Removal method, solution composition, and method for manufacturing semiconductor device

Abstract

The present invention provides a removal method for removing a metal compound or a semimetal compound. This removal method includes a step for removing a metal compound or a semi-metal compound using a solution composition containing a solvent (B) containing a compound (B1) represented by general formula (b-1). [In formula (b-1), R1 represents an alkyl group having 1-10 carbon atoms.]

Description

Removal method, solvent composition, and method for manufacturing semiconductor device

[0001] The present invention relates to a removal method, a solvent composition, and a method for manufacturing a semiconductor device.

[0002] In the manufacture of semiconductor devices and liquid crystal devices, microfabrication using lithography with photoresist materials is performed. The lithography process involves coating a wafer with a photosensitive resin composition, transferring a designed pattern, and then etching the wafer to create a fine circuit pattern, similar to that of a semiconductor integrated circuit. This process involves coating, exposing, developing, etching, and peeling to create the desired fine circuit pattern. In particular, in the manufacture of semiconductor devices, the recent trend toward higher integration and higher speeds of LSIs has led to a demand for even finer pattern dimensions. To accommodate this trend, the wavelength of lithography light sources used in resist pattern formation has been shortened from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm) and extreme ultraviolet (EUV) light sources (13.5 nm), making them more susceptible to contamination. Therefore, residues and contaminants of a resist film, a resist auxiliary film (e.g., a Bottom Anti-Reflective Coating (BARC)), an SOC or an SOG, which are applied to a substrate in a coating process, can become a source of contamination in an exposure process and therefore need to be removed in advance. In this case, a solvent composition has been used in an EBR (edge ​​bead removing) process or a back-rinse process.

[0003] Recently, with the use of photoresists and their underlayer films utilizing short-wavelength light sources, the impact of the amount of photoresist and its underlayer film used on the manufacturing cost of integrated circuits has become significant. Therefore, there is a demand for reducing the amount of photoresist and its underlayer film used to reduce costs. To this end, a reducing resist consumption (RRC) process has been adopted in which a pre-wetting process is performed in which a solvent composition (thinner composition) is applied to the substrate surface to wet it before applying the photoresist and its underlayer film, thereby allowing the photoresist to be applied uniformly over the entire substrate surface even with only a small amount of photoresist and its underlayer film.

[0004] Furthermore, in the development step after exposure, a solvent composition has been used to dissolve the photoresist film and the underlayer film to form a high-resolution pattern.

[0005] JP 2011-253185 A JP 2022-100618 A

[0006] In recent years, the use of compositions containing metal compounds or semi-metal compounds as compositions for semiconductor manufacturing, such as resist compositions and resist auxiliary film compositions for forming resist films and resist auxiliary films, has been investigated in order to further reduce pattern dimensions (see, for example, Patent Documents 1 and 2). Even when a metal compound or semi-metal compound is used, it is desirable that EBR, back-rinse, RRC, development, rework, and other processes can be carried out effectively, but a solvent composition capable of achieving these processes to a high degree has not yet been developed.

[0007] Therefore, an object of the present invention is to provide a removal method and a solvent composition that can remove metal compounds or semi-metal compounds to a high degree even when a metal compound or semi-metal compound is used in a composition for semiconductor production, and a manufacturing method that can effectively manufacture semiconductor devices even when such a composition for semiconductor production is used.

[0008] The present invention provides, for example, the following removal method, solvent composition, and semiconductor device manufacturing method: [1] A method for removing a metal compound or a semi-metal compound, the removal method comprising a step of removing the metal compound or semi-metal compound using a solvent composition containing a solvent (B) that includes a compound (B1) represented by the following general formula (b-1): [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.] [2] R in the general formula (b-1) １is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, or a t-butyl group. [3] The removal method according to [1] or [2], wherein the solvent (B) contains a solvent (B2) other than the compound (B1). [4] The removal method according to [3], wherein the solvent (B) contains, as the solvent (B2), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate. [5] The removal method according to [3], wherein the solvent (B2) contains 100 mass% or less of the total amount (100 mass%) of the compound (B1). [6] The removal method according to [3], wherein the solvent (B2) contains 0.0001 mass% or more of the total amount (100 mass%) of the compound (B1). [7] The removal method according to any one of [1] to [6], wherein the metal compound or metalloid compound contains an element belonging to any one of Periods 3 to 7 of Groups 3 to 16 of the Periodic Table. [8] The removal method according to any one of [1] to [7], wherein the metal compound or metalloid compound contains one or more elements selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, zinc, germanium, tin, and tellurium. [9] The removal method according to any one of [1] to [8], wherein the ligand bonded to the metal compound or metalloid compound is a halogen ligand, a hydroxo ligand, a carboxy ligand, an alkoxy ligand, a carboxylate ligand, an alkyl ligand, or an amide ligand.

[10] A solvent composition used for removing a metal compound or metalloid compound, the solvent composition comprising a solvent (B) containing a compound (B1) represented by the following general formula (b-1): [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.]

[11] The solvent composition according to

[10] , wherein the solvent (B) contains a solvent (B2) other than the compound (B1).

[12] A method for producing a semiconductor device, comprising the step of applying a solvent composition containing a solvent (B) containing a compound (B1) represented by the following general formula (b-1) onto a substrate before applying a metal compound or a semi-metal compound onto the substrate: [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.]

[13] The method for producing a semiconductor device according to

[12] , wherein the solvent (B) contains, as a solvent (B2) other than the compound (B1), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate.

[14] A method for producing a semiconductor device, comprising the steps of applying a metal compound or a semimetallic compound onto a substrate, and then, after an exposure step, applying the solvent composition according to

[10] or

[11] onto the substrate.

[15] A method for producing a semiconductor device, comprising the steps of forming a film of a metal compound or a semimetallic compound on a substrate, and removing the film formed of the metal compound or semimetallic compound using the solvent composition according to

[10] or

[11] .

[0009] According to the present invention, it is possible to provide a removal method and a solvent composition that can remove metal compounds or semi-metal compounds to a high degree even when a metal compound or semi-metal compound is used in a composition for semiconductor production, and a manufacturing method that can effectively manufacture semiconductor devices even when such a composition for semiconductor production is used.

[0010] Hereinafter, an embodiment of the present invention will be described in detail, but the present invention is not limited to this embodiment. In this specification, "A to B" (A and B are numerical values) means "greater than or equal to A and less than or equal to B."

[0011] 1. Solvent Composition The solvent composition of the present embodiment is a solvent composition used to remove a metal compound or a semi-metal compound (hereinafter also referred to as "compound (A)"), and contains a solvent (B) that includes a compound (B1) represented by the following general formula (b-1): [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

[0012] In this embodiment, since the compound (B1) has high solubility, the solvent composition containing the solvent (B) containing the compound (B1) also has high solubility. Metal compounds or semimetallic compounds tend to be poorly soluble in solvents, but the solvent composition of this embodiment has high solubility, so it can effectively dissolve the metal compounds or semimetallic compounds. Therefore, the metal compounds or semimetallic compounds can be removed to a high degree. Therefore, for example, residues and contaminants of a resist film or a resist auxiliary film containing a metal compound or semimetallic compound can be appropriately removed, and EBR processes, back-rinse processes, development processes, rework processes, etc. can be effectively performed.

[0013] The configuration of this embodiment will be further described below. <Solvent (B)> The solvent composition of this embodiment contains a solvent (B) containing a compound (B1) represented by general formula (b-1). The compound (B1) may be used alone or in combination of two or more types.

[0014] In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms. The alkyl group may be a linear alkyl group or a branched alkyl group. １ Examples of the alkyl group that can be selected as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group, an i-pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group.

[0015] Among these, in this embodiment, R in the general formula (b-1) １ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, or an i-pentyl group. １ is more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, or a t-butyl group. １ is more preferably a methyl group or an ethyl group. １is even more preferably a methyl group.

[0016] The solvent composition of this embodiment may contain a solvent (B2) other than the compound (B1) as component (B). Examples of the solvent (B2) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, and diacetone alcohol; alcohols such as 4-methyl-2-pentanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; and monoalkyl ethers or monophenyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the polyhydric alcohols such as 1-methoxy-2-propanol or the compounds having an ester bond. compounds having an ether bond such as methyl lactate, methyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl α-methoxyisobutyrate, methyl β-methoxyisobutyrate, ethyl 2-ethoxyisobutyrate, methyl methoxypropionate, ethyl ethoxypropionate, methyl α-formyloxyisobutyrate, methyl β-formyloxyisobutyrate, methyl 3-hydroxyisobutyrate, and other esters other than compound (B1); aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; dimethyl sulfoxide (DMSO), etc. These solvents (B2) may be used alone or in combination of two or more.

[0017] However, from the viewpoint of effectively achieving the EBR step, in the solvent composition of the present embodiment, the content of compound (B1) in component (B) is preferably 20 to 100 mass%, more preferably 30 to 100 mass%, even more preferably 50 to 100 mass%, still more preferably 60 to 100 mass%, and particularly preferably 70 to 100 mass%, relative to the total amount (100 mass%) of component (B) contained in the solvent composition.

[0018] From the viewpoint of removing the semiconductor manufacturing composition, it is preferable that the component (B) used in this embodiment contains, as the solvent (B2), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate. The inclusion of methyl α-methoxyisobutyrate is preferable from the viewpoint of obtaining high solubility in the semiconductor manufacturing composition. The inclusion of methyl α-formyloxyisobutyrate is preferable from the viewpoint of obtaining high solubility in the semiconductor manufacturing composition. The inclusion of methyl α-acetyloxyisobutyrate is preferable from the viewpoint of obtaining high solubility in the semiconductor manufacturing composition. The inclusion of methyl 3-hydroxyisobutyrate is preferable from the viewpoint of obtaining high solubility in the semiconductor manufacturing composition. The method for mixing methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, or methyl 3-hydroxyisobutyrate is not particularly limited, and the compound can be incorporated by either adding methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, or methyl 3-hydroxyisobutyrate to compound (B1), or by producing it as a by-product or mixing it in during the production process of compound (B1).

[0019] The content of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, or methyl 3-hydroxyisobutyrate is not particularly limited, but is preferably less than 100% by mass, more preferably 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 1% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, based on the total amount (100% by mass) of the solvent composition, from the viewpoint of improving productivity by shortening the drying time of the solvent composition. From the viewpoint of obtaining high solubility in the semiconductor manufacturing composition, the content is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more.

[0020] The content of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, or methyl 3-hydroxyisobutyrate is preferably 100% by mass or less, more preferably 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, based on the total amount (100% by mass) of compound (B1). From the viewpoint of obtaining high solubility in the composition for manufacturing semiconductors, the content is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more.

[0021] In the solvent composition of this embodiment, the content of component (B) is appropriately set depending on the application, but can be 1% by mass or more, 10% by mass or more, 30% by mass or more, 50% by mass or more, 54% by mass or more, 58% by mass or more, 60% by mass or more, 65% by mass or more, 69% by mass or more, 74% by mass or more, 77% by mass or more, 80% by mass or more, 82% by mass or more, 84% by mass or more, 88% by mass or more, 90% by mass or more, 94% by mass or more, or 97% by mass or more, based on the total amount (100% by mass) of the solvent composition. Furthermore, the upper limit of the content of component (B) is appropriately set, but can be 99% by mass or less, 98% by mass or less, 96% by mass or less, 93% by mass or less, 91% by mass or less, 86% by mass or less, 81% by mass or less, 76% by mass or less, 71% by mass or less, 66% by mass or less, or 61% by mass or less, based on the total amount (100% by mass) of the resist composition. The content of component (B) can be determined in any combination by appropriately selecting from the above-mentioned upper and lower limit values.

[0022] <Other Components> The solvent composition of this embodiment may contain other components in addition to the component (B) described above, depending on the intended use. Examples of other components include one or more selected from surfactants and antioxidants. The content of each of these other components is appropriately selected depending on the type of component, but is preferably 0.000000001 to 1 part by mass, more preferably 0.000001 to 0.1 part by mass, and even more preferably 0.00001 to 0.001 part by mass per part by mass of component (B) contained in the solvent composition.

[0023] (Surfactant) The surfactant that can be used in this embodiment is not particularly limited and can be any surfactant known in the art. Preferred surfactants include ethylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, and diethylene glycol dipropyl ether. These surfactants can be used alone or in combination of two or more.

[0024] (Antioxidant) The antioxidant that can be used in the present embodiment is not particularly limited and may be any antioxidant known in the art, and examples thereof include tocopherol-based antioxidants, phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, benzotriazole-based antioxidants, benzophenone-based antioxidants, hydroxylamine-based antioxidants, salicylic acid ester-based antioxidants, and triazine-based antioxidants.

[0025] (Tocopherol-based antioxidant) A tocopherol-based compound is generally vitamin E and is a naturally occurring chemical substance. Therefore, it is highly safe and has a small environmental impact. In addition, since it is oil-soluble and liquid at room temperature, it has excellent compatibility with solvent compositions and the like and excellent resistance to precipitation.

[0026] Examples of tocopherol compounds include tocopherol and its derivatives, and tocotrienol and its derivatives. Tocopherols and tocotrienols are known to be classified into natural compounds (d-forms), non-natural compounds (l-forms), and racemic mixtures (dl-forms) which are equal mixtures of these compounds. Natural compounds (d-forms) and racemic compounds (dl-forms) are preferred because some of them are used as food additives, etc.

[0027] Specific examples of tocopherols include d-α-tocopherol, dl-α-tocopherol, d-β-tocopherol, dl-β-tocopherol, d-γ-tocopherol, dl-γ-tocopherol, d-δ-tocopherol, and dl-δ-tocopherol.

[0028] Specific examples of tocotrienol include d-α-tocotrienol, dl-α-tocotrienol, d-β-tocotrienol, dl-β-tocotrienol, d-γ-tocotrienol, dl-γ-tocotrienol, d-δ-tocotrienol, and dl-δ-tocotrienol.

[0029] Specific examples of tocopherol derivatives include acetate esters, nicotinate esters, linoleate esters, succinate esters, etc. of the above-mentioned tocopherols.Specific examples of tocotrienol derivatives include acetate esters, etc. of the above-mentioned tocotrienols.

[0030] (Phenol-Based Antioxidant) Examples of the phenol-based antioxidant include hindered phenol-based antioxidants. Examples of hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 2,2'-thio-bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 4,4'-butylidenebis-(6-t-butyl-3-methylphenol), 2,2'-methylenebis-(4-ethyl-6-t-butylphenol), and butylhydroxyanisole. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used. In addition to the above-mentioned hindered phenol type antioxidants, hydroquinone can also be used as the phenol type antioxidant.

[0031] (Hindered Amine Antioxidant) Examples of the hindered amine antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino- N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate), poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethyl{ (2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine. Other examples include oligomeric and polymeric compounds having a hindered amine structure.

[0032] (Phosphorus-Based Antioxidants) Examples of phosphorus-based antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl)phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl) phenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, tris(2-ethylhexyl)phosphite, triisodecyl phosphite, and ethylbis(2,4-ditert-butyl-6-methylphenyl) phosphite. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.

[0033] (Sulfur-Based Antioxidants) Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, and ditetradecyl 3,3'-thiodipropionate. In addition, oligomer and polymer compounds having a thioether structure can also be used.

[0034] (Benzotriazole-Based Antioxidant) As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

[0035] (Benzophenone-Based Antioxidants) Examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 2-hydroxy-4-chlorobenzophenone. In addition, oligomer and polymer compounds having a benzophenone structure can also be used.

[0036] (Hydroxylamine-Based Antioxidants) Examples of hydroxylamine-based antioxidants include hydroxylamine, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine phosphate, hydroxylamine hydrochloride, hydroxylamine citrate, and hydroxylamine oxalate.

[0037] (Salicylate-Based Antioxidants) Examples of salicylate-based antioxidants include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

[0038] (Triazine-based antioxidants) Examples of triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine, etc. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

[0039] (Organic Acid) Examples of organic acids include carboxylic acids, sulfonic acids, sulfinic acids, organic phosphinic acids, organic phosphonic acids, phenols, enols, thiols, acid imides, oximes, and sulfonamides.

[0040] Examples of the carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic 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, shikimic acid, glycolic acid, lactic acid, and 2-hydroxyisobutyric acid; dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, tartaric acid, and malic acid; and carboxylic acids having three or more carboxy groups, such as citric acid.

[0041] Examples of the sulfonic acids include benzenesulfonic acid and p-toluenesulfonic acid. Examples of the sulfinic acids include benzenesulfinic acid and p-toluenesulfinic acid. Examples of the organic phosphinic acids include diethylphosphinic acid, methylphenylphosphinic acid, and diphenylphosphinic acid. Examples of the organic phosphonic acids include methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid, and phenylphosphonic acid. Examples of the phenols include monohydric phenols such as phenol, cresol, 2,6-xylenol, and naphthol; dihydric phenols such as catechol, resorcinol, hydroquinone, and 1,2-naphthalenediol; and trihydric or higher phenols such as pyrogallol and 2,3,6-naphthalenetriol.

[0042] Examples of the enol include 2-hydroxy-3-methyl-2-butene and 3-hydroxy-4-methyl-3-hexene. Examples of the thiol include mercaptoethanol and mercaptopropanol. Examples of the acid imide include carboxylic acid imides such as maleimide and succinimide, as well as sulfonic acid imides such as di(trifluoromethanesulfonic acid)imide and di(pentafluoroethanesulfonic acid)imide. Examples of the oxime include aldoximes such as benzaldoxime and salicylaldoxime, and ketoximes such as diethyl ketoxime, methyl ethyl ketoxime, and cyclohexanone oxime. Examples of the sulfonamide include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, and toluenesulfonamide.

[0043] The solvent composition of this embodiment has excellent solubility for a variety of resist films, resist underlayer films (films coated on the underlayer of a resist, such as bottom antireflective coating (BARC) and spin-on carbon film), and resist overlayer films (top antireflective coating (TARC)), and can improve EBR characteristics, etc. In particular, in the case of photoresists for g-line, i-line, KrF, ArF, EUV, or EB, the basic structures of the constituent photoresists are different, so in order to improve the solubility and coatability of all of these, it is necessary to adjust the composition content of the organic solvent, and the solvent composition of this embodiment satisfies this requirement.

[0044] <Uses of Solvent Composition> As described above, the solvent composition of this embodiment is a solvent composition used to remove a metal compound or a semi-metal compound (compound (A)). The solvent composition of this embodiment may be one that removes compound (A) present as a residue or a contaminant, for example. The solvent composition of this embodiment may remove compound (A) either before or after exposure. Removing compound (A) with the solvent composition of this embodiment means that, when compound (A) is contained in a semiconductor manufacturing composition, not only compound (A) contained in the semiconductor manufacturing composition but also other components constituting the semiconductor manufacturing composition may be dissolved and removed, or only compound (A) may be removed. Such removal may be performed, for example, in an EBR process, a back-rinse process, a development process, or a rework process.

[0045] <Metal Compound or Metalloid Compound (Compound (A))> In this embodiment, compound (A) is a compound having one or more metal atoms or metalloid atoms. Compound (A) is not particularly limited, but may be contained in a film such as a resist film, a resist top layer film, or a photoresist bottom layer film formed directly or indirectly on a substrate. The film may be a film formed from a semiconductor manufacturing composition containing compound (A) as one of its main components, or a semiconductor manufacturing composition containing compound (A) as a partial additive, or a film formed from a semiconductor manufacturing composition containing compound (A) unintentionally. Furthermore, the film may be a film substantially composed of compound (A).

[0046] Here, "metal atom" refers to an atom of an element classified as a metal in the periodic table, and "metalloid atom" includes boron, silicon, germanium, arsenic, selenium, antimony, tellurium, polonium, and astatine.

[0047] Examples of the metal atom and metalloid atom (hereinafter also referred to as "metal atom (a)") contained in compound (A) include metal atoms of groups 3 to 16 of the periodic table. Examples of the metal atom (a) of Group 3 include scandium, yttrium, lanthanum, and cerium. Examples of the metal atom (a) of Group 4 include titanium, zirconium, and hafnium. Examples of the metal atom (a) of Group 5 include vanadium, niobium, and tantalum. Examples of the metal atom (a) of Group 6 include chromium, molybdenum, and tungsten. Examples of the metal atom (a) of Group 7 include manganese, technetium, and rhenium. Examples of the metal atom (a) of Group 8 include iron, ruthenium, and osmium. Examples of the metal atom (a) of Group 9 include cobalt, rhodium, and iridium. Examples of the metal atom (a) of Group 10 include nickel, palladium, and platinum. Examples of the metal atom (a) of Group 11 include copper, silver, and gold. Examples of the metal atom (a) of Group 12 include zinc, cadmium, and mercury. Examples of the metal atom (a) of Group 13 include boron, aluminum, gallium, indium, and thallium; examples of the metal atom (a) of Group 14 include silicon, germanium, tin, and lead; examples of the metal atom (a) of Group 15 include arsenic, antimony, and bismuth; and examples of the metal atom (a) of Group 16 include selenium and tellurium.

[0048] The metal atom (a) is preferably a metal atom (a) of Groups 3 to 16, and more preferably an atom of an element belonging to any one of Periods 3 to 7 of Groups 3 to 16. Furthermore, the metal element (a) is preferably a metal atom (a) of Groups 4 to 16, and more preferably an atom of an element belonging to any one of Periods 3 to 7 of Groups 4 to 16. The metal atom (a) contained in compound (A) is preferably an atom of any one of titanium, zirconium, hafnium, tantalum, tungsten, zinc, germanium, tin, and tellurium.

[0049] In this embodiment, the compound (A) is not particularly limited as long as it has a metal atom (a), but it may contain a ligand that bonds to the metal atom or metalloid atom of the compound (A). Specific examples of the ligand include a halogen ligand, a hydroxo ligand, a carboxy ligand, an alkoxy ligand, a carboxylate ligand, an alkyl ligand, and an amide ligand.

[0050] The compound (A) will be described in more detail below. The compound (A) may contain one or more types of compounds.

[0051] (First Aspect) In the first aspect of this embodiment, the compound (A) may be, for example, the following compound (A1-1), complex (A1-2), and / or polymetalloxane (A1-3). Each compound will be described below.

[0052] ((A1-1) Compound) The (A1-1) compound is a metal compound or semimetal compound represented by the following formula (i) (hereinafter also referred to as "metal compound (I1)"), a hydrolyzate of the metal compound (I1), a hydrolysis condensate of the metal compound (I1), or a combination thereof. [L ｘ M.Y. ｙ ] (i)

[0053] In the above formula (i), M is a metal atom. L is a ligand. x is an integer of 0 to 5. When x is 2 or more, multiple Ls are the same or different. Y is a hydrolyzable group selected from a halogen atom, an alkoxy group, and a carboxylate group. y is an integer of 1 to 6. When y is 2 or more, multiple Ys are the same or different, provided that x+y is 6 or less. L is a ligand that does not correspond to Y.

[0054] Here, the term "hydrolyzable group" refers to a group that can generate M-OH by hydrolysis. The hydrolyzate of metal compound (I1) may have a hydrolyzable group that is not hydrolyzed. The term "hydrolyzed condensate" of metal compound (I1) refers to a product in which a hydrolyzable group in metal compound (I1) is hydrolyzed to convert it to -OH, and the two resulting -OH groups are dehydration-condensed to form -0-.

[0055] The metal atom represented by M is preferably a metal atom of Groups 3 to 16 of the periodic table, more preferably a metal atom of Groups 4 to 6, 12 or 16, still more preferably zirconium, tellurium, hafnium, tantalum, zinc, germanium, tin or silicon, particularly preferably zirconium, tellurium, hafnium, tantalum, zinc, germanium or tin, and even more particularly preferably zirconium, tellurium, hafnium or tin.

[0056] The ligand represented by L includes monodentate and polydentate ligands. Examples of the monodentate ligand include a hydroxo ligand, a carboxy ligand, an amide ligand, and ammonia.

[0057] The amide ligand may be, for example, an unsubstituted amide ligand (NH ２ ), methylamide ligand (NHMe), dimethylamide ligand (NMe ２ ), diethylamide ligand (NEt ２ ), dipropylamide ligand (NPr ２ ) etc.

[0058] Examples of the polydentate ligand include hydroxy acid esters, β-diketones, β-ketoesters, β-dicarboxylic acid esters, hydrocarbons having a π bond, and carboxylate anions.

[0059] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxyisobutyric acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, and salicylic acid ester.

[0060] Examples of the β-diketone include acetylacetone, methylacetylacetone, and ethylacetylacetone.

[0061] Examples of the β-ketoester include acetoacetic acid ester, α-alkyl-substituted acetoacetic acid ester, β-ketopentanoic acid ester, and benzoylacetic acid ester.

[0062] Examples of the β-dicarboxylic acid ester include malonic acid diester, α-alkyl-substituted malonic acid diester, α-cycloalkyl-substituted malonic acid diester, and α-aryl-substituted malonic acid diester.

[0063] Examples of the hydrocarbon having a π bond include: chain olefins such as ethylene and propylene; cyclic olefins such as cyclopentene, cyclohexene and norbornene; chain dienes such as butadiene and isoprene; cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene and norbornadiene; and aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene and indene.

[0064] The above x is preferably an integer of 0 to 2, and more preferably 0 or 1.

[0065] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0066] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group.

[0067] Examples of the carboxylate group include an acetoxy group, an ethyryloxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.

[0068] As the above Y, a chlorine atom, an ethoxy group, an isopropoxy group, a butoxy group, or an acetoxy group is more preferable.

[0069] The above y is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

[0070] Examples of the (A1-1) compound include metal compounds having four hydrolyzable groups, such as tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetraethoxytitanium, tetramethoxytitanium, tetra-i-propoxyzirconium, tetra-n-butoxyzirconium, tetraethoxyzirconium, tetramethoxyzirconium, tetra-i-propoxytellurium, tetra-n-butoxytellurium, tetraethoxytellurium, tetramethoxytellurium, tetra-i-propoxytin, tetra-n-butoxytin, tetraethoxytin, and tetramethoxytin; Methyltrimethoxytitanium, methyltriethoxytitanium, methyltri-i-propoxytitanium, methyltributoxyzirconium, methyltrimethoxyzirconium, ethyltriethoxyzirconium, ethyltri-i-propoxyzirconium, ethyltributoxyzirconium, methyltributoxytellurium, methyltrimethoxytellurium, ethyltriethoxytellurium, ethyltri-i-propoxytellurium, ethyltributoxytellurium, methyltributoxytin, methyltrimethoxytin, ethyltriethoxytin, ethyltri-i-propoxytin, ethyltributoxytin, butyltrimethoxytitanium, phenyltrimethoxytitanium, naphthyltrimethoxytitanium, phenyltriethoxytitanium, naphthyltriethoxytitanium, aminopropyltrimethoxytitanium metal compounds having three hydrolyzable groups, such as titanium dioxide, aminopropyltriethoxyzirconium, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium, γ-glycidoxypropyltrimethoxyzirconium, 3-isocyanopropyltrimethoxyzirconium, 3-isocyanopropyltriethoxyzirconium, triethoxymono(acetylacetonato)titanium, tri-n-propoxymono(acetylacetonato)titanium, tri-i-propoxymono(acetylacetonato)titanium, triethoxymono(acetylacetonato)zirconium, tri-n-propoxymono(acetylacetonato)zirconium, tri-i-propoxymono(acetylacetonato)zirconium, and titanium tributoxymonostearate;Metal compounds having two hydrolyzable groups, such as dimethyldimethoxytitanium, diphenyldimethoxytitanium, dibutyldimethoxyzirconium, diisopropyloxybisacetylacetonate, di-n-butoxybis(acetylacetonato)titanium, and di-n-butoxybis(acetylacetonato)zirconium; metal compounds having one hydrolyzable group, such as trimethylmethoxytitanium, triphenylmethoxytitanium, tributylmethoxytitanium, tri(3-methacryloxypropyl)methoxyzirconium, and tri(3-acryloxypropyl)methoxyzirconium; hydrolysates of the above metal compounds, hydrolyzed condensates of the above metal compounds, and combinations thereof;

[0071] ((A1-2) Complex) The (A1-2) complex is a complex containing multiple metal atoms and a bridging ligand derived from a compound represented by the following formula (ii) (hereinafter also referred to as "compound (I1)"). Here, the "bridging ligand" refers to a ligand that forms a bridge by bonding to multiple metal atoms.

[0072] As the metal atom, a metal atom of Groups 3 to 16 of the periodic table is preferred, a metal atom of Groups 4 to 16 is more preferred, a metal atom of Groups 4 to 16, Periods 4 to 7 is even more preferred, and zirconium, tellurium, hafnium, tantalum, zinc, or tin is particularly preferred.

[0073] In the above formula (ii), R Ｘ is an n-valent organic group, where n is an integer of 1 to 4. When n is 1, X is —COOH. When n is 2 to 4, X is —OH, —COOH, —NCO, or —NHR. ａ , -COOR Ａ or -CO-C(R Ｌ ) ２ -CO-R Ａ It is. ａ is a hydrogen atom or a monovalent organic group. Ａ are each independently a monovalent organic group. Ｌ are each independently a hydrogen atom or a monovalent organic group. Ｌare the same or different from each other. When n is 2 or more, multiple Xs are the same or different from each other.

[0074] R Ｘ Examples of the n-valent organic group represented by the formula (I) include an n-valent hydrocarbon group, a group (α) containing a divalent heteroatom-containing group between carbon atoms of the hydrocarbon group, and a group in which some or all of the hydrogen atoms in the hydrocarbon group and group (α) have been substituted with a monovalent heteroatom-containing group.

[0075] Here, "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. This "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. "Linear hydrocarbon group" refers to a hydrocarbon group that does not contain a cyclic structure and is composed only of a linear structure, and includes both linear hydrocarbon groups and branched hydrocarbon groups. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic structure as a ring structure and does not contain an aromatic ring structure, and includes both monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic hydrocarbon groups. However, an alicyclic hydrocarbon group does not necessarily have to be composed only of an alicyclic structure, and may contain a linear structure as part of it. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, an aromatic hydrocarbon group does not necessarily have to be composed only of an aromatic ring structure, and may contain a linear structure or an alicyclic structure as part of it. The "number of ring members" refers to the number of atoms constituting the ring of an aromatic ring structure, aromatic heterocyclic structure, alicyclic structure, or aliphatic heterocyclic structure, and in the case of a polycyclic ring structure, refers to the number of atoms constituting the polycyclic ring.

[0076] Examples of the n-valent hydrocarbon group include groups in which n hydrogen atoms have been removed from hydrocarbons such as chain hydrocarbons having 1 to 30 carbon atoms, such as alkanes such as methane, ethane, propane, and butane; alkenes such as ethene, propene, butene, and pentene; and alkynes such as ethyne, propyne, butyne, and pentyne; alicyclic hydrocarbons having 3 to 30 carbon atoms, such as cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, and adamantane; cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, and norbornene; and aromatic hydrocarbons having 6 to 30 carbon atoms, such as arenes such as benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, dimethylnaphthalene, and anthracene.

[0077] Examples of the divalent heteroatom-containing group include an oxygen atom, a nitrogen atom, a silicon atom, a phosphorus atom, a sulfur atom, and groups having a combination thereof, and specific examples include -O-, -NH-, -CO-, -S-, and groups having a combination thereof. Of these, -O- is preferred.

[0078] Examples of the monovalent heteroatom-containing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and propoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; alkoxycarbonyloxy groups such as methoxycarbonyloxy group and ethoxycarbonyloxy group; acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, and benzoyl group; cyano group, and nitro group.

[0079] R ａ Examples of the monovalent organic group represented by the formula (I) include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group (β) containing a divalent heteroatom-containing group between carbon atoms of the hydrocarbon group, and groups in which some or all of the hydrogen atoms of the hydrocarbon group and group (β) have been substituted with a monovalent heteroatom-containing group.

[0080] 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, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0081] Examples of the monovalent chain hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, and i-propyl; alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl. Examples of the monovalent alicyclic hydrocarbon groups having 3 to 30 carbon atoms include monocyclic saturated alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl; monocyclic unsaturated alicyclic hydrocarbon groups such as cyclopentenyl and cyclohexenyl; polycyclic saturated alicyclic hydrocarbon groups such as norbornyl, adamantyl, and tricyclodecyl; and polycyclic unsaturated alicyclic hydrocarbon groups such as norbornenyl and tricyclodecenyl.

[0082] Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthryl; and aralkyl groups such as benzyl, phenethyl, naphthylmethyl, and anthrylmethyl.

[0083] Examples of heteroatoms constituting the monovalent or divalent heteroatom-containing group include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, and halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0084] Examples of the divalent heteroatom-containing group include -O-, -CO-, -S-, -CS-, -NR'-, and groups formed by combining two or more of these. R' is a hydrogen atom or a monovalent hydrocarbon group. Of these, -O- is preferred.

[0085] Examples of the monovalent heteroatom-containing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, hydroxy group, carboxy group, cyano group, amino group, sulfanyl group (—SH), etc. Among these, a fluorine atom is preferred.

[0086] R ａ As the alkyl group, a monovalent hydrocarbon group is preferable, a monovalent chain hydrocarbon group is more preferable, an alkyl group is further preferable, and a methyl group is particularly preferable.

[0087] R Ａ or R Ｌ The monovalent organic group represented by the above R ａ Examples of the groups include the same groups as those exemplified as the groups.

[0088] R Ｘ As the group where n is 1, a monovalent chain hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent heteroatom-containing group is preferred, an alkyl group, an alkenyl group, or an aryl group is more preferred, and a propyl group, a 2-propenyl group, or a 3-methylphenyl group is even more preferred.

[0089] R Ｘ As the alkyl group, when n is 2, a divalent chain hydrocarbon group, a divalent aromatic hydrocarbon group, or a divalent heteroatom-containing group is preferred, an alkanediyl group, an alkenediyl group, an arenediyl group, or an alkanediyloxyalkanediyl group is more preferred, and a 1,2-ethanediyl group, a 1,2-propanediyl group, a butanediyl group, a hexanediyl group, an ethenediyl group, a xylenediyl group, or an ethanediyloxyethanediyl group is even more preferred.

[0090] R Ｘ As the alkyl group, when n is 3, a trivalent chain hydrocarbon group is preferable, an alkanetriyl group is more preferable, and a 1,2,3-propanetriyl group is even more preferable.

[0091] R Ｘ As the alkyl group, when n is 4, a tetravalent chain hydrocarbon group is preferred, an alkanetetrayl group is more preferred, and a 1,2,3,4-butanetetrayl group is even more preferred.

[0092] Examples of compound (I1) include compounds represented by the following formulas (ii-1) to (ii-7) (hereinafter also referred to as "compounds (I1-1) to (I1-7)").

[0093] In the above formulas (ii-1) to (ii-7), R Ｘ , R ａ , R Ａ and R Ｌhas the same meaning as formula (ii) above. In formulas (ii-1) and (ii-3) to (ii-6) above, n is an integer of 2 to 4. In formula (ii-2) above, n is an integer of 1 to 4. In formula (ii-7) above, p is an integer of 1 to 3. q is an integer of 1 to 3. However, p+q is 2 to 4.

[0094] Examples of compound (I1-1) include those in which n is 2: alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexamethylene glycol; dialkylene glycols such as diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, and tripropylene glycol; cycloalkylene glycols such as cyclohexanediol, cyclohexanedimethanol, norbornanediol, norbornanedimethanol, and adamantanediol; aromatic ring-containing glycols such as 1,4-benzenedimethanol and 2,6-naphthalenedimethanol; dihydric phenols such as catechol, resorcinol, and hydroquinone; and those in which n is 3: alkanetriols such as glycerin and 1,2,4-butanetriol; cycloalkanetriols such as 1,2,4-cyclohexanetriol and 1,2,4-cyclohexanetrimethanol; aromatic ring-containing glycols such as 1,2,4-benzenetrimethanol and 2,3,6-naphthalenetrimethanol; Examples of the phenols in which n is 4 include trihydric phenols such as pyrogallol and 2,3,6-naphthalenetriol; trimethylolpropane ethoxylate, etc. Examples of the phenols in which n is 4 include alkane tetraols such as erythritol and pentaerythritol; cycloalkane tetraols such as 1,2,4,5-cyclohexanetetraol; aromatic ring-containing tetraols such as 1,2,4,5-benzenetetramethanol; and tetrahydric phenols such as 1,2,4,5-benzenetetraol. Among these, those in which n is 2 or 3 are preferred, alkylene glycol, dialkylene glycol, alkanetriol, or trimethylolpropane ethoxylate is more preferred, and propylene glycol, diethylene glycol, glycerin, or trimethylolpropane ethoxylate is even more preferred.

[0095] Examples of compound (I1-2) include those in which n is 1: chain saturated monocarboxylic acids such as acetic acid and propionic acid; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and tiglic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, 2-hydroxyisobutyric acid, malic acid and citric acid; alicyclic monocarboxylic acids such as cyclohexanedicarboxylic acid, norbornanecarboxylic acid and adamantanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, 3-methylbenzoic acid and naphthalenecarboxylic acid; those in which n is 2: chain saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid; chain unsaturated dicarboxylic acids such as maleic acid and fumaric acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, norbornanedicarboxylic acid and adamantanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid; and those in which n is 3: Examples of the tricarboxylic acids include: linear saturated tricarboxylic acids such as 1,2,3-propanetricarboxylic acid; linear unsaturated tricarboxylic acids such as 1,2,3-propenetricarboxylic acid; alicyclic tricarboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid; and aromatic tricarboxylic acids such as trimellitic acid and 2,3,7-naphthalenetricarboxylic acid. Examples of the tricarboxylic acids in which n is 4 include: linear saturated tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid; linear unsaturated tetracarboxylic acids such as 1,2,3,4-butadienetetracarboxylic acid; alicyclic tetracarboxylic acids such as 1,2,5,6-cyclohexanetetracarboxylic acid and 2,3,5,6-norbornanetetracarboxylic acid; and aromatic tetracarboxylic acids such as pyromellitic acid and 2,3,6,7-naphthalenetetracarboxylic acid. Among these, those in which n is 1 or 2 are preferred, chain saturated monocarboxylic acid, chain unsaturated monocarboxylic acid, aromatic monocarboxylic acid or chain saturated dicarboxylic acid are more preferred, those in which n is 1 are even more preferred, and acetic acid, propionic acid, methacrylic acid, tiglic acid or 3-methylbenzoic acid are particularly preferred.

[0096] Examples of the compound (I1-3) include those in which n is 2, such as chain diisocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate; and aromatic diisocyanates such as tolylene diisocyanate, 1,4-benzene diisocyanate, and 4,4'-diphenylmethane diisocyanate; those in which n is 3, such as chain triisocyanates such as trimethylene triisocyanate; alicyclic triisocyanates such as 1,2,4-cyclohexane triisocyanate; and aromatic triisocyanates such as 1,2,4-benzene triisocyanate; and those in which n is 4, such as chain tetraisocyanates such as tetramethylene tetraisocyanate; Examples of the tetraisocyanates include alicyclic tetraisocyanates such as 1,2,4,5-cyclohexane tetraisocyanate, and aromatic tetraisocyanates such as 1,2,4,5-benzene tetraisocyanate. Among these, those in which n is 2 are preferred, chain diisocyanates are more preferred, and hexamethylene diisocyanate is even more preferred.

[0097] Examples of compound (I1-4) include those in which n is 2, such as chain diamines such as ethylenediamine, N-methylethylenediamine, N,N'-dimethylethylenediamine, trimethylenediamine, N,N'-dimethyltrimethylenediamine, tetramethylenediamine, and N,N'-dimethyltetramethylenediamine; alicyclic diamines such as 1,4-cyclohexanediamine and 1,4-di(aminomethyl)cyclohexane; and aromatic diamines such as 1,4-diaminobenzene and 4,4'-diaminodiphenylmethane; those in which n is 3, such as chain triamines such as triaminopropane and N,N',N"-trimethyltriaminopropane; alicyclic triamines such as 1,2,4-triaminocyclohexane; and aromatic triamines such as 1,2,4-triaminobenzene; and those in which n is 4, such as chain tetraamines such as tetraaminobutane; Alicyclic tetraamines such as 1,2,4,5-tetraaminocyclohexane and 2,3,5,6-tetraaminonorbornane; and aromatic tetraamines such as 1,2,4,5-tetraaminobenzene. Among these, those in which n is 2 are preferred, chain diamines are more preferred, and N,N'-dimethylethylenediamine is even more preferred.

[0098] Examples of compound (I1-5) include those in which n is 2, such as chain saturated dicarboxylic acid diesters, such as oxalic acid diester, malonic acid diester, succinic acid diester, glutaric acid diester, and adipic acid diester; chain unsaturated dicarboxylic acid diesters, such as maleic acid diester and fumaric acid diester; alicyclic dicarboxylic acid diesters, such as 1,4-cyclohexanedicarboxylic acid diester, norbornanedicarboxylic acid diester, and adamantanedicarboxylic acid diester; aromatic dicarboxylic acid diesters, such as phthalic acid diester, terephthalic acid diester, 2,6-naphthalenedicarboxylic acid diester, and 2,7-naphthalenedicarboxylic acid diester; and those in which n is 3, such as chain saturated tricarboxylic acid triesters, such as 1,2,3-propanetricarboxylic acid triester; chain unsaturated tricarboxylic acid triesters, such as 1,2,3-propenetricarboxylic acid triester; alicyclic tricarboxylic acid triesters, such as 1,2,4-cyclohexanetricarboxylic acid triester; Examples of the tetracarboxylic acid tetraesters include aromatic tricarboxylic acid tetraesters such as trimellitic acid triester and 2,3,7-naphthalene tricarboxylic acid triester, and those in which n is 4 include: linear saturated tetracarboxylic acid tetraesters such as 1,2,3,4-butanetetracarboxylic acid tetraester; linear unsaturated tetracarboxylic acid tetraesters such as 1,2,3,4-butadienetetracarboxylic acid tetraester; alicyclic tetracarboxylic acid tetraesters such as 1,2,5,6-cyclohexanetetracarboxylic acid tetraester and 2,3,5,6-norbornanetetracarboxylic acid tetraester; and aromatic tetracarboxylic acid tetraesters such as pyromellitic acid tetraester and 2,3,6,7-naphthalenetetracarboxylic acid tetraester. Among these, those in which n is 2 are preferred, linear saturated dicarboxylic acid diesters are more preferred, and succinic acid diesters and maleic acid diesters are even more preferred.

[0099] Compound (I1-6) is preferably one in which n is 2, and examples of compounds in which n is 2 include 2,4,6,8-nonanetetrone, 2,4,7,9-decanetetrone, 3,5-dioxo-heptane-1,7-dicarboxylic acid ester, and 3,6-dioxo-octane-1,8-dicarboxylic acid ester.

[0100] Compound (I1-7) is preferably one in which p is 1 and q is 1, and examples thereof include glycolic acid esters, lactate esters, 2-hydroxyisobutyric acid esters, 2-hydroxycyclohexane-1-carboxylic acid esters, salicylic acid esters, etc. Among these, lactate esters are preferred, and ethyl lactate is more preferred.

[0101] The lower limit of the amount of compound (I1) in complex (A1-2) is preferably 0.01 mol, more preferably 0.1 mol, relative to 1 mol of metal atoms in complex (A1-2).The upper limit of the amount is preferably 30 mol, more preferably 20 mol, and even more preferably 15 mol.

[0102] ((A1-3) Polymetalloxane) The (A1-3) polymetalloxane is a polymetalloxane having a structural unit represented by the following formula (iii) or (iv) (hereinafter also referred to as "structural unit (I)"). "Polymetalloxane" refers to a compound having two or more structural units (I). In the (A1-3) polymetalloxane, the structural unit (I) may form a chain structure or a cyclic structure. In the above formulas (iii) and (iv), each M is independently a germanium atom, a tin atom, or a lead atom. １ , R ２ and R ３ are each independently a monovalent organic group having 1 to 30 carbon atoms and bonded to M via a carbon atom.

[0103] M is preferably a germanium atom or a tin atom, and more preferably a tin atom. １ , R ２ or R ３ Examples of the monovalent organic group having 1 to 30 carbon atoms represented by the formula (ii) include Rａ Examples of the organic group include the same groups as those exemplified above. １ , R ２ and R ３ The upper limit of the number of carbon atoms in the organic group is preferably 20, more preferably 10, and even more preferably 5.

[0104] R in the above formula (iii) １ and R in the above formula (iv) ２ As the group bonded to M in the structural unit (I), a hydrocarbon group is preferable, an alkyl group is more preferable, and an i-propyl group or a t-butyl group is more preferable. By using such a group as the group bonded to M in the structural unit (I), the sensitivity of the composition for manufacturing a semiconductor as a radiation-sensitive composition is further improved.

[0105] The lower limit of the content of the structural unit (I) is preferably 50 mol%, more preferably 70 mol%, and even more preferably 90 mol%, based on all structural units constituting the polymetalloxane (A1-3). The upper limit of this content is, for example, 100 mol%. By ensuring that the content of the structural unit (I) falls within this range, the sensitivity of the radiation-sensitive composition can be further improved.

[0106] The polymetalloxane (A1-3) may have structural units other than the structural unit (I). When the polymetalloxane (A1-3) has other structural units, the upper limit of the content of the other structural units is preferably 10 mol %, more preferably 5 mol %.

[0107] The lower limit of the weight average molecular weight (Mw) of the polymetalloxane (A1-3) is preferably 700, more preferably 1,000, even more preferably 1,200, and particularly preferably 1,400. The upper limit of the Mw is preferably 20,000, more preferably 10,000, even more preferably 8,000, and particularly preferably 7,000.

[0108] (([B1] Electron Acceptor)) In the first aspect of this embodiment, when the compound (A) includes the (A1-1) compound, the (A1-2) complex, and / or the (A1-3) polymetalloxane, the composition for manufacturing a semiconductor that includes the compound (A) may further include a [B1] electron acceptor. The [B1] electron acceptor is a substance that captures secondary electrons that are generated from metal atoms included in the compound (A) upon exposure. The "electron acceptor" refers to a substance that functions as an oxidizing agent in a redox reaction. The [B1] electron acceptor may be used alone or in combination of two or more.

[0109] [B1] Examples of the electron acceptor include a compound having a sulfonyl group, a compound having an aromatic hydroxy group, a tetracyanoquinodimethane compound, and potassium ferricyanide.

[0110] Examples of compounds having a sulfonyl group include dimethyl sulfone, ethyl methyl sulfone, methyl phenyl sulfone, diphenyl sulfone, and di-p-toluyl sulfone.

[0111] Examples of compounds having an aromatic hydroxy group include compounds in which some or all of the hydrogen atoms bonded to an aromatic carbon ring such as a benzene ring or a naphthalene ring, or an aromatic heterocycle such as a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring are substituted with hydroxy groups. Examples of compounds having an aromatic hydroxy group include triphenylsulfonium 2-hydroxy-4-trifluoromethylbenzoate, diphenyliodonium 2-hydroxy-4-trifluoromethylsulfonate, and thymine.

[0112] Examples of the tetracyanoquinodimethane compound include 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrachloro-7,7,8,8-tetracyanoquinodimethane, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, 2-chloro-7,7,8,8-tetracyanoquinodimethane, 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane, and 2,5-dichloro-7,7,8,8-tetracyanoquinodimethane.

[0113] (Second Aspect) In a second aspect of this embodiment, compound (A) can be a compound containing a metal atom or a metalloid atom and an oxygen atom. The components other than the metal atom and the metalloid atom constituting compound (A) (hereinafter also referred to as "compound [X2]") are preferably organic acids (hereinafter also referred to as "organic acids [a2]"), hydroxy acid esters, β-diketones, α,α-dicarboxylic acid esters, and amine compounds. Here, "organic acids" refer to organic compounds that exhibit acidity, and "organic compounds" refer to compounds having at least one carbon atom.

[0114] [a2] Examples of the organic acid include carboxylic acids, sulfonic acids, sulfinic acids, organic phosphinic acids, organic phosphonic acids, phenols, enols, thiols, acid imides, oximes, and sulfonamides.

[0115] Examples of the carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic 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, shikimic acid, glycolic acid, lactic acid, and 2-hydroxyisobutyric acid; dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, tartaric acid, and malic acid; and carboxylic acids having three or more carboxy groups, such as citric acid.

[0116] Examples of the sulfonic acid include benzenesulfonic acid and p-toluenesulfonic acid.

[0117] Examples of the sulfinic acid include benzenesulfinic acid and p-toluenesulfinic acid.

[0118] Examples of the organic phosphinic acid include diethylphosphinic acid, methylphenylphosphinic acid, and diphenylphosphinic acid.

[0119] Examples of the organic phosphonic acid include methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid, and phenylphosphonic acid.

[0120] Examples of the phenols include monohydric phenols such as phenol, cresol, 2,6-xylenol, and naphthol; dihydric phenols such as catechol, resorcinol, hydroquinone, and 1,2-naphthalenediol; and trihydric or higher phenols such as pyrogallol and 2,3,6-naphthalenetriol.

[0121] Examples of the enol include 2-hydroxy-3-methyl-2-butene and 3-hydroxy-4-methyl-3-hexene.

[0122] Examples of the thiol include mercaptoethanol and mercaptopropanol.

[0123] Examples of the acid imide include carboxylic acid imides such as maleimide and succinimide, and sulfonic acid imides such as di(trifluoromethanesulfonic acid)imide and di(pentafluoroethanesulfonic acid)imide.

[0124] Examples of the oxime include aldoximes such as benzaldoxime and salicylaldoxime, and ketoximes such as diethylketoxime, methylethylketoxime and cyclohexanoneoxime.

[0125] Examples of the sulfonamide include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, and toluenesulfonamide.

[0126] The organic acid [a2] is preferably a carboxylic acid, more preferably a monocarboxylic acid, and even more preferably methacrylic acid or benzoic acid.

[0127] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxyisobutyric acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, salicylic acid ester, and the like.

[0128] Examples of the β-diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione.

[0129] Examples of the β-ketoester include acetoacetic ester, α-alkyl-substituted acetoacetic ester, β-ketopentanoic ester, benzoylacetic ester, and 1,3-acetonedicarboxylic ester.

[0130] Examples of the β-ketoester include acetoacetic ester, α-alkyl-substituted acetoacetic ester, β-ketopentanoic ester, benzoylacetic ester, and 1,3-acetonedicarboxylic ester.

[0131] Examples of the amine compound include diethanolamine and triethanolamine.

[0132] The compound (A) is preferably a metal compound composed of a metal atom or a metalloid compound and an organic acid [a2]. Also, the compound (A) is more preferably a metal compound composed of a metal atom of Groups 4, 5, 14, and 16 and a carboxylic acid, and even more preferably a metal oxide composed of titanium, zirconium, tellurium, hafnium, tantalum, tungsten, or tin and methacrylic acid or benzoic acid.

[0133] The compound (A) may contain one or more of the above metal compounds.

[0134] The compound (A) may contain one or more organic acids (a2).

[0135] (([D2] Orthoester)) In the second aspect of this embodiment, when compound (A) includes a compound constituted of a metal atom or a metalloid atom together with other [X2] compounds, the semiconductor manufacturing composition containing compound (A) may include a [D2] orthoester. The [D2] orthoester is an ester of an orthocarboxylic acid. The [D2] orthoester reacts with water to give a carboxylic acid ester or the like. The semiconductor manufacturing composition can use one type of [D2] orthoester alone or two or more types in combination.

[0136] Examples of the orthoester [D2] include orthoformic acid esters such as methyl orthoformate, ethyl orthoformate, and propyl orthoformate; orthoacetic acid esters such as methyl orthoacetate, ethyl orthoacetate, and propyl orthoacetate; and orthopropionic acid esters such as methyl orthopropionate, ethyl orthopropionate, and propyl orthopropionate. Among these, orthoformic acid esters or orthoacetic acid esters are preferred, and methyl orthoformate, ethyl orthoformate, methyl orthoacetate, or ethyl orthopropionate are more preferred.

[0137] ((Organic Acid [E2])) In the second aspect of this embodiment, when the compound (A) includes a compound (A) composed of a metal atom or a metalloid atom together with other [X2] compounds, the compound (A) can include an organic acid [E2] in addition to the orthoester [D2]. As the organic acid [E2], the same organic acids as those exemplified as the organic acid [a2] above can be used. The composition for manufacturing a semiconductor may contain one or more organic acids [E2].

[0138] (Third Aspect) In a third aspect of the present embodiment, the compound (A) can be a particulate compound (A3) having one or more first functional groups (hereinafter also referred to as "functional groups (I)"), which includes a metal oxide containing a metal atom or a metalloid atom and an oxygen atom.

[0139] The metal oxide may contain atoms other than metal atoms and oxygen atoms, such as carbon atoms, hydrogen atoms, nitrogen atoms, phosphorus atoms, sulfur atoms, and halogen atoms.

[0140] The lower limit of the total content of metal atoms and oxygen atoms in the metal oxide is preferably 30 mass%, more preferably 50 mass%, further preferably 70 mass%, and particularly preferably 90 mass%, while the upper limit of the total content is preferably 99.9 mass%.

[0141] Compound (A3) has one or more functional groups (I). Examples of compound (A3) include compounds containing the metal atom and a ligand (hereinafter also referred to as a "[p] ligand") derived from an organic acid (hereinafter also referred to as an "[a3] organic acid") having the functional group (I) (hereinafter also referred to as a "compound (A3-1)"). Examples of the [p] ligand include an [a3] organic acid and an ion derived from an [a3] organic acid. It is believed that the [p] ligand is coordinately bonded to the [m3] metal atom in compound (A3-1). Compound (A3) usually has multiple functional groups (I). Here, "organic acid" refers to an organic compound that exhibits acidity, and "organic compound" refers to a compound having at least one carbon atom.

[0142] ((Organic acid [a3])) The organic acid [a3] is an organic acid having a functional group (I). The lower limit of the pKa of the organic acid [a3] is preferably 0, more preferably 1, even more preferably 1.5, and particularly preferably 3. On the other hand, the upper limit of the pKa is preferably 7, more preferably 6, even more preferably 5.5, and particularly preferably 5.

[0143] The organic acid [a3] may be a low molecular weight compound or a high molecular weight compound, but a low molecular weight compound is preferred from the viewpoint of adjusting the interaction with the metal atom to a more appropriately weak one. Here, a low molecular weight compound refers to a compound having a molecular weight of 1,500 or less, and a high molecular weight compound refers to a compound having a molecular weight of more than 1,500. The lower limit of the molecular weight of the organic acid [a3] is preferably 50, more preferably 80. On the other hand, the upper limit of the molecular weight is preferably 1,000, more preferably 500, even more preferably 400, and particularly preferably 300.

[0144] [a3] Examples of organic acids include carboxylic acids, sulfonic acids, sulfinic acids, organic phosphinic acids, organic phosphonic acids, phenols, enols, thiols, acid imides, oximes, and sulfonamides, which are compounds having a functional group (I).

[0145] Examples of the carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, arachidonic acid, benzoic acid, p-aminobenzoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, gallic acid, shikimic acid, glycolic acid, lactic acid, and 2-hydroxyisobutyric acid; dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, and malic acid; and carboxylic acids having three or more carboxy groups such as citric acid.

[0146] Examples of the sulfonic acid include benzenesulfonic acid and p-toluenesulfonic acid.

[0147] Examples of the sulfinic acid include benzenesulfinic acid and p-toluenesulfinic acid.

[0148] Examples of the organic phosphinic acid include diethylphosphinic acid, methylphenylphosphinic acid, and diphenylphosphinic acid.

[0149] Examples of the organic phosphonic acids include methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid, phenylphosphonic acid, etc. Examples of the phenols include monohydric phenols such as phenol, cresol, 2,6-xylenol, naphthol, etc.; dihydric phenols such as catechol, resorcinol, hydroquinone, 1,2-naphthalenediol, etc.; and trihydric or higher phenols such as pyrogallol, 2,3,6-naphthalenetriol, etc.

[0150] Examples of the enol include 2-hydroxy-3-methyl-2-butene and 3-hydroxy-4-methyl-3-hexene.

[0151] Examples of the thiol include mercaptoethanol and mercaptopropanol.

[0152] Examples of the acid imide include carboxylic acid imides such as maleimide and succinimide; and sulfonic acid imides such as di(trifluoromethanesulfonic acid)imide and di(pentafluoroethanesulfonic acid)imide.

[0153] Examples of the oxime include aldoximes such as benzaldoxime and salicylaldoxime; and ketoximes such as diethylketoxime, methylethylketoxime and cyclohexanoneoxime.

[0154] Examples of the sulfonamide include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, and toluenesulfonamide.

[0155] The organic acid [a3] is preferably a carboxylic acid having a functional group (I), more preferably a monocarboxylic acid having a functional group (I), still more preferably a monocarboxylic acid having an ethylenic carbon-carbon double bond-containing group, and particularly preferably methacrylic acid.

[0156] As the compound (A3-1), particles containing a metal atom [m3] and a ligand [p] are preferred, particles containing a metal atom [m3] of Group 4, Group 5, Group 14, or Group 16 and a ligand derived from a carboxylic acid having a functional group (I) are more preferred, particles containing titanium, zirconium, tellurium, hafnium, tantalum, tungsten, or tin and a ligand derived from a monocarboxylic acid having an ethylenic carbon-carbon double bond-containing group are even more preferred, and particles containing zirconium and methacrylic acid are particularly preferred.

[0157] The lower limit of the content of the [p] ligand in the compound (A3-1) is preferably 1 mass %, more preferably 5 mass %, and even more preferably 10 mass %, while the upper limit of the content is preferably 90 mass %, more preferably 70 mass %, and even more preferably 50 mass %.

[0158] The upper limit of the average particle size of compound (A3) is preferably 20 nm, more preferably 15 nm, even more preferably 10 nm, particularly preferably 8 nm, even more particularly preferably 5 nm, and most preferably 3 nm. The lower limit of the average particle size is preferably 0.5 nm, more preferably 1 nm. By setting the average particle size of compound (A3) within the above range, the generation of secondary electrons by compound (A3) can be more effectively promoted, the sensitivity of the radiation-sensitive composition can be further improved, and as a result, the pattern formability and scum suppression properties can be further improved. Here, "average particle size" refers to the harmonic mean particle size based on scattered light intensity measured by DLS.

[0159] ((Compound [B])) In the third aspect of this embodiment, when compound (A) includes a particulate compound (A3) having one or more first functional groups (hereinafter also referred to as "functional group (I)"), which includes a metal oxide containing a metal atom or a metalloid atom and an oxygen atom, the semiconductor manufacturing composition containing compound (A) may also include compound [B3]. Compound [B3] is a compound having one or more functional groups (II). Functional group (II) is a functional group that reacts with functional group (I) of compound (A3).

[0160] ((Functional Group (II))) The functional group (II) is a functional group that reacts with the functional group (I) possessed by the compound (A3). The reaction between the functional group (I) and the functional group (II) is not particularly limited as long as it changes the structures of the functional group (I) and the functional group (II) before and after the reaction, resulting in a change in polarity. Examples of the reaction include an oxidation-reduction reaction, a disproportionation reaction, a condensation reaction, a polymerization reaction, and an addition reaction. Among these, the addition reaction is preferred. Examples of the addition reaction include a reaction in which a thioether group is formed from an ethylenic carbon-carbon double bond-containing group and a sulfanyl group, a reaction in which a substituted amino group is formed from an ethylenic carbon-carbon double bond-containing group and an amino group, a reaction in which an ether group is formed from an ethylenic carbon-carbon double bond-containing group and a hydroxy group, a reaction in which a thiocarbamate group is formed from an isocyanate group and a sulfanyl group, a reaction in which a urea group is formed from an isocyanate group and an amino group, a reaction in which a carbamate group is formed from an isocyanate group and a hydroxy group, a reaction in which a triazole ring is formed from a carbon-carbon triple bond-containing group and an azide group, and a reaction in which a carbonyloxy(hydroxy)alkanediyl group is formed from a carboxy group and an epoxy group (oxiranyl group or oxetanyl group).

[0161] Examples of the combination of the functional group (I) and the functional group (II) include a combination in which one of the functional group (I) and the functional group (II) is an ethylenic carbon-carbon double bond-containing group, a protected or unprotected isocyanate group, or a combination thereof, and the other is a protected or unprotected sulfanyl group, a protected or unprotected amino group, a protected or unprotected hydroxy group, or a combination thereof; a combination in which one of the functional group (I) and the functional group (II) is a carbon-carbon triple bond-containing group, and the other is an azide group; and the like.

[0162] Examples of the ethylenic carbon-carbon double bond-containing group include an ethenyl group, an allyl group, a styryl group, and a (meth)acrylic group.

[0163] Examples of the carbon-carbon triple bond-containing group include an ethynyl group, a propargyl group, and an ethynylphenyl group.

[0164] Protecting groups for isocyanate groups, sulfanyl groups, amino groups, and hydroxy groups include, for example, groups that can be deprotected by the action of an acid, groups that can be deprotected by the action of a base, and groups that can be deprotected by the action of EUV or EB. Groups that can be deprotected by the action of an acid are deprotected, for example, by the action of an acid generated from an acid generator [D3] or the like under the action of radiation. Groups that can be deprotected by the action of a base are deprotected, for example, by the action of a base generated from a radiation-sensitive base generator or the like under the action of radiation. Groups that can be deprotected by the action of EUV or EB are deprotected by the action of EUV or EB to generate an isocyanate group, sulfanyl group, amino group, or hydroxy group. Among these, groups that can be deprotected by the action of an acid or groups that can be deprotected by the action of EUV or EB are preferred, and groups that can be deprotected by the action of an acid are more preferred.

[0165] Examples of the protecting group for the isocyanate group include blocking agents such as dimethylpyrazole, diethylpyrazole, methylethylketoxime, and caprolactam.

[0166] Examples of the protective group for the sulfanyl group include arylcarbamoyl groups such as phenylcarbamoyl group, and triarylmethyl groups such as triphenylmethyl group.

[0167] "Amino group" includes -NH ２ The protecting groups for the amino group include not only the above but also substituted amino groups such as methylamino group, dimethylamino group, etc. Examples of the protecting groups for the amino group include alkoxycarbonyl groups such as t-butoxycarbonyl group, etc.

[0168] Examples of the protecting group for the hydroxy group include tertiary alkyl groups such as t-butyl and t-amyl, trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, and alkoxymethyl groups such as methoxymethyl and ethoxymethyl. Examples of the organic acid [a3] when the functional group (I) is an ethylenic carbon-carbon double bond-containing group include acrylic acid, methacrylic acid, vinylacetic acid, vinylbenzoic acid, allyloxybenzoic acid, and 3-butenyloxybenzoic acid.

[0169] When the functional group (I) is a protected or unprotected isocyanate group, examples of the organic acid [a3] include isocyanate acetic acid, isocyanate propionic acid, and isocyanate benzoic acid.

[0170] When the functional group (I) is a carbon-carbon triple bond-containing group, examples of the organic acid [a3] include ethynylacetic acid, ethynylpropionic acid, and ethynylbenzoic acid.

[0171] When the functional group (II) is a protected or unprotected sulfanyl group, examples of the compound [B3] include 3-sulfanylpropionic acid and di(4-sulfanylphenyl)thioether.

[0172] When the functional group (II) is a protected or unprotected amino group, examples of the compound [B3] include 3-Nt-butoxycarbonylaminopropionic acid and N,N'-di(t-butoxycarbonyl)ethylenediamine.

[0173] When the functional group (II) is a protected or unprotected hydroxy group, examples of the compound [B3] include 3-hydroxypropionic acid and di(4-hydroxyphenyl) ether.

[0174] When the functional group (II) is a combination of a sulfanyl group and a protected or unprotected amino group, examples of the compound [B3] include 1-sulfanyl-2-N-(t-butoxycarbonyl)aminoethane.

[0175] When the functional group (II) is an azide group, examples of the compound [B3] include phenyl azide and cyclohexyl azide.

[0176] The number of functional groups (II) contained in the compound [B3] is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2.

[0177] From the viewpoint of further improving the pattern formability of the radiation-sensitive composition, it is preferred that the functional group (I) is an ethylenic carbon-carbon double bond-containing group, a protected or unprotected isocyanate group, or a combination thereof, or a carbon-carbon triple bond-containing group, and the functional group (II) is a protected or unprotected sulfanyl group, a protected or unprotected amino group, a protected or unprotected hydroxy group, or a combination thereof, or an azide group.

[0178] ((Acid Generator [D3])) In the third aspect of this embodiment, when compound (A) includes a particulate compound (A3) having a functional group (I), which includes a metal oxide containing a metal atom or a metalloid atom and an oxygen atom, the semiconductor manufacturing composition containing compound (A) may also include acid generator [D3]. Acid generator [D3] is a component that generates an acid when irradiated with radiation. The action of the acid generated from acid generator [D3] can further promote changes in the solubility of compound (A3) in a developer in the semiconductor manufacturing composition. As acid generator [D3], the acid generators described below can be used.

[0179] (([E3] Radical Scavenger)) In the third aspect of this embodiment, when compound (A) includes a particulate compound (A3) having a functional group (I), which includes a metal oxide containing a metal atom or a metalloid atom and an oxygen atom, the semiconductor manufacturing composition containing compound (A) may also include [E3] radical scavenger. [E3] radical scavenger is a compound that can capture radicals and suppress radical chain reactions. Examples of [E3] radical scavengers include stable nitroxyl radical compounds, sulfide compounds, quinone compounds, phenol compounds, amine compounds, and phosphite compounds (excluding those corresponding to compound (A3) and compound [B3]).

[0180] Examples of stable nitroxyl radical compounds include piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical.

[0181] Examples of sulfide compounds include phenothiazine, pentaerythritol-tetrakis(3-laurylthiopropionate), didodecyl sulfide, dioctadecyl sulfide, didodecyl thiodipropionate, dioctadecyl thiodipropionate, dimyristyl thiodipropionate, dodecyl octadecyl thiodipropionate, and 2-mercaptobenzimidazole.

[0182] Examples of the quinone compound include benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, p-xyloquinone, and 2-hydroxy-1,4-naphthoquinone.

[0183] Examples of phenol compounds include hydroquinone, 4-methoxyphenol, 4-tert-butoxyphenol, catechol, 4-tert-butylcatechol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-m-cresol, pyrogallol, and 2-naphthol.

[0184] Examples of the amine compound include N-(2,2,6,6-tetramethyl-4-piperidyl)dodecyl succinimide, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)butanetetracarboxylate, tetra(1,2,2,6,6-pentamethyl-4-piperidyl)butanetetracarboxylate, and N,N'-di-sec-butyl-1,4-phenylenediamine.

[0185] Examples of the phosphite compound include triisodecyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and trinonylphenyl phosphite.

[0186] [E3] As the radical scavenger, in addition to the above compounds, high molecular weight radical scavengers such as "Chimasorb 2020" from BASF and "Adekastab LA-68" from ADEKA can also be used.

[0187] [E3] As the radical scavenger, among these, stable nitroxyl radical compounds are preferred, and 2,2,6,6-tetramethylpiperidine 1-oxyl free radical is more preferred.

[0188] ((Other Optional Components)) The composition for manufacturing a semiconductor containing compound (A) may contain, as other optional components, a surfactant, an adhesion aid, an acid generator, a polymer additive, a polymerization inhibitor, a radiation-sensitive radical generator, an acid diffusion controller, a photodegradable base, a sensitizer, an organic carboxylic acid or a phosphorus oxoacid or a derivative thereof, etc. Furthermore, the composition for manufacturing a semiconductor may contain, in addition to the other components described above, a dye, a pigment, an adhesion aid, an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improver, etc.

[0189] By including a polymer additive in the composition for semiconductor manufacturing, for example, when the composition for semiconductor manufacturing is used as a resist auxiliary film, the coating properties on a substrate or an organic underlayer film and the film continuity can be further improved. Examples of the polymer additive include a (poly)oxyalkylene polymer compound, a fluorine-containing polymer compound, and a non-fluorine-containing polymer compound.

[0190] The storage stability of the semiconductor manufacturing composition can be improved by including a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone compounds such as 2,5-di-tert-butylhydroquinone, and nitroso compounds such as N-nitrosophenylhydroxylamine and its aluminum salt.

[0191] The radiation-sensitive radical generator is a component that generates radicals upon irradiation with radiation. Known compounds can be used as the radiation-sensitive radical generator.

[0192] The acid diffusion controller controls the diffusion phenomenon in the film of acid generated from an acid generator or the like upon exposure, thereby suppressing undesirable chemical reactions in unexposed regions. The storage stability of the semiconductor manufacturing composition is further improved, and the resolution is further improved. Furthermore, changes in the line width of the pattern due to variations in the exposure time until development can be suppressed, resulting in a semiconductor manufacturing composition with excellent process stability. Examples of the acid diffusion controller include nitrogen-containing compounds and photodecomposable bases that generate weak acids upon irradiation with radiation.

[0193] Examples of photodegradable bases include onium salt compounds that decompose upon exposure to light and lose their acid diffusion control properties, such as triphenylsulfonium salts and diphenyliodonium salts.

[0194] The acid generator may be any compound that can generate an acid directly or indirectly by heating or by irradiation with radiation such as visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, or ion beam. Examples of the acid generator include onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, diazoketone compounds, etc. Examples of the onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, and pyridinium salts.

[0195] The acid diffusion controller is an additive that has the effect of controlling the diffusion of the acid generated from the acid generator in the resist film or the resist auxiliary film, thereby preventing undesirable chemical reactions, etc. The acid diffusion controller is not particularly limited, and examples thereof include radiation-decomposable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

[0196] A sensitizer is an additive that absorbs the energy of irradiated radiation and transfers that energy to an acid generator, thereby increasing the amount of acid produced. It is also an additive that absorbs light of a specific wavelength. Examples of sensitizers include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes.

[0197] The surfactant is an additive that has the effect of improving the coatability and striation of the resist film composition or resist auxiliary film composition, the developability of the resist film composition or resist auxiliary film composition, etc. The surfactant may be any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, but nonionic surfactants are preferred. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol.

[0198] Organic carboxylic acids or phosphorus oxo acids or derivatives thereof are additives that have the effect of preventing sensitivity degradation or improving resist pattern shape, deposition stability, etc. Examples of organic carboxylic acids include, but are not limited to, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. Examples of phosphorus oxo acids or derivatives thereof include phosphoric acids or ester derivatives thereof, such as phosphoric acid, di-n-butyl phosphoric acid ester, diphenyl phosphoric acid ester, etc.; phosphonic acids or ester derivatives thereof, such as phosphonic acid, dimethyl phosphonic acid ester, di-n-butyl phosphonic acid ester, phenylphosphonic acid, diphenyl phosphonic acid ester, dibenzyl phosphonic acid ester, etc.; and phosphinic acids or ester derivatives thereof, such as phenylphosphinic acid and phenylphosphinic acid.

[0199] 2. Removal Method The removal method of the present embodiment is a method for removing a metal compound or a semi-metal compound, and includes a step of removing the metal compound or semi-metal compound using a solvent composition containing a solvent (B) that includes a compound (B1) represented by the following general formula (b-1): [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

[0200] In this embodiment, since the compound (B1) has high solubility, the solvent composition containing the solvent (B) containing the compound (B1) also has high solubility. Metal compounds or semimetallic compounds tend to be poorly soluble in solvents, but the solvent composition of this embodiment has high solubility, so it can effectively dissolve the metal compounds or semimetallic compounds. Therefore, the metal compounds or semimetallic compounds can be removed to a high degree. Therefore, by carrying out the removal method of this embodiment in, for example, an EBR process, a back-rinse process, a rework process, a development process, or the like, which are performed to remove residues and contaminants from a resist film or resist auxiliary film containing a metal compound or semimetallic compound, the metal compounds and semimetallic compounds can be effectively removed.

[0201] In the removal method of this embodiment, the same configuration as that described for the solvent composition of this embodiment can be employed, and the description thereof will be omitted. Specifically, in the removal method of this embodiment, for example, the solvent composition of this embodiment described above can be used as the solvent composition, and the metal compound or semimetal compound (compound (A)) to be removed can be the same as that of the solvent composition of this embodiment.

[0202] 3. Semiconductor Device Manufacturing Method The semiconductor device manufacturing method of this embodiment is a manufacturing method in which a solvent composition containing a solvent (B) containing a compound (B1) represented by the above-mentioned general formula (b-1) is used in one step of the semiconductor device manufacturing process. Hereinafter, each aspect of the semiconductor device manufacturing method of this embodiment (hereinafter also referred to as the "manufacturing method") will be described. Note that the manufacturing method of this embodiment can employ the same configuration as that described for the solvent composition of this embodiment above, and the description thereof will be omitted. Specifically, for example, the solvent (B) in the manufacturing method of this embodiment can be the same as the solvent (B) in the solvent composition of this embodiment above, and the solvent composition in the manufacturing method of this embodiment can employ a configuration related to other components that can be contained in the solvent composition of this embodiment. The solvent composition in the manufacturing method of this embodiment can also employ a configuration related to the application of the solvent composition, as necessary. Furthermore, the metal compound or semimetallic compound (compound (A)), and further the semiconductor manufacturing composition containing compound (A), in the semiconductor device manufacturing method of this embodiment can employ the same configuration as that of compound (A) and the semiconductor manufacturing composition described for the solvent composition of this embodiment above.

[0203] More specifically, the production method of the first aspect of the present embodiment is a method for producing a semiconductor device, comprising a step of directly or indirectly applying, onto a substrate, a solvent composition containing a solvent (B) that includes a compound (B1) represented by the following general formula (b-1), before applying a metal compound or a semi-metal compound onto the substrate: [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

[0204] According to the manufacturing method of the first aspect of this embodiment, before applying compound (A) to a substrate, a solvent composition containing a solvent (B) containing a highly soluble compound (B1) is applied directly or indirectly to the substrate, thereby suppressing defects due to precipitation of compound (A). In the first aspect and aspects described below, applying compound (A) to a substrate does not only mean applying compound (A) alone, but also means applying a semiconductor manufacturing composition containing compound (A) as a main component, applying a semiconductor manufacturing composition containing compound (A) as a partial additive, or applying a semiconductor manufacturing composition containing compound (A) unintentionally. In the first aspect, a resist underlayer film can be formed on a substrate by applying compound (A) directly or indirectly to the substrate.

[0205] In the production method of the first aspect, and the production methods of the second and third aspects described below, the solvent (B) preferably contains, as the solvent (B2) other than the compound (B1), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate.

[0206] Furthermore, a manufacturing method of a second aspect of this embodiment is a manufacturing method of a semiconductor device, which includes a step of applying a metal compound or a semi-metal compound onto a substrate, an exposure step, and then applying the solvent composition of this embodiment onto the substrate. According to the manufacturing method of the second aspect of this embodiment, a step of applying a solvent composition having high solubility to compound (A) onto the substrate, an exposure step, and then applying the solvent composition to the substrate, which can efficiently dissolve unexposed areas and improve the resolution of patterning.

[0207] Furthermore, a manufacturing method of a third aspect of this embodiment is a method for manufacturing a semiconductor device, comprising the steps of forming a film of a metal compound or a semimetal compound on a substrate, and removing the film formed of the metal compound or semimetal compound using the solvent composition of this embodiment described above. According to the manufacturing method of the third aspect of this embodiment, the film of compound (A) formed on the substrate is removed using a solvent composition having high solubility, so that compound (A) can be effectively removed. The film formed of a metal compound or a semimetal compound can be, for example, a resist film or a resist underlayer film.

[0208] In the third aspect, the resist film or resist underlayer film is preferably removed by contacting the edge and / or back surface of the substrate on which the resist film or resist underlayer film is formed with the solvent composition. Also, in this embodiment, the resist film or resist underlayer film is preferably removed by spraying the solvent composition onto the edge and / or back surface of the substrate while rotating the substrate on which the resist film or resist underlayer film is formed.

[0209]

[0023] Also preferred is an embodiment further comprising a step of drying the solvent composition remaining on the substrate after the step of removing the resist film or resist underlayer film. Also preferred is an embodiment further comprising a step of soft-baking the resist film, a step of partially exposing the soft-baked resist film using a mask, and a step of developing the exposed resist film with a developer to form a resist pattern. Furthermore, when a resist film or resist underlayer film is formed on the edge and / or back surface of the substrate, also preferred is an embodiment further comprising a step of removing the resist film or resist underlayer film from the edge and / or back surface of the substrate after forming the resist film or resist underlayer film on the substrate.

[0210] By treating a substrate with the solvent composition and then coating the substrate with a resist or a resist underlayer film, it is possible to coat the substrate with a small amount of resist or resist underlayer film, thereby improving process costs and productivity.

[0211] The method for manufacturing a semiconductor device of the present invention can include a step of treating the substrate with the solvent composition, applying a resist or a resist underlayer film thereto, and further treating the substrate with the solvent composition before the exposure step.

[0212] In the above step, by further treating the substrate with a solvent composition, unnecessary resist or resist underlayer film applied to the peripheral portion or rear surface of the substrate can be rapidly and effectively removed before the exposure step.

[0213] Although the embodiments of the present invention have been described above, the present invention is not limited to the above examples and can be modified as appropriate.

[0214] The present invention will be described in more detail below with reference to examples. However, the materials, amounts used, ratios, processing details, processing procedures, etc. shown in the examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "%" in the examples is based on mass.

[0215] The solvent compositions of each example and comparative example were prepared as follows, and each evaluation was performed. 1: Preparation of Metal Compounds and Metalloid Compounds Synthesis Example 1: Synthesis of Metal Compound (A-1) Using a 50 mL glass round-bottom flask reaction apparatus, 3.18 g of an 85% zirconium (IV) tetrabutoxide / 1-butanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 9 g of methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed under a nitrogen atmosphere and stirred at 65°C for 2 hours. The resulting compound was washed twice with 100 mL of hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and dried in vacuo at 40°C to obtain 1.8 g of metal compound (A-1) containing a metal atom and an organic ligand.

[0216] Synthesis Example 2: Synthesis of metalloid compound (A-2) Using the same reaction apparatus as in Synthesis Example 1, 3.1 g of an 85% tellurium (IV) ethoxide ethanol solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as the raw material for the metalloid atom, and 9 g of methacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as the organic ligand, 1.5 g of a metalloid compound (A-2) containing a metalloid atom and an organic ligand was obtained by the same reaction method as in Synthesis Example 1.

[0217] Synthesis Example 3 Synthesis of Metalloid Compound (A-3) 1.4 g of a metalloid compound (A-3) containing a metalloid atom and an organic ligand was obtained by the same reaction method as in Synthesis Example 2, except that 3.1 g of an 85% tellurium (IV) ethoxide ethanol solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used as the raw material for the metalloid atom, and 7 g of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used as the organic ligand.

[0218] Synthesis Example 4 Synthesis of Metalloid Compound (A-4) 1.2 g of a metalloid compound (A-4) containing a metalloid atom and an organic ligand was obtained by the same reaction method as in Synthesis Example 2, except that 3.1 g of an 85% tellurium (IV) ethoxide ethanol solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used as the raw material for the metalloid atom, and 9 g of benzoic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used as the organic ligand.

[0219] Synthesis Example 5 Synthesis of Metalloid Compound (A-5) 1.5 g of a metalloid compound (A-5) containing a metalloid atom and an organic ligand was obtained by the same reaction method as in Synthesis Example 2, except that 3.1 g of an 85% tellurium (IV) ethoxide ethanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the raw material for the metalloid atom, and 10 g of 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Gas Chemical Company, Ltd.) was used as the organic ligand.

[0220] Synthesis Example 6 Synthesis of Metalloid Compound (A-6) 1.2 g of a metalloid compound (A-6) containing a metalloid atom and an organic ligand was obtained by the same reaction method as in Synthesis Example 2, except that 3.1 g of an 85% tellurium (IV) ethoxide ethanol solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the raw material for the metalloid atom, and 10 g of 4-vinylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the organic ligand.

[0221] 2: Preparation of Solvent Compositions The solvent compositions of each Example and Comparative Example were prepared as follows. The compound (B1) and solvent (B2) used are as follows: - 2-Methyl 2-hydroxyisobutyrate (HBM): manufactured by Mitsubishi Gas Chemical Company, Inc. - Methyl α-methoxyisobutyrate (α-MBM): synthesized with reference to "US 2014 / 0275016". - Methyl α-formyloxyisobutyrate (α-FBM): synthesized with reference to "WO 2020 / 004467". - Methyl 3-hydroxyisobutyrate (3-HBM): manufactured by Tokyo Chemical Industry Co., Ltd. - Propylene glycol monomethyl ether acetate (PGMEA): manufactured by Sigma-Aldrich Co., Ltd. - Cyclohexanone (CHN): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. - γ-Butyrolactone (GBL): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0222] Example 1 Methyl 2-hydroxyisobutyrate (HBM) was used as the solvent composition.

[0223] Example 2 A solvent composition prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-methoxyisobutyrate (α-MBM) in a mass ratio of 50:50 was used.

[0224] Example 3 A solvent composition prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-methoxyisobutyrate (α-MBM) in a mass ratio of 99:1 was used.

[0225] Example 4 A solvent composition was used in which methyl 2-hydroxyisobutyrate (HBM) and methyl α-formyloxyisobutyrate (α-FBM) were mixed in a mass ratio of 50:50.

[0226] Example 5 A solvent composition prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-formyloxyisobutyrate (α-FBM) in a mass ratio of 99:1 was used.

[0227] Example 6 A solvent composition prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-formyloxyisobutyrate (α-FBM) in a mass ratio of 99.9:0.1 was used.

[0228] Example 7 A solvent composition prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl 3-hydroxyisobutyrate (3-HBM) in a mass ratio of 50:50 was used.

[0229] Example 8 A solvent composition prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl 3-hydroxyisobutyrate (3-HBM) in a mass ratio of 99:1 was used.

[0230] Example 9 A solvent composition prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl 3-hydroxyisobutyrate (3-HBM) in a mass ratio of 99.9:0.1 was used.

[0231] Comparative Example 1 Propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent composition.

[0232] Comparative Example 2 Cyclohexanone (CHN) was used as the solvent composition.

[0233] Comparative Example 3 γ-butyrolactone (GBL) was used as the solvent composition.

[0234] The solvent compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1 below.

[0235] 3: Solubility Test The metal compounds, semi-metal compounds, and photoacid generators used in the following solubility tests are as follows: Metal compounds and semi-metal compounds: metal compound (A-1), semi-metal compounds (A-2) to (A-6) Photoacid generator (PAG): acid generator (C-1) (TPS-CS (manufactured by Toyo Gosei Co., Ltd.))

[0236] (1) Solubility Test 1 Solubility evaluation of the metal compound (A-1) or the semi-metallic compounds (A-2) to (A-6) was carried out using the solvent compositions of Examples 1 to 9 and Comparative Examples 1 to 3. Specifically, the metal compound or semi-metallic compound was added to the solvent composition and stirred at room temperature for 24 hours. The state of the solution after stirring was visually confirmed and evaluated according to the following criteria (composition for manufacturing semiconductors being 100 wt%). The evaluation results are shown in Table 2. - Rating S: 10 wt% dissolved (clear solution confirmed visually) - Rating A: 5 wt% dissolved (clear solution confirmed visually) - Rating C: Insoluble (cloudy solution confirmed visually when 5 wt% of the metal compound or photoacid generator was added)

[0237] As shown in Table 2 below, the solvent compositions prepared in Examples 1 to 9 were found to have superior solubility for metal compounds and photoacid generators compared to the solvent compositions of Comparative Examples 1 to 3, and were found to be particularly useful as solvent compositions for EBR, back-rinse, rework, and development. This was presumably due to the high solubility of compound (B1) contained in solvent (B). Furthermore, solvent compositions in which solvent (B) contains α-FBM or 3-HBM as solvent (B2) in particular exhibit high solubility for metal compounds and photoacid generators and are therefore suitable for use. On the other hand, when the solvent compositions of Comparative Examples were used, some of the metal compounds or semimetallic compounds (A-1) to (A-6) were insoluble, confirming that they were not useful as solvent compositions.

[0238] In this way, when a solvent composition satisfying the requirements of this embodiment is used, better solubility can be imparted compared to solvent compositions of comparative examples that do not satisfy these requirements. As long as the requirements of this embodiment are satisfied, solvent compositions other than those described in the examples also exhibit the same effect.

[0239] (2) Solubility Test 2 The solvent compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were used to evaluate the solubility of the metal compound (A-1) and the photoacid generator (C-1). Specifically, the metal compound (A-1) and the photoacid generator (C-1) were added to the solvent composition so that the concentrations of both were 10 wt % or 5 wt %, based on 100 wt % of the final semiconductor manufacturing composition. In other words, the metal compound (A-1) and the photoacid generator (C-1) were added so that the total concentration was 20 wt % or 10 wt %, based on 100 wt % of the final semiconductor manufacturing composition. The solution was stirred for 24 hours at room temperature. The state of the solution after stirring was visually confirmed and evaluated according to the following criteria (based on the semiconductor manufacturing composition being 100 wt %). The evaluation results are shown in Table 2. Grade S: 10 wt % dissolved (visually confirmed as clear solution) Grade A: 5 wt % dissolved (visually confirmed as clear solution) Grade C: Insoluble (visually confirmed as cloudy solution when 5 wt % of metal compound and photoacid generator were added)

[0240] Table 2 below shows that the solvent compositions prepared in Examples 1 to 9 had superior solubility for metal compounds and photoacid generators compared to the solvent compositions of Comparative Examples 1 to 3. This is presumably due to the high solubility of compound (B1) contained in solvent (B). In particular, solvent compositions in which solvent (B) contained α-FBM or 3-HBM as solvent (B2) exhibited high solubility for metal compounds and photoacid generators and were preferably used.

[0241] The solvent composition of the present invention has excellent solubility for a variety of photoresist films, photoresist underlayer films (films coated on the underlayer of a photoresist, such as bottom antireflective coating (BARC) or spin-on carbon film), and photoresist overlayer films (top antireflective coating (TARC)), and is capable of improving not only EBR properties and rework properties but also RRC properties. In particular, in the case of photoresists for g-line, i-line, KrF, ArF, EUV, or EB, the basic structures of the constituent photoresists are different, so that in order to improve the solubility and coatability of all of these, it is necessary to adjust the compositional content of the organic solvent, and the solvent composition of the present invention satisfies this requirement. As long as the requirements of this embodiment are met, similar effects can be obtained with solvent compositions other than those described in the examples.

[0242]

[0243] According to the present invention, it is possible to provide a removal method and a solvent composition that can remove metal compounds or semi-metal compounds to a high degree even when a semiconductor manufacturing composition containing a metal compound or semi-metal compound is used, and a manufacturing method that can effectively manufacture semiconductor devices even when such a semiconductor manufacturing composition is used.

Claims

1. A method for removing a metal compound or a semi-metal compound, comprising the step of removing the metal compound or semi-metal compound using a solvent composition containing a solvent (B) which contains a compound (B1) represented by the following general formula (b-1): [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

2. R in the general formula (b-1) １ The removal method according to claim 1, wherein is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, or a t-butyl group.

3. The removal method according to claim 1 or 2, wherein the solvent (B) contains a solvent (B2) other than the compound (B1).

4. The removal method according to claim 3, wherein the solvent (B) includes, as the solvent (B2), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate.

5. The removal method according to claim 3, wherein the solvent (B2) contains 100 mass % or less of the compound (B1) based on the total amount (100 mass %) of the compound (B1).

6. The removal method according to claim 3, wherein the solvent (B2) contains 0.0001 mass % or more of the compound (B1) based on the total amount (100 mass %) of the compound (B1).

7. The removal method according to claim 1 or 2, wherein the metal compound or metalloid compound contains an element belonging to any one of the third to seventh periods of groups 3 to 16 of the periodic table.

8. The removal method according to claim 1 or 2, wherein the metal compound or semimetal compound comprises one or more selected from the group consisting of titanium, zirconium, hafnium, tantalum, tungsten, zinc, germanium, tin, and tellurium.

9. The removal method according to claim 1 or 2, wherein the ligands that bind to the metal compound or metalloid compound include a halogen ligand, a hydroxo ligand, a carboxy ligand, an alkoxy ligand, a carboxylate ligand, an alkyl ligand, or an amide ligand.

10. A solvent composition used to remove a metal compound or a semi-metal compound, comprising a solvent (B) containing a compound (B1) represented by the following general formula (b-1): [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

11. The solvent composition according to claim 10, wherein the solvent (B) contains a solvent (B2) other than the compound (B1).

12. A method for producing a semiconductor device, comprising a step of directly or indirectly applying a solvent composition containing a solvent (B) that includes a compound (B1) represented by the following general formula (b-1) onto a substrate before applying a metal compound or a semimetallic compound onto the substrate: [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

13. The method for producing a semiconductor device according to claim 12, wherein the solvent (B) contains, as a solvent (B2) other than the compound (B1), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate.

14. A method for producing a semiconductor device, comprising the steps of applying a metal compound or a semi-metal compound onto a substrate, and then, after an exposure step, applying the solvent composition according to claim 10 or 11 onto the substrate.

15. A method for manufacturing a semiconductor device, comprising: forming a film of a metal compound or a semi-metal compound on a substrate; and removing the film formed of the metal compound or the semi-metal compound using the solvent composition according to claim 10 or 11.

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