] The [B] compound may have other substituents other than the aromatic hydrocarbon ring structure (I) and the partial structure (II), or may not have other substituents. The [B] compound is preferably a compound without other substituents. When the [B] compound has no other substituents, the carbon atom content of the [B] compound is higher than when it has other substituents, so the etching resistance of the film formed by the composition can be further improved.

[0187] Examples of the other substituent include a halogen atom, a hydroxyl group, a nitro group, and a monovalent organic group having 1 to 20 carbon atoms. Examples of the monovalent organic group having 1 to 20 carbon atoms as the other substituent include the same as R in the formula (i) to (iv). 1 ~R 6 The same groups as those exemplified as the monovalent organic group having 1 to 20 carbon atoms represented by .

[0188] When the compound [B] has the above-mentioned other substituent, the site to which the other substituent is bonded is not particularly limited, and the other substituent may be bonded to the above-mentioned aromatic hydrocarbon ring structure (I) or to the above-mentioned partial structure (II).

[0189] The compound [B] preferably has no oxygen atom, thereby improving the storage stability of the composition.

[0190] The composition is suitable for embedding a pattern in a substrate having a pattern.

[0191] The lower limit of the molecular weight of the compound [B] is preferably 300, more preferably 400, further preferably 500, and particularly preferably 600. The upper limit of the molecular weight is preferably 5,000, more preferably 4,000, further preferably 3,500, and particularly preferably 3,000.

[0192] The lower limit of the content of the aromatic compound is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, further preferably 0.1 parts by mass, and particularly preferably 0.2 parts by mass relative to 10 parts by mass of the metal compound. The upper limit of the content is preferably 50 parts by mass, more preferably 20 parts by mass, further preferably 10 parts by mass, and particularly preferably 3 parts by mass.

[0193] [[B] Method for synthesizing compound]

[0194] The compound [B] can be synthesized by a conventional method according to, for example, the following synthesis scheme.

[0195] [Chemistry 13]

[0196]

[0197] (In the process, * is the bond to the fluorene ring; R 7 has the same meaning as the above formula (2-1) and formula (2-2); Q is a halogen atom; R B and R of the formula (ii) 4 have the same meaning)

[0198] A substituted product of fluorene is prepared as a starting material and cyclized in the presence of a catalyst or the like, thereby obtaining an intermediate represented by the formula (1-a1) or the formula (1-b1). By reacting the intermediate represented by the formula (1-a1) with a halogenated acetylene derivative providing a partial structure (II), the group represented by the formula (2-1) can be introduced. Thus, the target compound represented by the formula (1-a2) can be synthesized. By subjecting the intermediate represented by the formula (1-b1) to a cyclization reaction in the presence of a catalyst or the like, the intermediate represented by the formula (1-b2) can be obtained. Subsequently, by reacting the intermediate represented by the formula (1-b2) with an aldehyde providing a partial structure (II), the target compound represented by the formula (1-b3) can be synthesized. It is also possible to synthesize a compound introduced with the partial structure (II) by reacting the intermediate represented by the formula (1-b1) directly with an aldehyde without passing through the intermediate represented by the formula (1-b2). Furthermore, the intermediate represented by the formula (1-a1) may be reacted with an aldehyde providing a partial structure (II), or the intermediate represented by the formula (1-b1) or (1-b2) may be reacted with a halogenated acetylene derivative providing a partial structure (II). Other structures may also be synthesized by appropriately selecting the structure of the starting material or halogenated acetylene derivative, aldehyde, etc.

[0199] [[C]solvent]

[0200] The solvent [C] is not particularly limited as long as it can dissolve or disperse at least the compound [A], the compound [B] and other optional components, etc. The composition may contain one or more solvents [C].

[0201] [C] The solvent may be an organic solvent, for example, an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent, a nitrogen-containing solvent, etc.

[0202] Examples of the alcohol solvent include monoalcohol solvents such as methanol, ethanol, n-propanol, isopropanol, and 1-butanol; and polyol solvents such as ethylene glycol, 1,2-propylene glycol, triethylene glycol, and tripropylene glycol.

[0203] Examples of the ketone solvent include chain ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone; and cyclic ketone solvents such as cyclohexanone.

[0204] Examples of the ether solvent include chain ether solvents such as n-butyl ether; polyol ether solvents such as cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane; and polyol partial ether solvents such as propylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and tetraethylene glycol monomethyl ether.

[0205] Examples of the ester solvent include carbonate solvents such as diethyl carbonate; acetic acid monoester solvents such as methyl acetate, ethyl acetate, and butyl acetate; lactone solvents such as γ-butyrolactone; polyol partial ether carboxylic acid ester solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; lactic acid ester solvents such as methyl lactate and ethyl lactate, etc.

[0206] Examples of the nitrogen-containing solvent include chain nitrogen-containing solvents such as N,N-dimethylacetamide and the like, and cyclic nitrogen-containing solvents such as N-methylpyrrolidone and the like.

[0207] In addition, aromatic solvents such as toluene, xylene, and mesitylene may be mentioned.

[0208] The solvent [C] is preferably an ether solvent and / or an ester solvent, more preferably a polyol partial ether solvent and / or a polyol partial ether carboxylate solvent, and still more preferably propylene glycol monoethyl ether and / or propylene glycol monomethyl ether acetate.

[0209] The lower limit of the content of the solvent [C] in the total amount of the components in the composition (the total amount when there are multiple types) is more preferably 50% by mass, preferably 60% by mass, and more preferably 70% by mass. The upper limit of the content is preferably 99% by mass, more preferably 95% by mass, and more preferably 90% by mass. By setting the content of the solvent [C] in the above range, the composition can be easily prepared and the coating property can be improved.

[0210] [Other optional ingredients]

[0211] The composition may contain, for example, an acid generator, a polymer additive, a polymerization inhibitor, a surfactant, and the like as components other than the above components.

[0212] When the composition contains other arbitrary components, the content of the other arbitrary components in the composition can be appropriately determined according to the type or function of the other arbitrary components used.

[0213] The acid generator is a compound that generates an acid by irradiation with radiation and / or heating. The composition may contain one or more acid generators.

[0214] Examples of the acid generator include onium salt compounds and N-sulfonyloxyimide compounds.

[0215] The composition can further improve the coating property on the substrate or the organic base film or the continuity of the film by containing the polymer additive. The composition can contain one or more polymer additives.

[0216] Examples of the polymer additive include (poly)oxyalkylene polymer compounds, fluorine-containing polymer compounds, and non-fluorine polymer compounds.

[0217] Examples of the (poly)oxyalkylene polymer compound include polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene adducts; (poly)oxyalkyl ethers such as diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether, and oxyethylene oxypropylene adducts of higher alcohols having 12 to 14 carbon atoms; (poly)oxyalkylene (alkyl) aromatic ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonyl phenyl ether; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1-butyryl alcohol, and the like. Acetylenic ethers formed by addition polymerization of alkylene oxides to acetylene alcohols such as acetylene-3-ol; (poly)oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, and ethylene glycol distearate; (poly)oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly)oxyalkylene alkyl (aryl) ether sulfates such as polyoxypropylene methyl ether sodium sulfate and polyoxyethylene dodecylphenol ether sodium sulfate; (poly)oxyalkylene alkyl phosphates such as (poly)oxyethylene stearyl phosphate; (poly)oxyalkylene alkylamines such as polyoxyethylene laurylamine, etc.

[0218] As the fluorine-containing polymer compound, for example, the compounds described in Japanese Patent Laid-Open No. 2011-89090 can be cited. As the fluorine-containing polymer compound, for example, the compounds containing repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) can be cited.

[0219] Examples of the non-fluorine-based polymer compound include: linear or branched alkyl (meth)acrylates such as lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, isostearyl (meth)acrylate, and isononyl (meth)acrylate; alkoxyethyl (meth)acrylates such as methoxyethyl (meth)acrylate; alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate and 1,3-butanediol di(meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate, nonylphenoxypolyethylene glycol (having -(CH2CH2O) n- structure, n=1 to 17) (meth)acrylate or the like; a compound containing one or two or more repeating units derived from a (meth)acrylate monomer or the like; and the like.

[0220] The composition may contain a polymerization inhibitor to improve the storage stability of the composition. The composition may contain one or more polymerization inhibitors.

[0221] Examples of the polymerization inhibitor include hydroquinone compounds such as 4-methoxyphenol and 2,5-di-tert-butylhydroquinone; and nitroso compounds such as N-nitrosophenylhydroxylamine and its aluminum salt.

[0222] The composition can further improve the coating property on the substrate or the organic base film or the continuity of the film by containing a surfactant. The composition can contain one or more surfactants.

[0223] Examples of commercially available surfactants include: "Newcol 2320", "Newcol 714-F", "Newcol 723", "Newcol 2307", "Newcol 2303" (all from Nippon Emulsifier Co., Ltd.); "Pionin D-1107-S", "Pionin D-1007", "Pionin D-1106-DIR", "Newkalge ... n)TG310", "Newkalgen TG310", "Pionin D-6105-W", "Pionin D-6112", "Pionin D-6512" (all of which are from Takemoto Oil & Fats Co., Ltd.); "Surfynol 420", "Surfynol 440", "Surfynol 465", "Surfynol 2502" (all of which are from Japan Air Products Co., Ltd.) Air Products (stock)); "Megafac F171", "Megafac F172", "Megafac F173", "Megafac F176", "Megafac F177", "Megafac F141", "Megafac F142", "Megafac F143", "Megafac F144", "Megafac R30", "Megafac F437", "Megafac F475", "Megafac Megafac F479", "Megafac F482", "Megafac F562", "Megafac F563", "Megafac F780", "Megafac R-40", "Megafac DS-21", "Megafac RS-56", "Megafac RS-90", "Megafac RS-72-K" (all DIC (stock)); "Fluorad FC430", "Fluorad FC431" (all Sumitomo 3M (stock));"Asahi Guard AG710", "Surflon S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106" (Asahi Glass (AGC) (stock)); "FTX-218", "NBX-15" (NEOS (stock)), etc. ;

[0224] [Method for preparing film-forming composition]

[0225] The film-forming composition can be prepared by mixing the [A] compound, the [B] compound, the [C] solvent, and any necessary components in a predetermined ratio, and filtering the obtained mixture preferably using a membrane filter having a pore size of 0.5 μm or less. In the composition, the [A] compound is preferably dissolved in the [C] solvent.

[0226] [Coating process]

[0227] In the coating step, the film-forming composition is coated on the substrate. The coating method of the film-forming composition is not particularly limited, and can be implemented by appropriate methods such as spin coating, cast coating, and roll coating. Thus, a coating film can be formed, and a film (metal hard mask) serving as a resist base film can be formed by causing volatilization of the [C] solvent.

[0228] As the substrate, for example, metal or metal-like substrates such as silicon substrates, aluminum substrates, nickel substrates, chromium substrates, molybdenum substrates, tungsten substrates, copper substrates, tantalum substrates, and titanium substrates can be cited, among which silicon substrates are preferred. The substrate may also be a substrate formed with a silicon nitride film, an aluminum oxide film, a silicon dioxide film, a tantalum nitride film, a titanium nitride film, and the like.

[0229] The substrate may have a pattern. Since the film-forming composition has excellent embedding properties, even if the substrate has a pattern, a good film can be formed while embedding the gap between the patterns. As the shape of the pattern, for example, groove patterns, line and space patterns, hole patterns, column patterns, etc. can be cited. As groove patterns and line and space patterns, for example, patterns of recesses with a width of 5nm or more and 100nm or less and a depth of 5nm or more and 500nm or less can be cited. As hole patterns, for example, patterns of holes with a diameter of 5nm or more and 100nm or less and a depth of 5nm or more and 500nm or less can be cited. As column patterns, for example, if it is a square column, a pattern of a column with a side of 5nm or more and 100nm or less and a height of 5nm or more and 500nm or less can be cited. If it is a cylindrical column, a pattern of a column with a diameter of 5nm or more and 100nm or less and a height of 5nm or more and 500nm or less can be cited.

[0230] The lower limit of the average thickness of the formed resist base film is preferably 3 nm, more preferably 5 nm, and further preferably 10 nm. The upper limit of the average thickness is preferably 500 nm, more preferably 200 nm, and further preferably 100 nm. In addition, the determination method of the average thickness is based on the description of the embodiments.

[0231] The method for manufacturing the semiconductor substrate preferably further includes a step of heating the coating film formed by the coating step (hereinafter also referred to as a "heating step"). The heating of the coating film can promote the formation of the resist base film. More specifically, the heating of the coating film can promote the volatilization of the [C] solvent, etc.

[0232] The heating of the coating film can usually be carried out in the atmosphere or in a nitrogen environment. The lower limit of the temperature during heating is preferably 400°C, more preferably 420°C, and further preferably 450°C. The upper limit of the temperature is preferably 600°C, more preferably 550°C, and further preferably 500°C. The lower limit of the time during heating 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.

[0233] [Organic base film forming step]

[0234] In this process, before the resist pattern forming process, an organic base film is formed directly or indirectly on the substrate having the resist base film formed in the coating process.

[0235] Regarding the case where the organic base film is indirectly formed on the substrate having the resist base film, for example, there is the case where the organic base film is formed on the surface modification film of the resist base film formed on the resist base film.

[0236] The organic base film can be formed by applying an organic base film-forming composition, etc. As a method for forming an organic base film by applying an organic base film-forming composition, for example, a method of directly or indirectly applying an organic base film-forming composition on a substrate having the resist base film, and heating or exposing the formed coating film to harden it, etc. can be cited. As the organic base film-forming composition, for example, "HM8006" of JSR (stock) can be used. The conditions for heating or exposure can be appropriately determined according to the type of organic base film-forming composition used, etc.

[0237] [Silicon-Containing Film Formation Step]

[0238] In this step, before the resist pattern forming step, a silicon-containing film is formed directly or indirectly on the substrate having the resist underlying film formed in the coating step.

[0239] As a case where the silicon-containing film is indirectly formed on the substrate having the resist underlayer film, for example, there is a case where a surface modification film of the resist underlayer film or the organic underlayer film is formed on the resist underlayer film.

[0240] The silicon-containing film can be formed by applying a silicon-containing film-forming composition, chemical vapor deposition (Chemical Vapor Deposition, CVD) method, atomic layer deposition (Atomic Layer Deposition, ALD), etc. As a method for forming a silicon-containing film by applying a silicon-containing film-forming composition, for example, a method of directly or indirectly applying the silicon-containing film-forming composition on the resist base film, exposing and / or heating the formed coated film to harden it, etc. can be cited. As a commercial product of the silicon-containing film-forming composition, for example, "NFC SOG01", "NFC SOG04", "NFC SOG080" (all manufactured by JSR (stock) Co., Ltd.) can be used. Silicon oxide film, silicon nitride film, silicon oxynitride film, amorphous silicon film can be formed by chemical vapor deposition (CVD) method or atomic layer deposition (ALD).

[0241] [Resist pattern forming step]

[0242] In this process, a resist pattern is formed directly or indirectly on the resist base film. As a method for performing this process, for example, a method using a resist composition, a method using a nanoimprint method, a method using a self-organized composition, etc. As a case where a resist pattern is indirectly formed on the resist base film, for example, when the manufacturing method of the semiconductor substrate includes the silicon-containing film forming step, a case where a resist pattern is formed on the silicon-containing film, etc. can be cited.

[0243] Specifically, the method of using the resist composition comprises applying the resist composition so that the formed resist film has a predetermined thickness, and then performing pre-baking to volatilize the solvent in the coated film, thereby forming the resist film.

[0244] Examples of the resist composition include positive or negative chemically amplified resist compositions containing a radiation-sensitive acid generator, positive resist compositions containing an alkali-soluble resin and a quinonediazide-based photosensitizer, negative resist compositions containing an alkali-soluble resin and a crosslinking agent, and metal-containing resist compositions containing metals such as tin, zirconium, and hafnium. In addition, in this step, a commercially available resist composition may be used as it is.

[0245] Next, the formed resist film is exposed by selective radiation irradiation. As the radiation used in exposure, it can be appropriately selected according to the type of the sensitive radiation acid generator used in the resist composition, for example, electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, gamma rays, etc., electron beams, molecular beams, ion beams, etc. are listed. Among these, far ultraviolet light is preferably used, more preferably KrF excimer laser light (248nm), ArF excimer laser light (193nm), F2 excimer laser light (wavelength 157nm), Kr2 excimer laser light (wavelength 147nm), ArKr excimer laser light (wavelength 134nm) or extreme ultraviolet light (wavelength 13.5nm, hereinafter also referred to as "EUV (ExtremeUltraviolet)"), and further preferably KrF excimer laser light, ArF excimer laser light or EUV.

[0246] After the exposure, post-baking may be performed to improve resolution, pattern profile, developability, etc. The temperature and time of the post-baking may be appropriately determined according to the type of resist composition used, etc.

[0247] Next, the exposed resist film is developed with a developer to form a resist pattern. The development may be alkali development or organic solvent development. As the developer, in the case of alkali development, alkaline aqueous solutions such as ammonia, triethanolamine, tetramethyl ammonium hydroxide (TMAH), and tetraethyl ammonium hydroxide may be cited. To these alkaline aqueous solutions, appropriate amounts of water-soluble organic solvents such as alcohols such as methanol and ethanol, surfactants, etc. may also be added. In addition, in the case of organic solvent development, as the developer, for example, various organic solvents exemplified as the [C] solvent of the composition described above may be cited.

[0248] After development with the developer, washing and drying are performed, thereby forming a predetermined resist pattern.

[0249] [Etching process]

[0250] In this process, a pattern is formed on the resist base film by etching using the resist pattern as a mask. The number of etchings may be once or multiple times, that is, etching is performed sequentially using the pattern obtained by etching as a mask. Multiple times are preferred from the perspective of obtaining a pattern with a better shape. When multiple etchings are performed, etching is performed sequentially in the order of the silicon-containing film, the organic base film, the resist base film and the substrate. As etching methods, dry etching, wet etching and the like can be cited. Among these, dry etching is preferred from the perspective of making the shape of the pattern of the substrate better. For example, gas plasma such as oxygen plasma can be used in the dry etching. A semiconductor substrate with a predetermined pattern can be obtained by the etching.

[0251] As dry etching, for example, a known dry etching device can be used. As the etching gas used in dry etching, it can be appropriately selected according to the mask pattern, the elemental composition of the film to be etched, etc., for example: 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, BCl3; inert gases such as He, N2, Ar, etc. These gases can also be used in combination. When etching the substrate using the pattern of the resist underlying film as a mask, a fluorine-based gas can usually be used.

[0252] 《Film-forming composition》

[0253] The film-forming composition contains [A] a compound, [B] a compound, and [C] a solvent. As such a film-forming composition, the film-forming composition used in the method for producing a semiconductor substrate can be preferably used.

[0254] Example

[0255] The following examples are intended to be representative examples of the present invention and are not intended to restrict the scope of the present invention.

[0256] The concentration of components other than the solvent in the mixture containing the [A] compound, the average thickness of the film, and the weight average molecular weight (Mw) in the present example were measured by the following method.

[0257] [Concentration of components other than the solvent in a mixture containing the [A] compound]

[0258] The mass of the residue obtained after calcining 0.5 g of the mixture containing the compound [A] at 250°C for 30 minutes was measured, and the concentration (mass %) of the components other than the solvent in the mixture containing the compound [A] was calculated by dividing the mass of the residue by the mass of the mixture containing the compound [A].

[0259] [Average thickness of resist base film]

[0260] The average thickness of the resist base film was determined by measuring the film thickness at nine random points with an interval of 5 cm including the center of the resist base film formed on a 12-inch silicon wafer (substrate) using a spectroscopic ellipsometer ("M2000D" produced by JA Woollanm), and calculating the average value of these film thicknesses.

[0261] [Weight average molecular weight (Mw)]

[0262] Unless otherwise specified, the Mw of the polymer is measured by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as the standard using GPC columns (2 "G2000HXL", 1 "G3000HXL", and 1 "G4000HXL" manufactured by Tosoh Co., Ltd.) under the analytical conditions of flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, and column temperature: 40°C.

[0263] <[A] Synthesis of compound>

[0264] The following shows the [m] compound, [x] compound, [d] solvent and [C] solvent used in the synthesis of the [A] compound. In the following synthesis examples, unless otherwise specified, "parts by mass" refers to the value when the mass of the [m] compound used is set to 100 parts by mass. In addition, "molar ratio" refers to the value when the amount of the [m] compound used is set to 1. The concentrations (mass %) of the components other than the solvent in the mixture containing the [A] compound are shown in Table 1.

[0265] As the [m] compound, the following compounds were used.

[0266] m-1: Tetra-n-propoxide zirconium (IV)

[0267] m-2: Tetra-n-butoxyzirconium (IV)

[0268] m-3: Tetra-n-propoxyhafnium(IV)

[0269] m-4: Tetraisopropoxide titanium (IV)

[0270] m-5: Tantalum pentaethoxide (V)

[0271] As the [x] compound, the following compounds were used.

[0272] x-1: Propionic acid

[0273] x-2: Butyric acid

[0274] x-3: Isobutyric acid

[0275] x-4: methacrylic acid

[0276] x-5: 2-ethylhexanoic acid

[0277] x-6: acetylacetone

[0278] x-7: diethanolamine

[0279] As [d] solvent, the following compounds were used.

[0280] d-1: n-propanol

[0281] d-2: Ethanol

[0282] d-3: 1-Butanol

[0283] d-4: Isopropyl alcohol

[0284] As [C] solvent, the following compounds were used.

[0285] C-1: Propylene glycol monomethyl ether acetate

[0286] C-2: Propylene glycol monoethyl ether

[0287] [Synthesis Example 1-1] ([A] Synthesis of Compound (A-1))

[0288] Compound (m-1) (molar ratio 1) and solvent (d-1) (40 parts by mass) were added to a reaction vessel under a nitrogen atmosphere. Compound (x-1) (molar ratio 5) was added dropwise to the reaction vessel at 50°C for 20 minutes while stirring. The reaction was then carried out at 80°C for 3 hours. After the reaction was completed, the reaction vessel was cooled to below 30°C. The precipitate obtained by cooling was separated by filtration, washed with n-hexane (100 parts by mass), and then vacuum dried to obtain compound (A-1).

[0289] [Synthesis Example 1-2] ([A] Synthesis of Compound (A-2))

[0290] Compound (m-1) (molar ratio 1) and solvent (d-1) (200 parts by mass) are added to a reaction vessel under a nitrogen atmosphere. Compound (x-2) (molar ratio 5) is added dropwise to the reaction vessel at 50°C for 20 minutes while stirring. Then, the reaction is carried out at 80°C for 3 hours. After the reaction is completed, the reaction vessel is cooled to below 30°C. After adding 900 parts by mass of solvent (C-1) to the cooled reaction solution, an evaporator is used to remove solvent (d-1), alcohol generated by the reaction, and remaining solvent (C-1) to obtain a mixture containing [A] compound (A-2). The concentration of components other than the solvent in the mixture containing [A] compound (A-2) is 14% by mass.

[0291] [Synthesis Examples 1-10, 1-14] (Synthesis of [A] Compound (A-10), [A] Compound (A-14))

[0292] [A] Compound (A-10) and [A] Compound (A-14) were obtained in the same manner as in 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.

[0293] [Synthesis Examples 1-3 to 1-9 and 1-11 to 1-13] (Synthesis of [A] Compounds (A-3) to (A-9) and [A] Compounds (A-11) to (A-13))

[0294] A mixture containing [A] compounds (A-3) to (A-9) and [A] compounds (A-11) to (A-13) was obtained in the same manner as in Synthesis Example 1-2 except that the [m] compound, [x] compound, [d] solvent, and [C] solvent were used in the types and amounts shown in Table 1 below.

[0295] [Synthesis Example 1-15] ([A] Synthesis of Compound (A-15))

[0296] Compound (m-4) (molar ratio 1) is added to the reaction container under a nitrogen environment. Compound (x-6) (molar ratio 2) is added dropwise to the reaction container at room temperature (25°C to 30°C) for 30 minutes while stirring. Then, the reaction is carried out at 60°C for 2 hours. After the reaction is completed, the reaction container is cooled to below 30°C. The cooled reaction solution is diluted with solvent (d-4) (900 parts by mass). In the reaction container, water (molar ratio 2) is added dropwise to the reaction container at room temperature (25°C to 30°C) for 10 minutes while stirring. Then, a hydrolysis condensation reaction is carried out at 60°C for 2 hours. After the hydrolysis condensation reaction is completed, the reaction container is cooled to below 30°C. After adding 1,000 parts by mass of the solvent (C-2) to the cooled reaction solution, water, isopropyl alcohol, alcohol generated by the reaction, water, and the remaining solvent (C-2) were removed using an evaporator to obtain a mixture containing the [A] compound (A-15). The concentration of components other than the solvent in the mixture containing the [A] compound (A-15) was 13% by mass.

[0297] [Synthesis Example 1-16] ([A] Synthesis of Compound (A-16))

[0298] A mixture containing the [A] compound (A-16) was obtained in the same manner as in Synthesis Example 1-15 except that the [m] compound, [x] compound, [d] solvent and [C] solvent were used in the types and amounts shown in Table 1 below.

[0299] [Table 1]

[0300]

[0301] <[B] Synthesis of compounds>

[0302] As the [B] compound, the compounds represented by the following formulae (B-1) to (B-13) (hereinafter also referred to as “compounds (B-1) to (B-13)”) were synthesized by the following procedure.

[0303] [Chemistry 14]

[0304]

[0305] [Chemistry 15]

[0306]

[0307] [Synthesis Example 1] (Synthesis of Compound (B-1))

[0308] 20.0 g of 2-acetylfluorene and 20.0 g of m-xylene were placed in a reaction vessel under a nitrogen atmosphere and dissolved at 110° C. Subsequently, 3.14 g of dodecyl benzenesulfonate was added, heated to 140° C. and reacted for 16 hours. After the reaction was completed, 80 g of xylene was added to the reaction solution for dilution, then cooled to 50° C., and put into 500 g of methanol for reprecipitation. After washing the obtained precipitate with toluene, the solid was recovered with filter paper and dried to obtain a compound (a-1) represented by the following formula (a-1).

[0309] [Chemistry 16]

[0310]

[0311] In a nitrogen environment, 10.0 g of the compound (a-1), 18.8 g of propargyl bromide and 50 g of toluene were added to the reaction vessel, and after stirring, 25.2 g of a 50% by mass sodium hydroxide aqueous solution and 1.7 g of tetrabutylammonium bromide were added, and the mixture was reacted at 92 ° C for 12 hours. After the reaction solution was cooled to 50 ° C, 25 g of tetrahydrofuran was added. After removing the aqueous phase, 50 g of a 1% by mass oxalic acid aqueous solution was added for liquid separation and extraction, and then the mixture was put into hexane for reprecipitation. The precipitate was recovered by filter paper and dried to obtain compound (B-1).

[0312] [Synthesis Example 2] (Synthesis of Compound (B-2))

[0313] The compound (B-2) was obtained in the same manner as in Synthesis Example 1 except that 18.8 g of propyne bromide was changed to 19.1 g of allyl bromide.

[0314] [Synthesis Example 3] (Synthesis of Compound (B-3))

[0315] The compound (B-3) was obtained in the same manner as in Synthesis Example 1 except that 18.8 g of propargyl bromide was changed to 9.9 g of 1-naphthaldehyde.

[0316] [Synthesis Example 4] (Synthesis of Compound (B-4))

[0317] The compound (B-4) was obtained in the same manner as in Synthesis Example 1 except that 18.8 g of propargyl bromide was changed to 14.6 g of 1-formylpyrene.

[0318] [Synthesis Example 5] (Synthesis of Compound (B-5))

[0319] 10.0 g of 2-cyanofluorene and 88.8 g of dichloromethane were added to a reaction container under a nitrogen atmosphere, cooled to 5° C., and 7.9 g of trifluoromethanesulfonic acid was added dropwise, and reacted at 20° C. to 25° C. for 24 hours. A large amount of sodium bicarbonate aqueous solution was added to the reaction solution for neutralization, and the precipitated solid was recovered with filter paper, washed with dichloromethane and dried to obtain a compound represented by the following formula (a-2).

[0320] [Chemistry 17]

[0321]

[0322] In a nitrogen environment, 5.0 g of the compound (a-2), 7.5 g of propargyl bromide, 12.6 g of a 50% sodium hydroxide aqueous solution, 0.8 g of tetrabutylammonium bromide and 25.7 g of toluene were added to a reaction vessel and reacted at 92 ° C for 12 hours. After the reaction solution was cooled to 50 ° C, 25 g of tetrahydrofuran was added for dilution. After removing the aqueous phase, 50 g of a 1% oxalic acid aqueous solution was added for liquid separation and extraction, and then put into hexane for reprecipitation. The precipitate was recovered by filter paper and dried to obtain the compound (B-5).

[0323] [Synthesis example 6]

[0324] 15.0 g of 2-acetyl-9-ethylcarbazole, 14.9 g of thionyl chloride and 2.8 g of ethanol were added to a reaction container under a nitrogen atmosphere, and reacted at 80° C. for 8 hours. 50 g of water and 50 g of dichloromethane were added to the obtained reaction solution for separation and extraction, and the obtained organic layer was concentrated and dried using an evaporator to obtain the compound (B-6).

[0325] [Synthesis Example 7] (Synthesis of Compound (B-7))

[0326] In a nitrogen environment, 10.0 g of the compound (a-1), 12.76 g of 4-(trimethylsilylethynyl)benzaldehyde and 50 g of tetrahydrofuran were added to a reaction vessel, and after stirring, 37.9 g of a 20% by mass sodium hydroxide aqueous solution and 1.7 g of tetrabutylammonium bromide were added, and the mixture was reacted at 35° C. for 3 hours. After the reaction solution was cooled to room temperature, 15 g of methyl isobutyl ketone was added. After removing the aqueous phase, liquid separation extraction with 50 g of a 1% by mass oxalic acid aqueous solution was repeated three times, and then the mixture was put into hexane for reprecipitation. The precipitate was recovered by filter paper and dried to obtain the compound (B-7).

[0327] [Synthesis Example 8] (Synthesis of Compound (B-8))

[0328] The compound (B-8) was obtained in the same manner as in Synthesis Example 7 except that 4-(trimethylsilylethynyl)benzaldehyde was changed to 3-(trimethylsilylethynyl)benzaldehyde.

[0329] [Synthesis Example 9] (Synthesis of Compound (B-9))

[0330] The compound (B-9) was obtained in the same manner as in Synthesis Example 1 except that 18.8 g of propargyl bromide was replaced with 6.5 g of 4-diethylaminobenzaldehyde.

[0331] [Synthesis Example 10] (Synthesis of Compound (B-10))

[0332] The compound (B-10) was obtained in the same manner as in Synthesis Example 1 except that 18.8 g of propargyl bromide was replaced with 12.3 g of N-ethylcarbazole-3-carboxaldehyde.

[0333] [Synthesis Example 11] (Synthesis of Compound (B-11))

[0334] The compound (B-11) was obtained in the same manner as in Synthesis Example 1 except that 18.8 g of propargyl bromide was changed to 11.4 g of 9-phenanthraldehyde.

[0335] [Synthesis Example 12] (Synthesis of Compound (B-12))

[0336] In a nitrogen atmosphere, 10.0 g of trimerene, 31.3 g of propargyl bromide and 50 g of toluene were added to a reaction vessel, stirred, and then 42.0 g of a 50% by mass sodium hydroxide aqueous solution and 2.8 g of tetrabutylammonium bromide were added, and the mixture was reacted at 92° C. for 12 hours. After the reaction solution was cooled to 50° C., the aqueous phase was removed, 50 g of a 1% by mass oxalic acid aqueous solution was added for liquid separation and extraction, and then the mixture was put into a methanol / water (70 / 30 (mass ratio)) mixed solvent for reprecipitation. The precipitate was recovered by filter paper and dried to obtain the compound (B-12).

[0337] [Synthesis Example 13] (Synthesis of Compound (B-13))

[0338] 20.0 g of 2-phenylethynylfluorene and 200 g of 1,4-dioxane were placed in a reaction vessel under a nitrogen atmosphere and dissolved at 50° C. Subsequently, 1.28 g of dicobalt octacarbonyl was added, heated to 110° C. and reacted for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and 600 g of methanol and 60.0 g of water were added to obtain a precipitate. The obtained precipitate was recovered using filter paper, washed with a large amount of methanol and dried to obtain a compound (a-3) represented by the following formula (a-3).

[0339] [Chemistry 18]

[0340]

[0341] In a nitrogen environment, 15.0 g of the compound (a-3) and 760 g of dichloromethane were placed in a reaction container, dissolved at room temperature, and then cooled to 0°C. Subsequently, a solution prepared by dissolving 60.9 g of anhydrous iron (III) chloride in 380 g of nitromethane was added dropwise. After reacting at 0°C for 2 hours, the mixture was heated to 20°C and reacted for another 2 hours. After the reaction was completed, 1,140 g of methanol was added to obtain a precipitate. The obtained precipitate was recovered using filter paper, washed with a large amount of methanol and tetrahydrofuran (hereinafter also referred to as "THF") and dried to obtain a compound (a-4) represented by the following formula (a-4).

[0342] [Chemistry 19]

[0343]

[0344] In a nitrogen environment, 14.0 g of the compound (a-4), 200 g of THF and 19.0 g of potassium tert-butoxide were added to the reaction vessel and stirred at 60 ° C for 30 minutes. Then, after cooling to -40 ° C, 20.1 g of bromopropyne was added dropwise and reacted at 0 ° C for 2 hours. After the reaction was completed, 500 g of 5% by mass oxalic acid aqueous solution and 100 g of methyl isobutyl ketone were added. After removing the aqueous phase, water was used for liquid separation extraction, and the organic layer was put into hexane for reprecipitation. The precipitate was recovered by filter paper and dried to obtain compound (B-13).

[0345] <Preparation of Composition>

[0346] [A] Compound, [B] Compound, [C] Solvent, and [F] Other optional components used in the preparation of the composition are shown below.

[0347] As the compound [A], the compounds (A-1) to (A-16) synthesized above were used.

[0348] As the [B] compound, the above-mentioned compounds (B-1) to (B-13) were used.

[0349] As the solvent [C], the following compounds were used in addition to (C-1) and (C-2) used in the synthesis of the compound [A].

[0350] C-3: Cyclohexanone

[0351] C-4: 2-Heptanone

[0352] C-5: Mesitylene

[0353] C-6: Butyl acetate

[0354] As [F] other optional components, the following compounds were used.

[0355] F-1: 4-Methoxyphenol

[0356] F-2: Surfactant ("NBX-15" of NEOS)

[0357] F-3: Surfactant (DIC's "F563")

[0358] F-4: A polymer (F-4) represented by the following formula (the numbers given to the repeating units represent the content ratio (mol %) of each repeating unit; the same shall apply hereinafter)

[0359] [Chemistry 20]

[0360]

[0361] F-5: A polymer represented by the following formula (F-5)

[0362] [Chemistry 21]

[0363]

[0364] F-6: A polymer represented by the following formula (F-6)

[0365] [Chemistry 22]

[0366]

[0367] (Synthesis of polymer (F-4))

[0368] 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 dimethyl 2,2'-azobis(2-methylpropionic acid) was added to prepare a monomer solution. 70 g of methyl isobutyl ketone was placed in a reaction container under a nitrogen atmosphere, heated to 80°C, and the monomer solution was added dropwise over 3 hours while stirring. The start of the addition was set as the start time of the polymerization reaction, and after 6 hours of polymerization reaction, the mixture was cooled to below 30°C. 300 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and methyl isobutyl ketone was removed by concentrating under reduced pressure to obtain a propylene glycol monomethyl ether acetate solution of polymer (F-4). The Mw of polymer (F-4) was 4,200.

[0369] (Synthesis of polymers (F-5) to (F-6))

[0370] Propylene glycol monomethyl ether acetate solutions of polymers (F-5) to (F-6) were obtained in the same manner as in the synthesis of polymer (F-4) except that monomers providing each structural unit represented by the above formula at each content ratio (mol %) were used. The Mw of polymer (F-5) was 4,000, and the Mw of polymer (F-6) was 4,300.

[0371] [Example 1-1] Preparation of composition (J-1)

[0372] As shown in Table 2 below, the mixture is mixed in such a manner that the amount of the [B] compound (B-1) is 0.3 parts by mass relative to 10 parts by mass of the [A] compound (A-1), and the amount of (C-3) as the [C] solvent is 90 parts by mass. The obtained solution is filtered using a polytetrafluoroethylene (PTFE) filter with a pore size of 0.2 μm to prepare a composition (J-1). The "-" in the [B] compound and [F] other arbitrary components in Table 2 below means that the [B] compound and [F] other arbitrary components are not used. The same applies below.

[0373] [Example 1-2] Preparation of composition (J-2)

[0374] As shown in Table 2 below, a mixture containing the [A] compound (A-2) and (C-1) as the [C] solvent were mixed in such a manner that the [B] compound (B-1) was 0.3 parts by mass and the [C] solvent was 90 parts by mass (including the [C] solvent contained in the mixture containing the [A] compound) relative to 10 parts by mass of the components other than the solvent in the [A] compound (A-2). The obtained solution was filtered using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.2 μm to prepare a composition (J-2).

[0375] [Examples 1-3 to 1-47] Preparation of compositions (J-3) to (J-47)

[0376] Compositions (J-3) to (J-47) were prepared in the same manner as in Example 1-1 or Example 1-2, except that the types and contents of the components were as shown in Table 2 below.

[0377] [Comparative Example 1-1] Preparation of composition (j-1)

[0378] A composition (j-1) was prepared in the same manner as in Example 1-2 except that the types and contents of the components were as shown in Table 2 below.

[0379] [Table 2]

[0380]

[0381]

[0382] <Evaluation>

[0383] In Examples 2-1 to 2-47 and Comparative Example 2-1, the compositions prepared in <Preparation of Composition> and the substrates with films obtained in <Film Formation> were evaluated for embedding properties and etching resistance by the following methods. The evaluation results are collectively shown in Table 3 below.

[0384] [Embeddability]

[0385] A spin coater ("LITHIUS Pro Z" of Tokyo Electron) was used to apply the composition to a substrate having a groove pattern with a depth of 50 nm and a width of 30 nm by a spin coating method. The rotation conditions of the spin coater were set to conditions such that a substrate with a film having an average thickness of 60 nm could be obtained. Next, the film was heated at 450°C for 60 seconds in an atmospheric environment and then cooled at 23°C for 60 seconds. The cross-sectional shape of the substrate was observed (200,000 times) using a scanning electron microscope ("S-4800" of Hitachi High-Technologies Corporation) and the embedding property was evaluated. Figure 1 This is an electron microscope photograph of a groove pattern when the composition of Example 1-1 is used to embed the groove pattern. Figure 2 This is an electron microscope photograph of the groove pattern when the composition of Comparative Example 1-1 is used to embed. Regarding embedding property, the case where the film is embedded to the bottom of the space pattern of the substrate (the case where there is no gap) is evaluated as "A" (good), and the case where the film is not embedded to the bottom of the space pattern (the case where there is a gap) is evaluated as "B" (bad).

[0386] <Film formation>

[0387] The prepared composition was applied onto a silicon wafer (substrate) by spin coating using a spin coater ("LITHIUS Pro Z" manufactured by Tokyo Electron). The substrate was then heated at 450°C for 60 seconds in an atmospheric environment and then cooled at 23°C for 600 seconds to obtain a substrate with a film having an average thickness of 60 nm.

[0388] [Etching resistance]

[0389] The film on the substrate with the film was treated using an etching device ("TACTRAS" of Tokyo Electron) under the conditions of CF4 / Ar = 110 / 440sccm, PRESS. = 30MT, HF RF (high frequency power for plasma generation) = 500W, LF RF (high frequency power for bias) = ​​3000W, DCS = -150V, RDC (gas sensor flow ratio) = 50%, and 30 seconds, and the etching rate (nm / minute) was calculated based on the average thickness of the film before and after the treatment. Then, the ratio relative to Comparative Example 2-1 was calculated based on the etching rate of Comparative Example 2-1, and set as the standard for etching resistance. Regarding etching resistance, the case where the ratio is less than 0.98 is evaluated as "A" (extremely good), the case where it is greater than 0.98 and less than 1.00 is evaluated as "B" (good), and the case where it is greater than 1.00 is evaluated as "C" (poor). In addition, "-" in the following Table 3 represents the evaluation criteria of etching resistance.

[0390] [Table 3]

[0391]

[0392] From the results in Table 3, it can be seen that the compositions of Examples and the resist underlayer films formed therefrom are superior in embedding properties and etching resistance as compared with Comparative Examples.

[0393] Industrial Applicability

[0394] By the method for manufacturing a semiconductor substrate of the present invention, a resist base film having excellent etching resistance and embedding property is formed, so a well-patterned semiconductor substrate can be obtained. By the film-forming composition of the present invention, a film having excellent etching resistance and embedding property can be formed. Therefore, these can be suitably used for the manufacture of semiconductor elements that are expected to be further miniaturized in the future.

Claims

1. A method for producing a semiconductor substrate, comprising the step of applying a film-forming composition on a substrate, The film-forming composition comprises: Metal compounds; An aromatic compound having an aromatic hydrocarbon ring structure and a partial structure represented by the following formula (1); as well as solvent, The aromatic hydrocarbon ring structure has 6 or more carbon atoms. [Chemistry 1] (In formula (1), X is a group represented by the following formula (i), formula (ii), formula (iii) or formula (iv). * represents the bonding site to two adjacent carbon atoms constituting the aromatic hydrocarbon ring structure.) [Chemistry 2] (In formula (i), R 1 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; R 2 It is a monovalent organic group having 1 to 20 carbon atoms. In formula (ii), R 3 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; R 4 It is a monovalent organic group having 1 to 20 carbon atoms. In formula (iii), R 5 It is a monovalent organic group having 1 to 20 carbon atoms. In formula (iv), R 6 It is a monovalent organic group having 1 to 20 carbon atoms. ) 2 . The method for manufacturing a semiconductor substrate according to claim 1 , wherein the metal atom contained in the metal compound belongs to Group 3 to Group 16 of the periodic table. 3 . The method for manufacturing a semiconductor substrate according to claim 1 , wherein the metal atom contained in the metal compound belongs to Group 4 of the periodic table. 4 . The method for manufacturing a semiconductor substrate according to claim 1 , wherein the aromatic compound has at least one group selected from the group consisting of a group represented by the following formula (2-1) and a group represented by the following formula (2-2). [Chemistry 3] (In the above formula (2-1) and formula (2-2), R 7 Each is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms or a single bond. * is a bond to a carbon atom in the aromatic compound. 5 . The method for manufacturing a semiconductor substrate according to claim 1 , wherein the aromatic compound does not have an oxygen atom. 6 . The method for producing a semiconductor substrate according to claim 1 , wherein the content of the aromatic compound is 0.1 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the metal compound. 7 . The method for manufacturing a semiconductor substrate according to claim 1 , wherein the substrate has a pattern.

8. A film-forming composition comprising: Metal compounds; An aromatic compound having an aromatic hydrocarbon ring structure and a partial structure represented by the following formula (1); as well as solvent, The aromatic hydrocarbon ring structure has 6 or more carbon atoms. [Chemistry 4] (In formula (1), X is a group represented by the following formula (i), formula (ii), formula (iii) or formula (iv). * represents the bonding site to two adjacent carbon atoms constituting the aromatic hydrocarbon ring structure.) [Chemistry 5] (In formula (i), R 1 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; R 2 It is a monovalent organic group having 1 to 20 carbon atoms. In formula (ii), R 3 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; R 4 It is a monovalent organic group having 1 to 20 carbon atoms. In formula (iii), R 5 It is a monovalent organic group having 1 to 20 carbon atoms. In formula (iv), R 6 It is a monovalent organic group having 1 to 20 carbon atoms. ) 9 . The film-forming composition according to claim 8 , which is used for embedding a pattern in a substrate having a pattern. 10 . The film-forming composition according to claim 8 , wherein the metal atom contained in the metal compound belongs to Group 3 to Group 16 of the periodic table. 11 . The film-forming composition according to claim 8 , wherein the metal atom contained in the metal compound belongs to Group 4 of the periodic table. 12 . The film-forming composition according to claim 8 , wherein the aromatic compound has at least one group selected from the group consisting of a group represented by the following formula (2-1) and a group represented by the following formula (2-2). [Chemistry 6] (In the above formula (2-1) and formula (2-2), R 7 Each is independently a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms or a single bond. * is a bond to a carbon atom in the aromatic compound. 13 . The film-forming composition according to claim 8 , wherein the aromatic compound has no oxygen atom. 14 . The film-forming composition according to claim 8 , wherein a content of the aromatic compound is 0.1 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the metal compound.

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