Composition for semiconductor manufacturing and film forming method

Abstract

The present invention provides a composition for semiconductor manufacturing, containing: a metal compound or a semimetal compound (A); and a solvent (B) containing a compound (B1) represented by general formula (b-1). The content of the active ingredient in the total amount of the composition for semiconductor manufacturing is 45 mass % or less. [In formula (b-1), R1 represents an alkyl group having 1-10 carbon atoms.]

Description

Composition for semiconductor manufacturing and film forming method

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

[0002] In the manufacture of semiconductors, microfabrication is carried out by lithography using photoresist materials. Lithography typically involves forming a resist on a wafer, followed by exposure and development, followed by etching or other processes to form a circuit pattern on the wafer, and finally peeling and removing the resist.

[0003] In recent years, semiconductors have become more sophisticated and smaller in size, and there is a demand for further miniaturization of pattern dimensions.

[0004] In order to cope with such miniaturization of pattern dimensions, short wavelength light sources are used as exposure light sources, including ultraviolet rays such as the g-line (wavelength 436 nm) and i-line (wavelength 365 nm) of a high-pressure mercury lamp, far ultraviolet rays such as KrF excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm), and extreme ultraviolet rays (EUV).

[0005] However, when a short-wavelength exposure light source is used, the resolution performance of the resist may be reduced due to the influence of reflection of the exposure light source from the wafer or standing waves. To address this problem, a technique is known in which a bottom anti-reflective coating (BARC) is formed between the resist and the wafer as a resist auxiliary film (see, for example, Patent Document 1).

[0006] On the other hand, instead of miniaturizing the pattern dimensions as described above, there is also known a technology relating to three-dimensional packaging in which semiconductor elements are integrated three-dimensionally using minute electrodes (bumps) to increase memory capacity (for example, Patent Document 2). Note that Patent Document 2 describes that in three-dimensional packaging, minute electrodes (bumps) are formed using a thick resist film to maintain the distance between semiconductor elements.

[0007] International Publication No. 2004 / 034148 Japanese Patent Application Laid-Open No. 2019-137612 Japanese Patent Application Laid-Open No. 2011-253185

[0008] In recent years, in order to further reduce pattern dimensions, the formation of resist films using semiconductor manufacturing compositions containing metal compounds or semimetal compounds has been investigated (see, for example, Patent Document 3). Semiconductor manufacturing compositions containing metal compounds or semimetal compounds have also been investigated as materials that can be used in resist auxiliary films (see, for example, Patent Document 3). However, when metal compounds or semimetal compounds are used in semiconductor manufacturing compositions, there is a need to further improve the productivity and quality of the resulting products in the production of semiconductor manufacturing compositions and in the semiconductor manufacturing process using such compositions. Specifically, for example, the solubility of metal compounds or semimetal compounds in solvents and the in-plane uniformity of the formed films are not sufficient, and further improvement is required. In addition, metal compounds or semimetal compounds are expensive materials, and there is a need to reduce the amount of such compounds used when forming resist films or resist auxiliary films.

[0009] Therefore, an object of the present invention is to provide a composition for semiconductor manufacturing that can improve the solubility of a metal compound or semi-metal compound in a solvent and the in-plane uniformity of the formed film, and further, can reduce the amount of the compound used, as well as a film formation method using the composition for semiconductor manufacturing.

[0010] The present invention provides, for example, the following composition for manufacturing a semiconductor and film forming method: [1] A composition for manufacturing a semiconductor, comprising (A) a metal compound or a metalloid compound and (B) a solvent containing (B1) a compound represented by the following general formula (b-1), wherein the content of an active ingredient in the composition for manufacturing a semiconductor is 45 mass % or less based on the total amount of the composition for manufacturing a semiconductor: [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.] [2] The composition for manufacturing a semiconductor according to the above [1], further comprising at least one additive (C) selected from a photosensitizer and an acid generator. [3] 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. [4] The semiconductor manufacturing composition according to any of [1] to [3] above, 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. [5] The semiconductor manufacturing composition according to [4] above, wherein the solvent (B2) accounts for 100% by mass or less of the total amount (100% by mass) of the compound (B1). [6] The semiconductor manufacturing composition according to [4] or [5] above, wherein the solvent (B2) accounts for 0.0001% by mass or more of the total amount (100% by mass) of the compound (B1). [7] The composition for manufacturing a semiconductor according to any one of [1] to [6] above, wherein the metal atom or metalloid atom contained in the compound (A) is an atom of an element belonging to any one of Periods 3 to 7 of Groups 3 to 16 of the Periodic Table. [8] The composition for manufacturing a semiconductor according to any one of [1] to [7] above, wherein the metal atom or metalloid atom contained in the compound (A) is an atom of any one of titanium, zirconium, hafnium, tantalum, tungsten, zinc, germanium, tin, and tellurium. [9] The composition for manufacturing a semiconductor according to any one of [1] to [8] above, wherein the compound (A) contains, as a ligand bonding to the metal atom or metalloid atom of the compound (A), a halogen ligand, a hydroxo ligand, a carboxy ligand, an alkoxy ligand, a carboxylate ligand, an alkyl ligand, or an amide ligand.

[10] A film forming method comprising: step (1): applying the composition for manufacturing a semiconductor according to any one of [1] to [9] above onto a substrate to form a coating film, step (2): performing a heat treatment after step (1), and step (3): forming a resist pattern.

[11] The composition for manufacturing a semiconductor according to any one of [1] to [9] above, wherein the composition for manufacturing a semiconductor is a resist composition.

[12] The composition for manufacturing a semiconductor according to any one of [1] to [9] above, wherein the composition for manufacturing a semiconductor is a resist auxiliary film composition.

[13] The composition for manufacturing a semiconductor according to the above

[12] , wherein the resist auxiliary film is a resist underlayer film or a resist intermediate layer film.

[0011] According to the present invention, it is possible to provide a composition for semiconductor manufacturing that can increase the solubility of a metal compound or semi-metal compound in a solvent and the in-plane uniformity of a formed film, and further, can reduce the amount of the compound used, as well as a film formation method using the composition for semiconductor manufacturing.

[0012] 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."

[0013] 1. Composition for manufacturing a semiconductor The composition for manufacturing a semiconductor of this embodiment is a composition for manufacturing a semiconductor containing a metal compound or semi-metal compound (A) (hereinafter also referred to as "compound (A)") and a solvent (B) containing a compound (B1) represented by the following general formula (b-1). Furthermore, in the composition for manufacturing a semiconductor of this embodiment, the content of the active ingredient based on the total amount of the composition for manufacturing a semiconductor is 45 mass% or less. The composition for manufacturing a semiconductor of this embodiment can be used as a radiation-sensitive composition. [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

[0014] In this embodiment, compound (B1) has high solubility. While compound (A) tends to be poorly soluble in solvents, solvent (B) containing highly soluble compound (B1) can also dissolve compound (A) more easily. Furthermore, solvent (B) containing compound (B1) has high solubility, making it less likely for defects to occur in coated films (e.g., resist films and resist auxiliary films), thereby improving the in-plane uniformity of the formed films. Furthermore, solvent (B) containing compound (B1) tends to have a relatively high viscosity, which can prevent scattering of the semiconductor manufacturing composition, for example, when forming a resist film or resist auxiliary film by spin coating. Therefore, a film of the desired thickness can be efficiently obtained without applying an excessive amount of compound (A), which can be an expensive material. Therefore, when a material such as a metal compound or a semimetal compound is used in a semiconductor manufacturing composition such as a resist film or resist auxiliary film, productivity and the quality of the resulting product can be improved in the production of the semiconductor manufacturing composition and in the semiconductor manufacturing process using the composition.

[0015] Here, in this specification, the term "active ingredient" refers to the components contained in the semiconductor manufacturing composition excluding the solvent (B) (hereinafter also referred to as "component (B)"). Specifically, the "active ingredient" contained in the semiconductor manufacturing composition of this embodiment includes the compound (A), the components added together with the compound (A) described below, and other additives. Examples of other additives include the additives described below, such as acid generators, acid diffusion controllers, dissolution promoters, dissolution controllers, sensitizers, surfactants, organic carboxylic acids or phosphorus oxoacids or derivatives thereof, organic acids, dyes, pigments, adhesion aids, antihalation agents, storage stabilizers, defoamers, and shape improvers. Generally, for example, in order to manufacture devices having high-resolution wiring patterns, it is necessary to form a resist film containing a metal. Furthermore, generally, for example, in order to use the compound (A) as a mask with high etching resistance, it is necessary to form a resist auxiliary film containing a metal. However, the metal-containing compound (A) contains rare metals and other substances that are rare and expensive on Earth, making it difficult to use a semiconductor manufacturing composition with a high content of the compound (A) as a resist composition or a resist auxiliary film composition. In contrast, the composition for manufacturing a semiconductor of this embodiment uses compound (B1) represented by general formula (b-1) as a solvent, and therefore can be a photoresist material capable of forming a resist film or a resist auxiliary film with a thickness suitable for manufacturing various devices, even if the content of the active ingredient including compound (A) is reduced. In addition, the composition for manufacturing a semiconductor of this embodiment has an economic advantage because the content of the active ingredient is reduced.

[0016] In the semiconductor manufacturing composition of this embodiment, the content of the active ingredient may be set appropriately depending on the application, such as 42% by mass or less, 40% by mass or less, 36% by mass or less, 31% by mass or less, 26% by mass or less, 23% by mass or less, 20% by mass or less, 18% by mass or less, 16% by mass or less, 12% by mass or less, 10% by mass or less, 6% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less, relative to the total amount (100% by mass) of the semiconductor manufacturing composition. Meanwhile, the lower limit of the active ingredient content is also set appropriately depending on the application, and may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 4% by mass or more, 7% by mass or more, or 10% by mass or more, relative to the total amount (100% by mass) of the semiconductor manufacturing composition. The content of the active ingredient can be specified in any combination by appropriately selecting from the above-mentioned upper and lower limit options.

[0017] In addition, in the composition for manufacturing a semiconductor of the present embodiment, from the viewpoint of using it as a photoresist material capable of forming a resist film or a resist auxiliary film, the content of compound (A) in the active ingredients is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, even more preferably 70 to 100 mass%, still more preferably 75 to 100 mass%, and particularly preferably 80 to 100 mass%, relative to the total amount (100 mass%) of the active ingredients contained in the composition for manufacturing a semiconductor.

[0018] The composition for manufacturing a semiconductor of this embodiment may contain other components in addition to the compound (A) and the solvent (B) depending on the application. However, in the composition for manufacturing a semiconductor of this embodiment, the total content of the compound (A) and the solvent (B) is preferably 30 to 100 mass%, more preferably 40 to 100 mass%, even more preferably 60 to 100 mass%, still more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%, based on the total amount (100 mass%) of the composition for manufacturing a semiconductor.

[0019] The composition of this embodiment will be further described below. <Solvent (B)> The composition for manufacturing a semiconductor of this embodiment contains a solvent (B) containing a compound (B1) represented by the following general formula (b-1). The compound (B1) may be used alone or in combination of two or more types.

[0020]

[0021] 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.

[0022] 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. １ is even more preferably a methyl group.

[0023] Furthermore, the semiconductor manufacturing composition of this embodiment preferably contains, as component (B), a solvent (B2) other than the compound (B1). 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.

[0024] However, from the viewpoint of using the composition for manufacturing a semiconductor of this embodiment as a photoresist material or a photoresist auxiliary film material capable of forming a resist film or a resist auxiliary film, the content of compound (B1) in component (B) is preferably 5 to 100 mass%, more preferably 20 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 composition for manufacturing a semiconductor.

[0025] Component (B) used in this embodiment preferably contains, as solvent (B2), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, methyl 3-hydroxyisobutyrate, and 1-methoxy-2-propanol. More preferably, component (B) contains, as solvent (B2), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate. Even more preferably, component (B) contains, as solvent (B2), one or more selected from the group consisting of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, and methyl 3-hydroxyisobutyrate. This allows the properties of the composition for manufacturing a semiconductor to be effectively adjusted. Specifically, by including the solvent (B2) as described above in component (B), it is possible to adjust, for example, the solubility of the semiconductor manufacturing composition, the in-plane uniformity of each film formed using the semiconductor manufacturing composition, and the reduction in the amount of materials used when forming each film. The inclusion of methyl α-methoxyisobutyrate is preferred from the viewpoint of effectively facilitating a reduction in the amount of materials used when forming each film. The inclusion of methyl α-formyloxyisobutyrate is preferred from the viewpoint of effectively improving the solubility of the semiconductor manufacturing composition. The inclusion of methyl 3-hydroxyisobutyrate is preferred from the viewpoint of effectively improving the solubility of the semiconductor manufacturing composition and the in-plane uniformity of each film formed using the semiconductor manufacturing composition. The method for mixing the solvent (B2) with the compound (B1) is not particularly limited, and the solvent (B2) can be mixed by either adding the solvent (B2) to the compound (B1) or by mixing the solvent (B2) as a by-product or by being mixed in the manufacturing process of the compound (B1).

[0026] The content of the solvent (B2) is not limited, but is preferably less than 100% by mass, based on the total amount (100% by mass) of the compound (B1), from the viewpoint of further improving productivity by shortening the drying time of the coating film, and is 70% by mass or less, and from the viewpoint of further increasing the dissolving power of the solvent while ensuring a moderate drying time, it is 60% by mass or less, 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, more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less. From the viewpoint of further improving the storage stability of the composition for manufacturing a semiconductor, it is preferably 0.0001% by mass or more, from the viewpoint of further improving the solubility of the active ingredient of the composition for manufacturing a semiconductor, it is more preferably 0.001% by mass or more, and from the viewpoint of further suppressing defects in the resist film and the resist auxiliary film, it is even more preferably 0.01% by mass or more.

[0027] The content of methyl α-methoxyisobutyrate, methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, or methyl 3-hydroxyisobutyrate is not limited, but is preferably less than 100% by mass, based on the total amount (100% by mass) of the semiconductor manufacturing composition, from the viewpoint of further improving productivity by shortening the drying time of the coated film, and more preferably 70% by mass or less, 60% by mass or less, 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. From the viewpoint of further improving the storage stability of the resist composition, the content is preferably 0.0001% by mass or more, from the viewpoint of further improving the solubility of the active ingredients of the resist composition, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more, from the viewpoint of further suppressing defects in the resist film and resist auxiliary film.

[0028] 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 70% by mass or less, 60% by mass or less, 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 further improving the storage stability of the composition for manufacturing a semiconductor, the content is preferably 0.0001% by mass or more, from the viewpoint of further improving the solubility of the active ingredients of the composition for manufacturing a semiconductor, more preferably 0.001% by mass or more, and from the viewpoint of further suppressing defects in the resist film or resist auxiliary film, even more preferably 0.01% by mass or more.

[0029] In another preferred embodiment, the component (B) used in this embodiment includes, as the solvent (B2), one or more selected from the group consisting of methyl α-formyloxyisobutyrate, methyl α-acetyloxyisobutyrate, and methyl 3-hydroxyisobutyrate.

[0030] In the composition for manufacturing a semiconductor of this embodiment, the content of component (B) is set appropriately depending on the application, but can be 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 composition for manufacturing a semiconductor. The upper limit of the content of component (B) is appropriately set in accordance with the content of compound (A), and can be 99.9% by mass or less, 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 composition for manufacturing a semiconductor. The content of component (B) can be specified in any combination by appropriately selecting from the respective options for the upper and lower limits described above.

[0031] <Metal Compound or Metalloid Compound (A)> In this embodiment, the composition for manufacturing a semiconductor contains a metal compound or metalloid compound (A) (hereinafter also referred to as "compound (A)"). Compound (A) is a compound having one or more metal atoms or metalloid atoms. 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.

[0032] 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.

[0033] 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.

[0034] Furthermore, the compound (A) of this embodiment is not particularly limited as long as it is a compound having a metal atom (a), but it may contain a ligand bonded 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. Examples of the halogen ligand include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the carboxy ligand include RCO ２ H (wherein R is a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms). Examples of the alkoxy ligand include OCH ３ , O.C. ２ H ５ , O.C. ３ H ７ , O.C. ４ H ９ , their isomers, or derivatives thereof. Examples of the carboxylate ligand include RCO ２ － (wherein R is a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms). Examples of alkyl ligands include alkyl groups having 1 to 18 carbon atoms. Examples of amide ligands include unsubstituted amide ligands (NH ２ ), methylamide ligand (NHMe), dimethylamide ligand (NMe２ ), diethylamide ligand (NEt ２ ), dipropylamide ligand (NPr ２ ) etc.

[0035] The compound (A) of this embodiment will be described in more detail below.

[0036] (First Aspect) In the first aspect of this embodiment, the compound (A) is preferably, for example, the compound (A1-1), the complex (A1-2), and / or the polymetalloxane (A1-3) shown below. A composition for manufacturing a semiconductor containing the compound (A) can be used as a radiation-sensitive composition, and by using the compound (A1-1), the complex (A1-2), and / or the polymetalloxane (A1-3) as the compound (A), the sensitivity of the composition for manufacturing a semiconductor as a radiation-sensitive composition can be further improved. The compound (A) may be used alone or in combination of two or more. Each compound will be described below.

[0037] ((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)

[0038] 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.

[0039] 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-.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] Examples of the β-diketone include acetylacetone, methylacetylacetone, and ethylacetylacetone.

[0046] Examples of the β-ketoester include acetoacetic acid ester, α-alkyl-substituted acetoacetic acid ester, β-ketopentanoic acid ester, and benzoylacetic acid ester.

[0047] 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.

[0048] 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.

[0049] The above x is preferably an integer of 0 to 2, and more preferably 0 or 1.

[0050] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0051] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group.

[0052] 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.

[0053] As the above Y, a chlorine atom, an ethoxy group, an isopropoxy group, a butoxy group, or an acetoxy group is more preferable.

[0054] 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.

[0055] 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;

[0056] The compound (A1-1) is preferably a compound having 2 to 4 hydrolyzable groups, a hydrolyzate thereof, a hydrolysis condensate thereof, or a combination thereof.

[0057] ((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.

[0058] 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.

[0059] 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. Ａare each independently a monovalent organic group. Ｌ are each independently a hydrogen atom or a monovalent organic group. Ｌ are the same or different from each other. When n is 2 or more, multiple Xs are the same or different from each other.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] Examples of the monovalent chain hydrocarbon group 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 group 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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)").

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] ((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.

[0089]

[0090] 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.

[0091] M is preferably a germanium atom or a tin atom, and more preferably a tin atom. １ , R ２ or R３ Examples of the monovalent organic group having 1 to 30 carbon atoms represented by the formula (ii) include R ａ 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.

[0092] R in the above formula (iii) １ and R in the above formula (iv) ２ The group bonded to M in the structural unit (I) is preferably a hydrocarbon group, more preferably an alkyl group, and more preferably an i-propyl group or a t-butyl group. 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 the radiation-sensitive composition is further improved.

[0093] 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.

[0094] 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 %.

[0095] 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.

[0096] Here, the Mw of polymetalloxane (A1-3) is a value measured using gel permeation chromatography (GPC) under the following conditions: GPC column: for example, two "G2000HXL" columns, one "G3000HXL" column, and one "G4000HXL" column, all manufactured by Tosoh Corporation; column temperature: 40°C; elution solvent: tetrahydrofuran; flow rate: 1.0 mL / min; sample concentration: 1.0 mass%; sample injection volume: 100 μL; detector: differential refractometer; standard material: monodisperse polystyrene.

[0097] The compound (A) is preferably at least one selected from the group consisting of (A1-2) complexes and (A1-3) polymetalloxanes.

[0098] The lower limit of the content of the compound (A) is 50 mass%, preferably 70 mass%, and more preferably 80 mass%, based on the total solid content of the composition for manufacturing a semiconductor, and the upper limit of the content is preferably 99 mass%, more preferably 95 mass%, and even more preferably 92 mass%.

[0099] (([B1] Electron Acceptor)) In the first aspect of this embodiment, when the composition for manufacturing a semiconductor contains, as compound (A), the (A1-1) compound, the (A1-2) complex, and / or the (A1-3) polymetalloxane, it can contain the electron acceptor [B1]. The electron acceptor [B1] is a substance that captures secondary electrons generated from metal atoms contained in the compound (A) upon exposure. The term "electron acceptor" refers to a substance that functions as an oxidizing agent in a redox reaction. The electron acceptor [B1] can be used alone or in combination of two or more types.

[0100] [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.

[0101] Examples of the compound having a sulfonyl group include a compound represented by the following formula (B-1) (hereinafter also referred to as "compound (B1-1)"). In the above formula (B-1), R Ｐ and R Ｑare each independently a monovalent organic group having 1 to 20 carbon atoms.

[0102] R Ｐ or R Ｑ Examples of the monovalent organic group having 1 to 20 carbon atoms represented by the formula (ii) include R ａ Examples of the organic group include the same groups as those exemplified above. Ｐ and R Ｑ As the aryl group, a substituted or unsubstituted aryl group is preferable, an unsubstituted aryl group is more preferable, and a phenyl group or a tolyl group is even more preferable.

[0103] Examples of the compound (B1-1) include dimethyl sulfone, ethyl methyl sulfone, methyl phenyl sulfone, diphenyl sulfone, and di-p-toluyl sulfone.

[0104] Examples of the compound 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 the compound having an aromatic hydroxy group include a compound represented by the following formula (B-2) (hereinafter also referred to as "compound (B1-2)"):

[0105] In the formula (B-2), Ar is a group obtained by removing (i+j) hydrogen atoms from an arene having 6 to 20 ring members or a heteroarene having 5 to 20 ring members. i is an integer from 0 to 11. j is an integer from 1 to 12. When i is 1, R Ｓ is a monovalent organic group having 1 to 20 carbon atoms. When i is 2 or more, multiple R Ｓ are the same or different and are monovalent organic groups having 1 to 20 carbon atoms, or a plurality of R Ｓ Two or more of the groups i and j are combined with each other to form a ring structure having 4 to 20 ring members together with the chain of atoms to which they are attached, provided that i+j is 12 or less.

[0106] Examples of arenes having 6 to 20 ring members that provide Ar include benzene, toluene, xylene, naphthalene, anthracene, phenanthrene, pyrene, etc. Examples of heteroarenes having 5 to 20 ring members that provide Ar include nitrogen atom-containing heterocyclic compounds such as pyrrole, pyridine, pyridazine, pyrimidine, and pyrazine; oxygen atom-containing heterocyclic compounds such as furan and pyran; and sulfur atom-containing heterocyclic compounds such as thiophene and benzothiophene.

[0107] The arene that provides Ar is preferably benzene, and the heteroarene that provides Ar is preferably pyrimidine.

[0108] R Ｓ Examples of the monovalent organic group having 1 to 20 carbon atoms represented by the formula (I) include: alkyl groups such as a methyl group and an ethyl group; fluorinated alkyl groups such as a trifluoromethyl group and a pentafluoroethyl group; alkoxy groups such as a methoxy group and an ethoxy group; a carboxy group; － Y ＋ , -SO ３ － Y ＋ (Y ＋ is a cation). ＋ Examples of the cation include a triphenylsulfonium cation, a tetrahydrosulfenium cation, and a diphenyliodonium cation.

[0109] i is preferably 0 to 3, more preferably 1 or 2, and even more preferably 1. j is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0110] Examples of the compound (B1-2) include triphenylsulfonium 2-hydroxy-4-trifluoromethylbenzoate, diphenyliodonium 2-hydroxy-4-trifluoromethylsulfonate, thymine, etc. Examples of the tetracyanoquinodimethane compound include a compound represented by the following formula (B-3) (hereinafter also referred to as "compound (B1-3)"):

[0111] In the above formula (B-3), RＴ , R Ｕ , R Ｖ and R Ｗ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms.

[0112] R Ｔ , R Ｕ , R Ｖ or R Ｗ Examples of the monovalent organic group having 1 to 20 carbon atoms represented by the formula (ii) include R ａ Examples of the organic group include the same groups as those exemplified above. Ｔ , R Ｕ , R Ｖ and R Ｗ is preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.

[0113] Examples of the compound (B1-3) 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.

[0114] The lower limit of the content of the electron acceptor [B1] is preferably 0.1 parts by mass, more preferably 1 part by mass, even more preferably 3 parts by mass, and particularly preferably 5 parts by mass, relative to 100 parts by mass of compound (A). The upper limit of the content is preferably 100 parts by mass, more preferably 70 parts by mass, even more preferably 50 parts by mass, and particularly preferably 20 parts by mass. By setting the content of the electron acceptor [B1] within the above range, the sensitivity of the radiation-sensitive composition can be further improved.

[0115] ((Other Optional Components)) In the first aspect of this embodiment, when the semiconductor manufacturing composition contains the (A1-1) compound, the (A1-2) complex, and / or the (A1-3) polymetalloxane as the compound (A), it can also contain the following other optional components. As other optional components, the semiconductor manufacturing composition may contain a surfactant, an adhesion aid, an acid generator, etc., which will be described later. Furthermore, in the first aspect, the semiconductor manufacturing composition can also contain components other than the compound (A) and the solvent (B) described in this specification.

[0116] (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.

[0117] [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.

[0118] 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.

[0119] Examples of the sulfonic acid include benzenesulfonic acid and p-toluenesulfonic acid.

[0120] Examples of the sulfinic acid include benzenesulfinic acid and p-toluenesulfinic acid.

[0121] Examples of the organic phosphinic acid include diethylphosphinic acid, methylphenylphosphinic acid, and diphenylphosphinic acid.

[0122] Examples of the organic phosphonic acid include methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid, and phenylphosphonic acid.

[0123] 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.

[0124] Examples of the enol include 2-hydroxy-3-methyl-2-butene and 3-hydroxy-4-methyl-3-hexene.

[0125] Examples of the thiol include mercaptoethanol and mercaptopropanol.

[0126] 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.

[0127] Examples of the oxime include aldoximes such as benzaldoxime and salicylaldoxime, and ketoximes such as diethylketoxime, methylethylketoxime and cyclohexanoneoxime.

[0128] Examples of the sulfonamide include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, and toluenesulfonamide.

[0129] The organic acid [a2] is preferably a carboxylic acid, more preferably a monocarboxylic acid, and even more preferably methacrylic acid or benzoic acid.

[0130] 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.

[0131] Examples of the β-diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione.

[0132] Examples of the β-ketoester include acetoacetic ester, α-alkyl-substituted acetoacetic ester, β-ketopentanoic ester, benzoylacetic ester, and 1,3-acetonedicarboxylic ester.

[0133] Examples of the β-ketoester include acetoacetic ester, α-alkyl-substituted acetoacetic ester, β-ketopentanoic ester, benzoylacetic ester, and 1,3-acetonedicarboxylic ester.

[0134] Examples of the amine compound include diethanolamine and triethanolamine.

[0135] 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.

[0136] The compound (A) may contain one or more of the above metal compounds.

[0137] The compound (A) may contain one or more organic acids (a2).

[0138] The lower limit of the content of compound (A) is preferably 2 mass%, more preferably 4 mass%, and even more preferably 6 mass%, based on all components contained in the composition for manufacturing a semiconductor, and the upper limit of the content is preferably 30 mass%, more preferably 20 mass%, and even more preferably 15 mass%, based on all components contained in the composition for manufacturing a semiconductor.

[0139] ((Method for Synthesizing Compound (A)) Compound (A) can be synthesized, for example, by a method of carrying out a hydrolysis condensation reaction using a metal-containing compound [b2], a method of carrying out a ligand exchange reaction using a metal-containing compound [b2], etc. Here, the term "hydrolysis condensation reaction" refers to a reaction in which a hydrolyzable group in the metal-containing compound [b2] is hydrolyzed to convert it to -OH, and the two resulting -OH groups are dehydration condensed to form -O-.

[0140] (([b2] Metal-Containing Compound)) The metal-containing compound [b2] is a metal compound (I2) having a hydrolyzable group, a hydrolysate of the metal compound (I2) having a hydrolyzable group, a hydrolysis condensate of the metal compound (I2) having a hydrolyzable group, or a combination thereof. The metal compound (I2) can be used alone or in combination of two or more.

[0141] Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group.

[0142] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0143] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxybutoxy group.

[0144] Examples of the acyloxy 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.

[0145] The hydrolyzable group is preferably an alkoxy group or an acyloxy group, more preferably an isopropoxy group or an acetoxy group.

[0146] [b2] When the metal-containing compound is a hydrolysis condensate of a metal compound (I2), the hydrolysis condensate of the metal compound (I2) may be a hydrolysis condensate of a metal (I2) having a hydrolyzable group and a compound containing a metalloid atom, as long as the effects of the present invention are not impaired. That is, the hydrolysis condensate of the metal compound (I2) may contain a metalloid atom within a range that does not impair the effects of the present invention. Examples of the metalloid atom include silicon, boron, germanium, antimony, tellurium, etc. The content of the metalloid atom in the hydrolysis condensate of the metal compound (I2) is usually less than 50 atomic % relative to the total of the metal atoms and metalloid atoms in the hydrolysis condensate. The upper limit of the content of the metalloid atom is preferably 30 atomic %, more preferably 10 atomic %, relative to the total of the metal atoms and metalloid atoms in the hydrolysis condensate.

[0147] Examples of the metal compound (I2) include a compound represented by the following formula (A) (hereinafter also referred to as "compound [M2]").

[0148] In the above formula (A), M is a metal atom. L is a ligand. a is an integer of 0 to 2. When a is 2, multiple Ls may be the same or different. Y is a hydrolyzable group selected from a halogen atom, an alkoxy group, and an acyloxy group. b is an integer of 2 to 6. Multiple Ys may be the same or different. Note that L is a ligand that does not correspond to Y.

[0149] Examples of the metal atom represented by M include the same metal atoms as those exemplified as the metal atoms constituting the metal oxide contained in compound (A).

[0150] The ligand represented by L may be a monodentate ligand or a polydentate ligand.

[0151] Examples of the monodentate ligand include a hydroxo ligand, a carboxy ligand, an amide ligand, and ammonia.

[0152] 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.

[0153] Examples of the polydentate ligand include hydroxy acid esters, β-diketones, β-ketoesters, β-dicarboxylic acid esters, hydrocarbons having a π bond, and diphosphines.

[0154] 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.

[0155] Examples of the β-diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione.

[0156] Examples of the β-ketoester include acetoacetic ester, α-alkyl-substituted acetoacetic ester, β-ketopentanoic ester, benzoylacetic ester, and 1,3-acetonedicarboxylic ester.

[0157] 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.

[0158] 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.

[0159] Examples of the diphosphines include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 1,1'-bis(diphenylphosphino)ferrocene.

[0160] Examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0161] Examples of the alkoxy group represented by Y include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0162] Examples of the acyloxy group represented by Y include an acetoxy group, an ethyryloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.

[0163] Y is preferably an alkoxy group or an acyloxy group, more preferably an isopropoxy group or an acetoxy group.

[0164] As b, 3 and 4 are preferred, and 4 is more preferred.

[0165] [b2] The metal-containing compound is preferably a metal alkoxide that has not undergone hydrolysis or hydrolytic condensation, or a metal acyloxide that has not undergone hydrolysis or hydrolytic condensation.

[0166] [b2] Examples of metal-containing compounds include zirconium tetra-n-butoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, hafnium tetraethoxide, indium triisopropoxide, hafnium tetraisopropoxide, hafnium tetrabutoxide, tantalum pentaethoxide, tantalum pentabutoxide, tungsten pentamethoxide, tungsten pentabutoxide, tungsten hexaethoxide, tungsten hexabutoxide, iron chloride, zinc diisopropoxide, zinc acetate dihydrate, tetrabutyl orthotitanate, titanium Titanium tetra-n-butoxide, titanium tetra-n-propoxide, zirconium di-n-butoxide bis(2,4-pentanedionate), titanium tri-n-butoxide stearate, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)tungsten dichloride, diacetato[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium, dichloro[ethylenebis(diphenylphosphine)]cobalt, titanium butoxide oligomer, aminopropyltrimethoxytitanium, aminopropyltriethoxyzirconium, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium, γ-glycidoxypropyltrimethoxyzirconium, 3-isocyanopropyltrimethoxyzirconium, 3-isocyanopropyltriethoxyzirconium, triethoxymono(acetylacetonate)titanium, tri-n-propoxymono(acetylacetonate)titanium, tri-i-propoxymono(acetylacetonate)titanium, triethoxymono(acetylacetonate)zirconium, tri-n-propoxymono(acetylacetonate) Examples of suitable acetylacetonates include tri(3-methacryloxypropyl)methoxyzirconium, tri-i-propoxymono(acetylacetonato)zirconium, diisopropoxybis(acetylacetonato)titanium, di-n-butoxybis(acetylacetonato)titanium, di-n-butoxybis(acetylacetonato)zirconium, tri(3-methacryloxypropyl)methoxyzirconium, tri(3-acryloxypropyl)methoxyzirconium, tin tetraisopropoxide, tin tetrabutoxide, lanthanum oxide, and yttrium oxide.

[0167] Of these, metal alkoxides and metal acyloxides are preferred, metal alkoxides are more preferred, and alkoxides of titanium, zirconium, hafnium, tantalum, tungsten and tin are even more preferred.

[0168] When an organic acid is used in the synthesis of compound (A), the lower limit of the amount of the organic acid used is preferably 10 parts by mass, more preferably 30 parts by mass, relative to 100 parts by mass of the metal-containing compound [b2], while the upper limit of the amount of the organic acid used is preferably 1,000 parts by mass, more preferably 700 parts by mass, even more preferably 200 parts by mass, and particularly preferably 100 parts by mass, relative to 100 parts by mass of the metal-containing compound [b2].

[0169] During the synthesis reaction of compound (A), in addition to metal compound (I2) and organic acid [a2], a compound capable of becoming a multidentate ligand represented by L in the compound of formula (A) or a compound capable of becoming a bridging ligand may be added. Examples of the compound capable of becoming a bridging ligand include compounds having multiple hydroxy groups, isocyanate groups, amino groups, ester groups, and amide groups.

[0170] Examples of methods for carrying out a hydrolysis condensation reaction using a metal-containing compound [b2] include a method of carrying out a hydrolysis condensation reaction of the metal-containing compound [b2] in a solvent containing water. In this case, other compounds having hydrolyzable groups may be added as needed. The lower limit of the amount of water used in this hydrolysis condensation reaction is preferably 0.2 times the molar amount of the hydrolyzable group contained in the metal-containing compound [b2], more preferably 1 time, and even more preferably 3 times. The upper limit of the amount of water is preferably 20 times, more preferably 15 times, and even more preferably 10 times.

[0171] Examples of methods for carrying out a ligand exchange reaction using the metal-containing compound [b2] include a method of mixing the metal-containing compound [b2] and the organic acid [a2]. In this case, the mixing may be carried out in a solvent or without using a solvent. In addition, a base such as triethylamine may be added to the mixing as needed. The amount of the base added is, for example, 1 part by mass or more and 200 parts by mass or less per 100 parts by mass of the total amount of the metal-containing compound [b2] and the organic acid [a2] used.

[0172] The solvent used in the synthesis reaction of compound (A) (hereinafter also referred to as "solvent [B']") is not particularly limited, and for example, the same solvents and organic solvents as those exemplified above as solvent (B) can be used. As solvent [B'], alcohol-based solvents, ether-based solvents, ester-based solvents, and hydrocarbon-based solvents are preferred, alcohol-based solvents, ether-based solvents, and ester-based solvents are more preferred, polyhydric alcohol partial ether-based solvents, monocarboxylic acid ester-based solvents, and cyclic ether-based solvents are even more preferred, and propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and 4-methyl-2-pentanol are particularly preferred.

[0173] When an organic solvent is used in the synthesis reaction of compound (A), the organic solvent used may be removed after the reaction, or may be contained as it is in solvent (B) of the composition for manufacturing a semiconductor without being removed after the reaction.

[0174] (([D2] Orthoester)) In the second aspect of this embodiment, when the semiconductor manufacturing composition contains a compound (A) constituted of a metal atom or a metalloid atom together with another [X2] compound, the semiconductor manufacturing composition can contain 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.

[0175] Examples of the orthoester [D2] include compounds represented by the following formula (4). (In formula (4), R １ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. ２ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0176] R １ Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms, and a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0177] Examples of the unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms include chain saturated hydrocarbon groups such as methanediyl group and ethanediyl group, and chain unsaturated hydrocarbon groups such as ethenediyl group and propenediyl group.

[0178] Examples of the unsubstituted divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as a cyclobutanediyl group, monocyclic unsaturated hydrocarbon groups such as a cyclobutenediyl group, polycyclic saturated hydrocarbon groups such as a bicyclo[2.2.1]heptanediyl group, and polycyclic unsaturated hydrocarbon groups such as a bicyclo[2.2.1]heptenediyl group.

[0179] Examples of the unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group, a biphenylene group, a phenyleneethylene group, and a naphthylene group.

[0180] R １ Examples of the substituent in the substituted divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkoxy group, an acyl group, and an acyloxy group.

[0181] R １ is preferably a hydrogen atom or an unsubstituted hydrocarbon group, more preferably a hydrogen atom or an unsubstituted chain hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a methyl group.

[0182] R ２ Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms, and a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0183] Examples of the unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms include chain saturated hydrocarbon groups such as methanediyl group and ethanediyl group, and chain unsaturated hydrocarbon groups such as ethenediyl group and propenediyl group.

[0184] Examples of the unsubstituted divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as a cyclobutanediyl group, monocyclic unsaturated hydrocarbon groups such as a cyclobutenediyl group, polycyclic saturated hydrocarbon groups such as a bicyclo[2.2.1]heptanediyl group, and polycyclic unsaturated hydrocarbon groups such as a bicyclo[2.2.1]heptenediyl group.

[0185] Examples of the unsubstituted divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group, a biphenylene group, a phenyleneethylene group, and a naphthylene group.

[0186] R ２Examples of the substituent in the substituted divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkoxy group, an acyl group, and an acyloxy group.

[0187] R ２ As the alkyl group, an unsubstituted hydrocarbon group is preferable, an unsubstituted chain hydrocarbon group is more preferable, an alkyl group is further preferable, and a methyl group or an ethyl group is particularly preferable.

[0188] 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.

[0189] The lower limit of the content of the orthoester [D2] is preferably 10 parts by mass, more preferably 100 parts by mass, even more preferably 300 parts by mass, and particularly preferably 500 parts by mass, relative to 100 parts by mass of compound (A). The upper limit of the content is preferably 10,000 parts by mass, more preferably 5,000 parts by mass, even more preferably 2,000 parts by mass, and particularly preferably 1,000 parts by mass. By setting the content of the orthoester [D2] within the above range, the storage stability of the composition for manufacturing a semiconductor can be further improved.

[0190] The lower limit of the content of the orthoester [D2] in the composition for manufacturing a semiconductor is preferably 0.1% by mass, more preferably 1% by mass, and even more preferably 2% by mass, relative to the composition for manufacturing a semiconductor, and the upper limit of the content is preferably 60% by mass, more preferably 55% by mass, and even more preferably 50% by mass, relative to the composition for manufacturing a semiconductor.

[0191] ((Organic acid [E2])) In the second aspect of this embodiment, when the composition for manufacturing a semiconductor contains a compound (A) constituted of a metal atom or a metalloid atom together with another [X2] compound, the composition can contain 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].

[0192] ((Other Optional Components)) In the second aspect of this embodiment, when the semiconductor manufacturing composition contains compound (A) constituted of a metal atom or a metalloid atom and other [X2] compounds, it can also contain the following other optional components. As other components, the semiconductor manufacturing composition may contain, for example, an acid generator, a polymer additive, a polymerization inhibitor, a surfactant, etc., which will be described later. Furthermore, in the second aspect, the semiconductor manufacturing composition can also contain components other than the compound (A) and solvent (B) described in this specification.

[0193] By including a polymer additive in the composition for manufacturing a semiconductor, for example, when the composition for manufacturing a semiconductor is used as a resist auxiliary film, the composition can further improve the coatability to a substrate or an organic underlayer film and the continuity of the film. The composition for manufacturing a semiconductor can include one or more polymer additives.

[0194] Examples of the polymer additive include (poly)oxyalkylene polymer compounds, fluorine-containing polymer compounds, and non-fluorine-containing polymer compounds.

[0195] Examples of the (poly)oxyalkylene polymer compound include polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene adducts; (poly)oxyalkyl ethers such as diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether, and oxyethylene oxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly)oxyalkylene (alkyl)aryl ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether; alkylene oxyalkylene aryl ethers of acetylene alcohols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, and 3-methyl-1-butyn-3-ol; Examples of suitable acetylene ethers include acetylene ethers obtained by addition polymerization of alkyl esters; (poly)oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, and ethylene glycol distearate; (poly)oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly)oxyalkylene alkyl (aryl) ether sulfate salts such as polyoxypropylene methyl ether sodium sulfate and polyoxyethylene dodecylphenol ether sodium sulfate; (poly)oxyalkylene alkyl phosphates such as (poly)oxyethylene stearyl phosphate; and (poly)oxyalkylene alkyl amines such as polyoxyethylene laurylamine.

[0196] Examples of fluorine-containing polymer compounds include compounds described in JP 2011-89090 A. Examples of fluorine-containing polymer compounds include compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups).

[0197] Examples of non-fluorine-based polymer compounds include linear or branched alkyl (meth)acrylates such as lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, isostearyl (meth)acrylate, and isononyl (meth)acrylate; alkoxyethyl (meth)acrylates such as methoxyethyl (meth)acrylate; alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate and 1,3-butylene glycol di(meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate; and nonylphenoxy polyethylene glycol (-(CH ２ CH ２ O) ｎ Examples of the compound include compounds containing one or more repeating units derived from a (meth)acrylate monomer such as (meth)acrylate having a - structure (n=1 to 17).

[0198] The composition for manufacturing a semiconductor may contain one or more polymerization inhibitors, which may enhance the storage stability of the composition for manufacturing a semiconductor.

[0199] 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.

[0200] (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.

[0201] 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.

[0202] 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%.

[0203] 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.

[0204] ((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.

[0205] 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.

[0206] [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).

[0207] 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.

[0208] Examples of the sulfonic acid include benzenesulfonic acid and p-toluenesulfonic acid.

[0209] Examples of the sulfinic acid include benzenesulfinic acid and p-toluenesulfinic acid.

[0210] Examples of the organic phosphinic acid include diethylphosphinic acid, methylphenylphosphinic acid, and diphenylphosphinic acid.

[0211] Examples of the organic phosphonic acid include methylphosphonic acid, ethylphosphonic acid, t-butylphosphonic acid, cyclohexylphosphonic acid, and phenylphosphonic acid.

[0212] 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.

[0213] Examples of the enol include 2-hydroxy-3-methyl-2-butene and 3-hydroxy-4-methyl-3-hexene.

[0214] Examples of the thiol include mercaptoethanol and mercaptopropanol.

[0215] 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.

[0216] Examples of the oxime include aldoximes such as benzaldoxime and salicylaldoxime; and ketoximes such as diethylketoxime, methylethylketoxime and cyclohexanoneoxime.

[0217] Examples of the sulfonamide include methylsulfonamide, ethylsulfonamide, benzenesulfonamide, and toluenesulfonamide.

[0218] 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.

[0219] 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.

[0220] 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 %.

[0221] ((Method for Synthesizing Compound (A3)) Compound (A3) containing a metal atom [m3] and a ligand [p] can be synthesized by, for example, a method of carrying out a hydrolysis-condensation reaction using a metal compound having a hydrolyzable group (hereinafter also referred to as "metal compound (I3)"), its hydrolysate or hydrolysis-condensate, or a combination thereof (hereinafter also referred to as "metal-containing compound [b3]"), and then adding an organic acid [a3] to the obtained hydrolysis-condensate, or a method of carrying out a ligand exchange reaction between the metal-containing compound [b3] and the organic acid [a3]. Here, the "hydrolysis-condensation reaction" refers to a reaction in which a hydrolyzable group in the metal-containing compound [b3] is hydrolyzed to —OH, and the two resulting —OH groups undergo dehydration condensation to form —O—.

[0222] (((([b3] Metal-Containing Compound))) The metal-containing compound [b3] is a metal compound (I3) having a hydrolyzable group, a hydrolysate or hydrolyzed condensate thereof, or a combination thereof. The metal compound (I3) can be used alone or in combination of two or more.

[0223] Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group.

[0224] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0225] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group.

[0226] Examples of the acyloxy group include an acetoxy group, an ethyryloxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a 1,1-dimethylpropylcarbonyloxy group, an n-hexylcarbonyloxy group, and an n-octylcarbonyloxy group.

[0227] The hydrolyzable group is preferably an alkoxy group or an acyloxy group, more preferably an isopropoxy group or an acetoxy group.

[0228] [b3] When the metal-containing compound is a hydrolysis condensate of a metal compound (I3), the hydrolysis condensate of the metal compound (I3) may be a hydrolysis condensate of a metal (I) having a hydrolyzable group and a compound containing a metalloid atom, as long as the effects of the present invention are not impaired. That is, the hydrolysis condensate of the metal compound (I3) may contain a metalloid atom within a range that does not impair the effects of the present invention. Examples of the metalloid atom include boron and silicon. The content of the metalloid atom in the hydrolysis condensate of the metal compound (I3) is usually less than 50 atomic % relative to the total of the metal atoms and metalloid atoms in the hydrolysis condensate. The upper limit of the content of the metalloid atom is preferably 30 atomic %, more preferably 10 atomic %, relative to the total of the metal atoms and metalloid atoms in the hydrolysis condensate.

[0229] Examples of the metal compound (I3) include a compound represented by the following formula (A) (hereinafter also referred to as "metal compound (I3-1)"). In the above formula (A), M is the metal atom [m3]. L is a ligand. a is an integer of 0 to 2. When a is 2, multiple Ls may be the same or different. Y is a hydrolyzable group selected from a halogen atom, an alkoxy group, and an acyloxy group. b is an integer of 2 to 6. Multiple Ys may be the same or different. Note that L is a ligand that does not correspond to Y.

[0230] Examples of the metal atom [m3] represented by M include the same metal atoms as those exemplified as the metal atom [m3] constituting the metal oxide contained in compound (A3). Examples of the ligand represented by L include monodentate ligands and polydentate ligands.

[0231] Examples of the monodentate ligand include a hydroxo ligand, a carboxy ligand, an amide ligand, and ammonia.

[0232] 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.

[0233] Examples of the polydentate ligand include hydroxy acid esters, β-diketones, β-ketoesters, β-dicarboxylic acid esters, hydrocarbons having a π bond, and diphosphines.

[0234] 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.

[0235] Examples of the β-diketone include 2,4-pentanedione, 3-methyl-2,4-pentanedione, and 3-ethyl-2,4-pentanedione.

[0236] Examples of the β-ketoester include acetoacetic ester, α-alkyl-substituted acetoacetic ester, β-ketopentanoic ester, benzoylacetic ester, and 1,3-acetonedicarboxylic ester.

[0237] 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.

[0238] 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.

[0239] Examples of the diphosphines include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 1,1'-bis(diphenylphosphino)ferrocene.

[0240] Examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0241] Examples of the alkoxy group represented by Y include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group.

[0242] Examples of the acyloxy group represented by Y include an acetoxy group, a propionyloxy group, an n-butyryloxy group, an i-butyryloxy group, a t-butyryloxy group, a 1,1-dimethylpropylcarbonyloxy group, an n-hexylcarbonyloxy group, and an n-octylcarbonyloxy group.

[0243] Y is preferably an alkoxy group or an acyloxy group, more preferably an isopropoxy group or an acetoxy group, and even more preferably an isopropoxy group.

[0244] a is preferably 0 or 1, and more preferably 0. b is preferably 3 or 4, and more preferably 4.

[0245] [b3] The metal-containing compound is preferably a metal alkoxide that has not undergone hydrolysis or hydrolytic condensation, or a metal acyloxide that has not undergone hydrolysis or hydrolytic condensation.

[0246] [b3] Examples of metal-containing compounds include zirconium tetra-n-butoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, tellurium tetra-n-butoxide, tellurium tetra-n-propoxide, tellurium tetraisopropoxide, hafnium tetraethoxide, indium triisopropoxide, hafnium tetraisopropoxide, hafnium tetrabutoxide, tantalum pentaethoxide, tantalum pentabutoxide, tungsten pentamethoxide, tungsten pentabutoxide, tungsten hexaethoxide, tungsten hexabutoxide, iron chloride, zinc diisopropoxide, acetic acid, Zinc acetate dihydrate, tetrabutyl orthotitanate, titanium tetra n-butoxide, titanium tetra n-propoxide, zirconium di-n-butoxide bis(2,4-pentanedionate), titanium tri-n-butoxide stearate, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)tungsten dichloride, diacetato[(S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]ruthenium, dichloro[ethylenebis(diphenylphosphine)]cobalt, titanium butoxide oligomer, aminopropyltrimethoxytitanium, aminopropyltriethoxyzirconium, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium, γ-glycidoxypropyltrimethoxyzirconium, 3-isocyanopropyltrimethoxyzirconium, 3-isocyanopropyltriethoxyzirconium, triethoxymono(acetylacetonate)titanium, tri-n-propoxymono(acetylacetonate)titanium, tri-i-propoxymono(acetylacetonate)titanium, triethoxymono(acetylacetonate)zirconium, tri-n-propoxymono(acetylacetonate) Examples of suitable metal alkoxides include titanium diisopropoxybis(acetylacetonate), titanium di-n-butoxybis(acetylacetonate), zirconium di-n-butoxybis(acetylacetonate), tri(3-methacryloxypropyl)methoxyzirconium, tri(3-acryloxypropyl)methoxyzirconium, tin tetraisopropoxide, tin tetrabutoxide, lanthanum oxide, and yttrium oxide. Among these, metal alkoxides or metal acyloxides are preferred, metal alkoxides are more preferred, and alkoxides of titanium, zirconium, tellurium, hafnium, tantalum, tungsten, or tin are even more preferred.

[0247] When compound (A3) is synthesized by a hydrolysis condensation reaction of the metal-containing compound [b3], the lower limit of the amount of the organic acid [a3] used is preferably 10 parts by mass, more preferably 100 parts by mass, per 100 parts by mass of the metal-containing compound [b3]. On the other hand, the upper limit of the amount of the organic acid used is preferably 1,000 parts by mass, more preferably 700 parts by mass, even more preferably 500 parts by mass, and particularly preferably 400 parts by mass, per 100 parts by mass of the metal-containing compound [b3]. By using the organic acid [a3] in the above range, the content of the organic acid [a3] in the obtained compound (A3) can be adjusted to an appropriate level, and as a result, the pattern formability and scum suppression properties of the radiation-sensitive composition can be further improved.

[0248] During the synthesis reaction of compound (A3), in addition to the metal-containing compound [b3] and the organic acid [a3], a compound capable of becoming a multidentate ligand represented by L in the compound of formula (A) or a compound capable of becoming a bridging ligand may be added. Examples of the compound capable of becoming a bridging ligand include compounds having multiple hydroxy groups, isocyanate groups, amino groups, ester groups, and amide groups.

[0249] Examples of methods for carrying out the hydrolysis condensation reaction using the metal-containing compound [b3] include a method of carrying out the hydrolysis condensation reaction of the metal-containing compound [b3] in a solvent containing water. In this case, other compounds having hydrolyzable groups may be added as necessary. The lower limit of the amount of water used in this hydrolysis condensation reaction is preferably 0.2 times the molar amount of the hydrolyzable groups of the metal-containing compound [b3] or the like, more preferably 1 time, and even more preferably 3 times. The upper limit of the amount of water is preferably 20 times the molar amount, more preferably 15 times, and even more preferably 10 times. By setting the amount of water in the hydrolysis condensation reaction within the above range, the metal oxide content in the resulting compound (A3) can be increased, and as a result, the pattern formability and scum suppression properties of the radiation-sensitive composition can be further improved.

[0250] Examples of methods for carrying out a ligand exchange reaction using the metal-containing compound [b3] include a method of mixing the metal-containing compound [b3] and the organic acid [a3]. In this case, the mixing may be carried out in a solvent or without a solvent. Furthermore, in the mixing, a base such as triethylamine may be added as needed. The amount of the base added is, for example, 1 part by mass or more and 200 parts by mass or less per 100 parts by mass of the total amount of the metal-containing compound [b3] and the organic acid [a3] used.

[0251] When the metal-containing compound [b3] and the organic acid [a3] are mixed to carry out a ligand exchange reaction, the lower limit of the amount of the organic acid [a3] used is preferably 10 parts by mass, more preferably 100 parts by mass, per 100 parts by mass of the metal-containing compound [b3]. On the other hand, the upper limit of the amount of the organic acid [a3] used is preferably 1,000 parts by mass, more preferably 700 parts by mass, even more preferably 500 parts by mass, and particularly preferably 400 parts by mass, per 100 parts by mass of the metal-containing compound [b3]. By setting the amount of the organic acid [a3] used within the above range, the content of the organic acid [a3] in the resulting compound (A3) can be adjusted to an appropriate level, and as a result, the pattern formability and scum suppression properties of the radiation-sensitive composition can be further improved.

[0252] The solvent used in the synthesis reaction of compound (A3) is not particularly limited, and for example, the same solvents or organic solvents as those exemplified above as solvent (B) can be used. The solvent used in the synthesis reaction is preferably an alcohol solvent, an ether solvent, an ester solvent, or a hydrocarbon solvent, more preferably an alcohol solvent, an ether solvent, or an ester solvent, even more preferably a polyhydric alcohol partial ether solvent or an alcohol solvent, and particularly preferably propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, or 4-methyl-2-pentanol.

[0253] When an organic solvent is used in the synthesis reaction of the compound (A3), the organic solvent used may be removed after the reaction, or may be included as it is in the solvent (B) of the composition for manufacturing a semiconductor without being removed after the reaction.

[0254] The lower limit of the temperature for the synthesis reaction of compound (A3) is preferably 0°C, more preferably 10°C. The upper limit of the temperature is preferably 150°C, more preferably 100°C. The lower limit of the time for the synthesis reaction of compound (A3) is preferably 1 minute, more preferably 10 minutes, and even more preferably 1 hour. The upper limit of the time is preferably 100 hours, more preferably 50 hours, and even more preferably 10 hours.

[0255] The reaction solution obtained in the synthesis reaction using the above-mentioned metal-containing compound (b3) and organic acid (a3) ​​can be washed multiple times with a solvent such as hexane to obtain compound (A3).

[0256] 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.

[0257] ((Compound [B])) In the third aspect of this embodiment, when the composition for manufacturing a semiconductor contains, as compound (A), 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 composition can also contain 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) possessed by compound (A3).

[0258] ((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).

[0259] 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.

[0260] 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.

[0261] Examples of the carbon-carbon triple bond-containing group include an ethynyl group, a propargyl group, and an ethynylphenyl group.

[0262] 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.

[0263] Examples of the protecting group for the isocyanate group include blocking agents such as dimethylpyrazole, diethylpyrazole, methylethylketoxime, and caprolactam.

[0264] Examples of the protective group for the sulfanyl group include arylcarbamoyl groups such as phenylcarbamoyl group, and triarylmethyl groups such as triphenylmethyl group.

[0265] "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.

[0266] 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.

[0267] 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.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] When the functional group (II) is an azide group, examples of the compound [B3] include phenyl azide and cyclohexyl azide.

[0274] 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.

[0275] 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.

[0276] The lower limit of the content of the compound [B3] is preferably 0.1 parts by mass, more preferably 1 part by mass, even more preferably 3 parts by mass, and particularly preferably 5 parts by mass, relative to 100 parts by mass of the compound (A3). The upper limit of the content is preferably 100 parts by mass, more preferably 60 parts by mass, even more preferably 40 parts by mass, and particularly preferably 30 parts by mass. By setting the content of the compound [B3] within the above range, pattern formability can be further improved.

[0277] ((Acid Generator [D3])) In the third aspect of this embodiment, when the semiconductor manufacturing composition contains, as compound (A), 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 can also contain an acid generator [D3]. The acid generator [D3] is a component that generates an acid when irradiated with radiation. The action of the acid generated from the acid generator [D3] can further promote changes in the solubility of the compound (A3) in the developer in the semiconductor manufacturing composition. As the acid generator [D3], the acid generators described below can be used.

[0278] When the semiconductor manufacturing composition contains the acid generator [D3], the lower limit of the content of the acid generator [D3] is preferably 1 mass %, more preferably 4 mass %, and even more preferably 8 mass %, based on all components of the semiconductor manufacturing composition other than the solvent (B). The upper limit of the content is preferably 40 mass %, more preferably 30 mass %, and even more preferably 20 mass %. When the semiconductor manufacturing composition contains the acid generator [D3], the lower limit of the content of the acid generator [D3] is preferably 1 part by mass, more preferably 4 parts by mass, and even more preferably 8 parts by mass, based on 100 parts by mass of the compound (A3). The upper limit of the content is preferably 40 parts by mass, more preferably 30 parts by mass, and even more preferably 20 parts by mass.

[0279] By setting the content of the acid generator [D3] within the above range, the pattern formability and scum suppression properties of the composition for manufacturing a semiconductor can be further improved. The acid generator [D3] can be used alone or in combination with two or more types.

[0280] (([E3] Radical Scavenger)) In the third aspect of this embodiment, when the semiconductor manufacturing composition contains, as compound (A), 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 composition can also contain a radical scavenger [E3]. The radical scavenger [E3] is a compound that can capture radicals and suppress radical chain reactions. Examples of the radical scavenger [E3] include stable nitroxyl radical compounds, sulfide compounds, quinone compounds, phenol compounds, amine compounds, and phosphite compounds (excluding those corresponding to compounds (A3) and [B3] compounds).

[0281] 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.

[0282] 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.

[0283] Examples of the quinone compound include benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, p-xyloquinone, and 2-hydroxy-1,4-naphthoquinone.

[0284] 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.

[0285] 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.

[0286] Examples of the phosphite compound include triisodecyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and trinonylphenyl phosphite.

[0287] [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.

[0288] [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.

[0289] When the composition for manufacturing a semiconductor contains the radical scavenger [E3], the lower limit of the content of the radical scavenger [E3] is preferably 0.01 parts by mass, more preferably 0.1 parts by mass, even more preferably 1 part by mass, and particularly preferably 2 parts by mass, relative to 100 parts by mass of the compound (A3). The upper limit of the content is preferably 50 parts by mass, more preferably 20 parts by mass, even more preferably 15 parts by mass, and particularly preferably 10 parts by mass. By setting the content of the radical scavenger [E3] within the above range, pattern formability can be further improved.

[0290] ((Other Optional Components)) In the third aspect of this embodiment, when the semiconductor manufacturing composition includes, as compound (A), 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 may also include the following other optional components. Examples of the other optional components include a radiation-sensitive radical generator, an acid diffusion controller, and a surfactant described below. The radiation-sensitive composition may use one or more of the other optional components. Furthermore, in the third aspect, the semiconductor manufacturing composition may also include components other than the compound (A) and the solvent (B) described in this specification.

[0291] (Radiation-sensitive radical generator) A 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. When the radiation-sensitive composition contains a radiation-sensitive radical generator, the content of the radiation-sensitive radical generator can be set in various amounts as long as the effects of the present invention are not impaired.

[0292] ((Acid Diffusion Controller)) The acid diffusion controller controls the diffusion phenomenon in the film of the acid generated from the acid generator [D3] or the like upon exposure, thereby suppressing undesirable chemical reactions in the non-exposed regions. Furthermore, the storage stability of the radiation-sensitive composition is further improved, and the resolution is further improved. Furthermore, it is possible to suppress changes in the line width of the pattern due to fluctuations in the incubation time from exposure to development, thereby obtaining a radiation-sensitive composition with excellent process stability.

[0293] Examples of the acid diffusion controller include nitrogen atom-containing compounds and photodecomposable bases that generate weak acids upon irradiation with radiation.

[0294] Examples of the nitrogen atom-containing compound include monoamines such as n-hexylamine and the like; dialkylamines such as di-n-butylamine and the like; trialkylamines such as triethylamine and the like; aromatic amines such as aniline and the like; diamines such as ethylenediamine and N,N,N',N'-tetramethylethylenediamine and the like; polyamines such as polyethyleneimine and polyallylamine and the like; amine compounds such as polymers such as dimethylaminoethylacrylamide and the like; amide group-containing compounds such as formamide and N-methylformamide and the like; urea compounds such as urea and methylurea; pyridine compounds such as pyridine and 2-methylpyridine; morpholine compounds such as N-propylmorpholine and N-(undecylcarbonyloxyethyl)morpholine; nitrogen-containing heterocyclic compounds such as pyrazine and pyrazole; and nitrogen-containing heterocyclic compounds having an acid-dissociable group such as N-t-butoxycarbonylpiperidine and N-t-butoxycarbonylimidazole.

[0295] 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.

[0296] Examples of photodegradable bases include triphenylsulfonium salicylate and triphenylsulfonium 10-camphorsulfonate.

[0297] When the composition for manufacturing a semiconductor contains an acid diffusion controller, the lower limit of the content of the acid diffusion controller is preferably 0.1 mass %, more preferably 0.3 mass %, and even more preferably 1 mass %, based on all components of the composition for manufacturing a semiconductor other than the solvent (B), and the upper limit of the content is preferably 20 mass %, more preferably 10 mass %, and even more preferably 5 mass %.

[0298] When the composition for manufacturing a semiconductor contains an acid diffusion controller, the lower limit of the content of the acid diffusion controller is preferably 0.1 parts by mass, more preferably 0.3 parts by mass, and even more preferably 1 part by mass, relative to 100 parts by mass of the compound (A3). The upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and even more preferably 5 parts by mass. By setting the content of the acid diffusion controller within the above range, the pattern formability of the composition for manufacturing a semiconductor can be further improved.

[0299] Next, components that can be further contained in the semiconductor manufacturing composition in this embodiment will be described. The semiconductor manufacturing composition can contain the following components in addition to the above-mentioned compound (A). <Acid Generator (Component C)> In this embodiment, the semiconductor manufacturing composition can contain an acid generator that can be selected as component (C). 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-rays, or ion beam. Specifically, preferred acid generators are compounds represented by any of the following general formulas (c-1) to (c-8).

[0300] (Compound represented by general formula (c-1))

[0301] In the above formula (c-1), R １３ are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group, a linear, branched, or cyclic alkoxy group, a hydroxyl group, or a halogen atom. － is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

[0302] Examples of the compound represented by the general formula (c-1) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethanesulfonate, bis(4-fluorophenyl)-4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis(4-hydroxyphenyl)-phenylsulfonium trifluoromethanesulfonate, tri(4-methylphenyl)-4-hydroxyphenylsulfonium trifluoromethanesulfonate, tri(4-fluorophenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenyl naphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate, and cyclo(1,It is preferable that the compound is at least one selected from the group consisting of 3-perfluoropropanedisulfone)imidate.

[0303] (Compound represented by general formula (c-2))

[0304] In the above formula (c-2), R １４ are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group, a linear, branched, or cyclic alkoxy group, a hydroxyl group, or a halogen atom. － is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

[0305] Examples of the compound represented by the general formula (c-2) include bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodonium perfluoro-n-octanesulfonate, bis(4-t-butylphenyl)iodonium p-toluenesulfonate, bis(4-t-butylphenyl)iodonium benzenesulfonate, and bis(4-t-butylphenyl)iodonium-2-trifluoromethylbenzenesulfonate. iodonium 4-trifluoromethylbenzenesulfonate, bis(4-t-butylphenyl)iodonium 2,4-difluorobenzenesulfonate, bis(4-t-butylphenyl)iodonium hexafluorobenzenesulfonate, bis(4-t-butylphenyl)iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoromethanesulfonate diphenyliodonium hexafluorobenzenesulfonate, di(4-trifluoromethylphenyl)iodonium trifluoromethanesulfonate, di(4-trifluoromethylphenyl)iodonium nonafluoro-n-butanesulfonate, di(4-trifluoromethylphenyl)iodonium perfluoro-n-octanesulfonate, di(4-trifluoromethylphenyl)iodonium p-toluenesulfonate, di(4-trifluoromethylphenyl)iodonium benzenesulfonate, and di(4-trifluoromethylphenyl)iodonium 10-camphorsulfonate.

[0306] (Compound represented by general formula (c-3))

[0307] In the above formula (c-3), Q is an alkylene group, an arylene group, or an alkoxylene group. １５ is an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

[0308] Examples of the compound represented by the general formula (c-3) include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthylimide, N-(10-camphorsulfonyloxy)succinimide, N-(10-camphorsulfonyloxy)succinimide, N-(10-camphorsulfonyloxy)phthalimide, N-(10-camphorsulfonyloxy)diphenylmaleimide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(10-camphorsulfonyloxy)naphthylimide, N-(n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(n-octanesulfonyloxy)naphthylimide, N-(p-toluenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide cyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(p-toluenesulfonyloxy)naphthylimide, N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylbenzenesulfonyloxy)naphthylimide, N-(4-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide N-(perfluorobenzenesulfonyloxy)naphthyl imide, N-(perfluorobenzenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(perfluorobenzenesulfonyloxy)naphthyl imide, N-(1-naphthalenesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-naphthalenesulfonyloxy)naphthyl imide, N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide,Preferably, the aryl group is at least one selected from the group consisting of N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluoro-n-butanesulfonyloxy)naphthylimide, N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, and N-(perfluoro-n-octanesulfonyloxy)naphthylimide.

[0309] (Compound represented by general formula (c-4))

[0310] In the above formula (c-4), R １６ are each independently a linear, branched, or cyclic alkyl group, an aryl group, a heteroaryl group, or an aralkyl group, and at least one hydrogen atom in these groups may be substituted with an optional substituent.

[0311] The compound represented by general formula (c-4) is preferably at least one selected from the group consisting of diphenyl disulfone, di(4-methylphenyl)disulfone, dinaphthyl disulfone, di(4-t-butylphenyl)disulfone, di(4-hydroxyphenyl)disulfone, di(3-hydroxynaphthyl)disulfone, di(4-fluorophenyl)disulfone, di(2-fluorophenyl)disulfone, and di(4-trifluoromethylphenyl)disulfone.

[0312] (Compound represented by general formula (c-5))

[0313] In the above formula (c-5), R １７ are each independently a linear, branched, or cyclic alkyl group, an aryl group, a heteroaryl group, or an aralkyl group, and at least one hydrogen atom in these groups may be substituted with an optional substituent.

[0314] The compound represented by general formula (c-5) is preferably at least one selected from the group consisting of α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-4-methylphenylacetonitrile, and α-(methylsulfonyloxyimino)-4-bromophenylacetonitrile.

[0315] (Compound represented by general formula (c-6))

[0316] In the above formula (c-6), R １８ are each independently a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

[0317] (Compounds represented by general formulas (c-7) and (c-8)) In the above formulas (c-7) and (c-8), R １９ and R ２０ are each independently an alkyl group having 1 to 3 carbon atoms (such as a methyl group, an ethyl group, an n-propyl group, or an i-propyl group), a cycloalkyl group having 3 to 6 carbon atoms (such as a cyclopentyl group or a cyclohexyl group), an alkoxyl group having 1 to 3 carbon atoms (such as a methoxy group, an ethoxy group, or a propoxy group), or an aryl group having 6 to 10 carbon atoms (such as a phenyl group, a toluyl group, or a naphthyl group), and preferably an aryl group having 6 to 10 carbon atoms.

[0318] L １９ and L ２０are each independently an organic group having a 1,2-naphthoquinonediazide group, and specifically, a 1,2-quinonediazide sulfonyl group such as a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, or a 1,2-naphthoquinonediazide-6-sulfonyl group is preferred, with a 1,2-naphthoquinonediazide-4-sulfonyl group or a 1,2-naphthoquinonediazide-5-sulfonyl group being more preferred. p is an integer of 1 to 3, q ​​is an integer of 0 to 4, and 1≦p+q≦5. J １９ represents a single bond, an alkylene group having 1 to 4 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, a phenylene group, a group represented by the following formula (c-7-i), a carbonyl group, an ester group, an amide group, or —O—. １９ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and X ２０ are each independently a group represented by the following formula (c-8-i):

[0319]

[0320] In the above formula (c-8-i), Z ２２ are each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ２２ are each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an alkoxyl group having 1 to 6 carbon atoms; and r is an integer of 0 to 3.

[0321] Acid generators that can be used in this embodiment may be other than the compounds represented by any one of general formulas (c-1) to (c-8). Examples of such other acid generators include bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, 1,3-bis(cyclohexylsulfonylazomethylsulfonyl)propane, 1,4-bis(phenyl and bissulfonyldiazomethanes such as 1,6-bis(phenylsulfonylazomethylsulfonyl)butane, 1,6-bis(phenylsulfonylazomethylsulfonyl)hexane, and 1,10-bis(cyclohexylsulfonylazomethylsulfonyl)decane; and halogen-containing triazine derivatives such as 2-(4-methoxyphenyl)-4,6-(bistrichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-(bistrichloromethyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, and tris(2,3-dibromopropyl)isocyanurate.

[0322] <Other Additives> The semiconductor manufacturing composition of this embodiment may contain other components in addition to the above-described compound (A), solvent (B), and component (C). Examples of other components include one or more selected from an acid diffusion controller, a sensitizer, a surfactant, an organic carboxylic acid, a phosphorus oxoacid, or a derivative thereof. The content of each of these other components is appropriately selected depending on the type of component and the type of compound (A), but is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 70 parts by mass, even more preferably 0.1 to 50 parts by mass, and still more preferably 0.3 to 30 parts by mass, relative to 100 parts by mass of compound (A) contained in the semiconductor manufacturing composition.

[0323] <<Acid Diffusion Controller>> 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. The acid diffusion controller used in this embodiment is not particularly limited, and examples thereof include radiation-decomposable basic compounds such as nitrogen-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds. These acid diffusion controllers may be used alone or in combination of two or more.

[0324] <<Sensitizer>> A sensitizer is an additive that has the effect of absorbing the energy of irradiated radiation and transferring that energy to an acid generator, thereby increasing the amount of acid produced. It is also an additive that has the effect of absorbing light of a specific wavelength. Examples of sensitizers used in this embodiment include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers may be used alone or in combination of two or more.

[0325] <<Surfactant>> A surfactant is an additive that has the effect of improving the coatability and striation of a resist film composition or a resist auxiliary film composition, the developability of a resist film composition or a resist auxiliary film composition, etc. The surfactant used in this embodiment 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. These surfactants may be used alone or in combination of two or more.

[0326] <<Organic Carboxylic Acid or Phosphorus Oxo Acid or Derivatives Thereof>> 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. The organic carboxylic acids used in this embodiment are not particularly limited, and examples include 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 phosphinic acid and phenylphosphinic acid. These may be used alone, or two or more may be used in combination.

[0327] <<Other Components>> Furthermore, the composition for manufacturing a semiconductor of this embodiment 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, and the like.

[0328] 2. Uses of the composition for manufacturing a semiconductor The composition for manufacturing a semiconductor according to this embodiment can be used for various applications. In one embodiment, the composition for manufacturing a semiconductor according to this embodiment may be a resist composition, and in another embodiment, the composition for manufacturing a semiconductor according to this embodiment may be a resist auxiliary film composition.

[0329] Depending on the intended use of the semiconductor manufacturing composition, the semiconductor manufacturing composition may further contain components suitable for that intended use. Each intended use will be described below. [Resist Composition] The resist composition contains a compound (A) and a solvent (B). Compound (A) is preferably a metal compound containing zirconium and a ligand, a semimetallic compound containing tellurium and a ligand, or a metal compound containing tin and a ligand. Compound (A) is more preferably a metal compound containing zirconium and methacrylic acid, or a metal compound containing tellurium and methacrylic acid. The resist composition may further contain, as needed, an acid generator, an acid crosslinker, an acid diffusion controller, a dissolution promoter, a dissolution controller, a sensitizer, a surfactant, or the like. Including the solvent (B) in the resist composition may enable the formation of a uniform resist film and the reduction of the metal compound concentration. In particular, the resist composition is suitable for use in producing highly uniform resist films for high-resolution fine wiring applications.

[0330] [Resist auxiliary film composition] The resist auxiliary film is a film that can be used together with the above-mentioned resist film, and examples thereof include a resist underlayer film used in a two-layer resist method, a resist underlayer film used in a three-layer resist method, a resist middle layer film, etc. Note that the resist auxiliary film does not include the resist film, i.e., the outermost film of the resist.

[0331] In one embodiment, the resist assist film is a resist underlayer film or a resist interlayer film. In other words, the resist assist film composition is a resist underlayer film composition or a resist interlayer film composition.

[0332] In one embodiment, the resist sub-coat is a bottom anti-reflective coating (BARC).

[0333] The resist auxiliary film composition varies depending on the desired function, but includes a compound (A) and a solvent (B).In addition, as the compound (A), it is preferable to use a metal compound containing zirconium and a ligand, a semimetal compound containing tellurium and a ligand, or a metal compound containing tin and a ligand, and it is more preferable to use a metal compound containing zirconium and methacrylic acid, or a metal compound containing tellurium and methacrylic acid.In addition, if necessary, it can further include an acid generator, an acid crosslinking agent, an acid diffusion control agent, a dissolution promoter, a dissolution control agent, a sensitizer, a surfactant, etc.In addition, by including a solvent (B), the resist auxiliary film composition can be made to have a low viscosity and form a uniform resist auxiliary film, etc.

[0334] 3. Film Forming Method The composition for manufacturing a semiconductor according to this embodiment can be used to form various films. Methods for forming films using the composition for manufacturing a semiconductor will be described according to the intended use of the composition for manufacturing a semiconductor.

[0335] [Method of Forming a Resist Film] As described above, the resist composition (composition for manufacturing a semiconductor) of this embodiment is capable of forming a resist film with a thickness suitable for manufacturing various devices, even though the content of the active ingredients including compound (A) is limited to a predetermined value or less. The method of forming the resist film is not particularly limited, but includes, for example, a method having the following step (1), and preferably a method further having steps (2) and (3). Step (1): A step of applying the resist composition of this embodiment described above onto a substrate to form a coating film. Step (2): A step of performing a heat treatment after step (1). Step (3): A step of forming a resist pattern.

[0336] <Step (1)> In step (1), the substrate on which the coating film is formed is not particularly limited and includes, for example, a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, etc. More specifically, examples include a silicon wafer, a metal substrate such as copper, chromium, iron, aluminum, etc., a glass substrate, etc. The material for the wiring pattern is not particularly limited and examples include copper, aluminum, nickel, gold, etc.

[0337] The substrate used in this embodiment may have an underlayer film formed of a material selected from organic materials and inorganic materials on the surface on which the coating film is formed, as necessary. When using such a substrate with an underlayer film, the coating film is formed on the underlayer film. Examples of the underlayer film-forming material include the underlayer film-forming composition described in WO 2016 / 021511.

[0338] The substrate used in this embodiment may be surface-treated, if necessary, by applying a prewetting agent to the surface on which the coating film is to be formed. Generally, a significant amount of resist composition is scattered from the outer periphery, where the peripheral speed is significantly higher than that of the center, resulting in increased consumption of the resist composition. To address this issue, applying a prewetting agent to the surface of the substrate facilitates diffusion of the resist composition on the substrate, thereby reducing the amount of resist composition supplied. Examples of prewetting agents include cyclohexanone, ethyl lactate, methyl-3-methoxypropionate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Specific surface treatment methods using a prewetting agent are not particularly limited, but examples include the method described in JP-A-2004-39828.

[0339] As a coating means for applying the resist composition onto a substrate, known means can be appropriately applied, for example, spin coating, cast coating, roll coating, etc. As described above, the resist composition of this embodiment can be used by these coating means to form a coating film with a thickness suitable for the production of various devices.

[0340] <Step (2)> In this embodiment, step (2) preferably includes a heat treatment step performed after step (1). Heat treatment can improve adhesion between the substrate and the resist film. The heating temperature for the heat treatment in this step is appropriately set depending on the composition of the resist composition, but is preferably 20 to 250°C, and more preferably 20 to 150°C.

[0341] <Step (3)> Step (3) is a step of exposing the formed resist film through a desired mask pattern to form a predetermined resist pattern. Examples of radiation to be irradiated during exposure include visible light, ultraviolet light such as g-line (wavelength 436 nm) and i-line (wavelength 365 nm), far ultraviolet light such as ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm), excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays such as synchrotron radiation, and ion beams. From the viewpoint of stably forming a highly accurate fine pattern during exposure, it is preferable to perform a heat treatment after radiation irradiation. The heating temperature for the heat treatment is preferably 20 to 250°C, more preferably 20 to 150°C.

[0342] The exposed resist film is then developed with a developer to form a desired resist pattern. The developer used is preferably a solvent having a solubility parameter (SP value) close to that of the compound (A) contained in the resist composition, and examples of the developer include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, hydrocarbon solvents, and aqueous alkaline solutions. Examples of alkaline compounds contained in aqueous alkaline solutions include mono-, di-, or tri-alkylamines; mono-, di-, or tri-alkanolamines; heterocyclic amines; tetraalkylammonium hydroxides; choline; 1,8-diazabicyclo[5,4,0]-7-undecene; and 1,5-diazabicyclo[4,3,0]-5-nonene.

[0343] Examples of the developing method include a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method), a method of developing by piling up the developer on the surface of the substrate by surface tension and leaving it standing for a certain period of time (puddle method), a method of spraying the developer onto the surface of the substrate (spray method), a method of continuously dispensing the developer while scanning a developer dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method), etc. The developing time is not particularly limited, but is preferably 10 to 90 seconds.

[0344] After development, a step of stopping development while replacing the solvent with another solvent may be carried out. After development, a step of rinsing using a rinse containing an organic solvent is preferably carried out. The rinse liquid used in the rinse step after development is not particularly limited as long as it does not dissolve the formed resist pattern, and a solution containing a general organic solvent or water can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is preferably used. The time for performing the rinse step is not particularly limited, but is preferably 10 to 90 seconds.

[0345] In the rinsing step, the developed substrate is washed with a rinse solution containing the organic solvent. The method of the washing treatment is not particularly limited, but examples thereof include a method of continuously applying the rinse solution onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with the rinse solution for a certain period of time (dipping method), and a method of spraying the rinse solution onto the surface of the substrate (spray method).

[0346] After forming a resist pattern, etching is performed to obtain a patterned wiring substrate. Etching can be performed by known methods such as dry etching using plasma gas and wet etching using an alkaline solution, cupric chloride solution, ferric chloride solution, etc. After forming the resist pattern, plating may be performed. The plating method is not particularly limited, but examples include copper plating, solder plating, nickel plating, and gold plating.

[0347] The remaining resist pattern after etching can be stripped using an organic solvent. Examples of such organic solvents include, but are not limited to, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). Examples of the stripping method include, but are not limited to, immersion and spraying. The wiring substrate on which the resist pattern is formed may be a multilayer wiring substrate and may have small-diameter through-holes. In this embodiment, the wiring substrate can also be formed by a method in which, after forming the resist pattern, a metal is vapor-deposited in a vacuum, and then the resist pattern is dissolved in a solution, i.e., a lift-off method.

[0348] [Pattern Forming Method] Next, a pattern forming method using the resist auxiliary film composition (composition for semiconductor manufacturing) of this embodiment will be described. One pattern forming method of this embodiment includes the steps of: (A-1) forming an underlayer film on a substrate using the resist underlayer film composition of this embodiment; (A-2) forming at least one photoresist layer on the underlayer film; and (A-3) irradiating predetermined regions of the photoresist layer with radiation and developing the layer after step (A-2). As described above, the resist auxiliary film composition of this embodiment can form a resist underlayer film suitable for manufacturing various devices, even though the content of the active ingredient containing compound (A) is limited to a predetermined value or less.

[0349] When the photoresist underlayer film material is used for a spin-on carbon film used in a two-layer resist method or a three-layer resist method, the method includes a step (B-1) of forming an underlayer film using the resist auxiliary film composition of this embodiment, a step (B-2) of forming an intermediate layer film on the underlayer film using a resist intermediate layer film material containing silicon atoms, a step (B-3) of forming at least one photoresist layer on the intermediate layer film, a step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing it to form a resist pattern, and a step (B-5) of etching the intermediate layer film using the resist pattern as a mask, etching the underlayer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained underlayer film pattern as an etching mask to form a pattern on the substrate.

[0350] The resist underlayer film of the present embodiment may be formed by any known method without particular limitation, as long as it is formed from the resist underlayer film composition of the present embodiment. For example, the resist underlayer film can be formed by applying the resist underlayer film composition of the present embodiment to a substrate by a known coating method or printing method such as spin coating or screen printing, and then removing the organic solvent by volatilization or the like.

[0351] When forming the underlayer film, it is preferable to bake it in order to suppress the occurrence of mixing with the upper layer resist and to promote the crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 600°C, more preferably 200 to 400°C. The baking time is also not particularly limited, but is preferably in the range of 10 to 300 seconds. The thickness of the underlayer film can be appropriately selected depending on the required performance, and is not particularly limited, but is usually preferably 3 to 20,000 nm, more preferably 10 to 15,000 nm, and even more preferably 50 to 1,000 nm.

[0352] After forming an underlayer film on a substrate, when the underlayer film is to be used as an anti-reflection film for KrF excimer laser or ArF excimer laser or as a photoresist underlayer film material for EUV lithography, it is preferable to form a single-layer resist layer thereon. In this case, known photoresist materials can be used to form this resist layer.

[0353] When an underlayer film is formed on a substrate and then used as a photoresist underlayer film material for a spin-on carbon film used in a two-layer resist method or a three-layer resist method, it is preferable to form a silicon-containing resist layer or a single-layer resist made of a normal hydrocarbon on the underlayer film in the two-layer process, or a silicon-containing intermediate layer and a silicon-free single-layer resist layer on the middle layer in the three-layer process. In this case, known photoresist materials can be used to form the resist layers.

[0354] From the viewpoint of oxygen gas etching resistance, silicon-containing resist materials for two-layer processes are preferably positive photoresist materials that use a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative as a base polymer, and further contain an organic solvent, an acid generator, and optionally a basic compound, etc. Here, the silicon atom-containing polymer can be any known polymer used in this type of resist material.

[0355] A polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer for the three-layer process. By providing the intermediate layer with an anti-reflective coating effect, reflection tends to be effectively suppressed. For example, in a 193 nm exposure process, if a material containing many aromatic groups and having high substrate etching resistance is used as the underlayer film, the k value (extinction coefficient) tends to be high and the substrate reflection tends to be high. However, by suppressing reflection with an intermediate layer, the substrate reflection can be reduced to 0.5% or less. Examples of intermediate layers with such anti-reflective effects include, but are not limited to, acid- or heat-crosslinkable polysilsesquioxanes incorporating phenyl groups or light-absorbing groups having silicon-silicon bonds for 193 nm exposure.

[0356] Alternatively, an intermediate layer formed by a chemical vapor deposition (CVD) method can be used. Examples of intermediate layers that are highly effective as anti-reflection films and are produced by a CVD method include, but are not limited to, SiON films. Generally, forming an intermediate layer by a wet process such as spin coating or screen printing is more convenient and cost-effective than using a CVD method. The upper layer resist in a three-layer process may be either a positive or negative type, and the same resist as a commonly used single-layer resist can be used.

[0357] When forming a resist layer using the photoresist material, wet processes such as spin coating and screen printing are preferably used, as in the case of forming the underlayer film. After applying the resist material by spin coating or the like, pre-baking is typically performed, preferably at 80 to 180°C for 10 to 300 seconds. Subsequently, exposure, post-exposure baking (PEB), and development are performed according to conventional methods to obtain a resist pattern. The thickness of the resist film is not particularly limited, but is generally preferably 5 to 50,000 nm, more preferably 10 to 10,000 nm, and even more preferably 10 to 1,000 nm.

[0358] The exposure light may be appropriately selected depending on the photoresist material used, and generally includes high-energy rays with a wavelength of 300 nm or less, specifically excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, X-rays, and the like.

[0359] The resist pattern formed by the above-described method is prevented from collapsing due to the underlayer film of this embodiment, and therefore, by using the underlayer film of this embodiment, a finer pattern can be obtained and the exposure dose required to obtain the resist pattern can be reduced.

[0360] Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used for etching the underlayer film in the two-layer process. As the gas etching, etching using oxygen gas is suitable. In addition to oxygen gas, inert gases such as He and Ar, CO, CO ２ , N.H. ３ , S.O. ２ , N ２ , NO ２ , H ２ It is also possible to add gases such as CO, CO2, etc. without using oxygen gas. ２ , N.H. ３ , N ２ , NO ２ , H ２ Gas etching can also be performed using only the gas, and the latter gas is particularly preferably used to protect the sidewalls of the pattern to prevent undercutting of the sidewalls.

[0361] On the other hand, gas etching is also preferably used for etching the intermediate layer in the three-layer process. The same gas etching as that described in the two-layer process can be applied. In particular, processing of the intermediate layer in the three-layer process is preferably performed using a fluorocarbon-based gas and a resist pattern as a mask. Then, as described above, the underlying film can be processed by, for example, oxygen gas etching using the intermediate layer pattern as a mask.

[0362] Here, when an inorganic hard mask intermediate layer film is formed as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The nitride film formation method is not limited to the following, but for example, the methods described in Japanese Patent Laid-Open No. 2002-334869 and WO 2004 / 066377 can be used. A photoresist film can be formed directly on such an intermediate layer film, or an organic antireflective coating (BARC) can be formed on the intermediate layer film by spin coating, and then a photoresist film can be formed on top of that.

[0363] A polysilsesquioxane-based intermediate layer is also preferably used as the intermediate layer. By providing the resist intermediate layer with an anti-reflection coating effect, reflection tends to be effectively suppressed. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, but may be, for example, those described in JP-A-2007-226170 and JP-A-2007-226204.

[0364] The next etching of the substrate can also be carried out by a conventional method. For example, if the substrate is SiO ２ For SiN, etching can be performed using primarily fluorocarbon-based gases, while for p-Si, Al, and W, etching can be performed using primarily chlorine- or bromine-based gases. When etching a substrate with fluorocarbon-based gases, the silicon-containing resist of a two-layer resist process and the silicon-containing intermediate layer of a three-layer process are stripped simultaneously with substrate processing. On the other hand, when etching a substrate with chlorine- or bromine-based gases, the silicon-containing resist layer or silicon-containing intermediate layer is stripped separately, and generally, dry etching stripping using fluorocarbon-based gases is performed after substrate processing.

[0365] The underlayer film of this embodiment is characterized by its excellent etching resistance against these substrates. The substrate can be selected from known materials as appropriate, and is not particularly limited, including Si, α-Si, p-Si, SiO ２ , SiN, SiON, W, TiN, Al, etc. The substrate may also be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such a film to be processed include Si, SiO ２ Examples of low-k films include various low-k films and stopper films thereof, such as SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and these films are usually made of a material different from that of the substrate (support). The thickness of the substrate or film to be processed is not particularly limited, but is usually preferably about 10 to 1,000,000 nm, and more preferably 75 to 500,000 nm.

[0366] 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.

[0367] 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.

[0368] Compositions for semiconductor manufacturing in each example and comparative example were prepared as follows, and each evaluation was performed. 1: Preparation of Metal Compounds and Metalloid Compounds Example 1-1: 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 vacuum dried at 40°C to obtain 1.8 g of metal compound (A-1) containing a metal atom and an organic ligand.

[0369] Example 1-2: Synthesis of metalloid compound (A-2) Using the same reaction apparatus as in Example 1-1, 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 Example 1-1.

[0370] Example 1-3: Synthesis of metalloid compound (A-3)

[0111] 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 Example 1-2, 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.

[0371] Example 1-4: Synthesis of metalloid compound (A-4)

[0111] 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 Example 1-2, 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.

[0372] Example 1-5: Synthesis of metalloid compound (A-5)

[0111] 1.5 g of metalloid compound (A-5) containing a metalloid atom and an organic ligand was obtained by the same reaction method as in Example 1-2, 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.

[0373] Example 1-6: Synthesis of metalloid compound (A-6)

[0111] 1.2 g of metalloid compound (A-6) containing a metalloid atom and an organic ligand was obtained by the same reaction method as in Example 1-2, 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.

[0374] 2: Preparation of Solvents Solvents in each Example and Comparative Example were prepared as follows. The compound (B1) and solvent (B2) used are as follows: - 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 - Propylene glycol monomethyl ether (PGME): manufactured by Sigma-Aldrich

[0375] Example 2-1 Methyl 2-hydroxyisobutyrate (HBM) was used as a solvent for a composition for manufacturing a semiconductor.

[0376] Example 2-2 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-methoxyisobutyrate (α-MBM) in a mass ratio of 50:50 was used.

[0377] Example 2-3 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-methoxyisobutyrate (α-MBM) in a mass ratio of 99:1 was used.

[0378] Example 2-4 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-formyloxyisobutyrate (α-FBM) in a 50:50 (mass ratio) mixture was used.

[0379] Example 2-5 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-formyloxyisobutyrate (α-FBM) in a mass ratio of 99:1 was used.

[0380] Example 2-6 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl α-formyloxyisobutyrate (α-FBM) in a mass ratio of 99.9:0.1 was used.

[0381] Example 2-7 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl 3-hydroxyisobutyrate (3-HBM) in a 50:50 (mass ratio) mixture was used.

[0382] Example 2-8 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl 3-hydroxyisobutyrate (3-HBM) in a mass ratio of 99:1 was used.

[0383] Example 2-9 A solvent prepared by mixing methyl 2-hydroxyisobutyrate (HBM) and methyl 3-hydroxyisobutyrate (3-HBM) in a mass ratio of 99.9:0.1 was used.

[0384] Comparative Example 2-1 Propylene glycol monomethyl ether acetate (PGMEA) was used as a solvent for the composition for manufacturing a semiconductor.

[0385] Comparative Example 2-2 Propylene glycol monomethyl ether (PGME) was used as a solvent for the composition for manufacturing semiconductors.

[0386] The solvents produced in Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-2 are shown in Table 1 below.

[0387] 3: Solubility Test The metal compounds, semi-metal compounds, and photoacid generators used in the following examples and comparative examples 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.))

[0388] (1) Solubility Test 1 Solubility evaluation of metal compound (A-1) or semi-metallic compounds (A-2) to (A-6) was carried out using the solvents of Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-2. Specifically, a metal compound or semi-metallic compound was added to a solvent and stirred at room temperature for 24 hours to obtain a composition for manufacturing a semiconductor. The state of the composition for manufacturing a semiconductor after stirring was visually confirmed and evaluated according to the following criteria (composition for manufacturing a semiconductor being 100 wt %). The evaluation results are shown in Table 2. - Grade S: 10 wt % dissolved (clear solution confirmed visually) - Grade A: 5 wt % dissolved (clear solution confirmed visually) - Grade C: Insoluble (cloudy solution confirmed visually when 5 wt % of metal compound or photoacid generator was added)

[0389] Table 2 below shows that the semiconductor manufacturing compositions prepared in Examples 2-1 to 2-9 have superior solubility for metal compounds and photoacid generators compared to the semiconductor manufacturing compositions of Comparative Examples 2-1 and 2-2. This is presumably due to the high solubility of compound (B1) contained in solvent (B). Furthermore, in particular, semiconductor manufacturing compositions in which solvent (B) contains α-FBM or 3-HBM as solvent (B2) exhibit high solubility for metal compounds and photoacid generators and have been suitably used. On the other hand, when the semiconductor manufacturing compositions of Comparative Examples were used, some of the metal compounds or semimetallic compounds (A-1) to (A-6) were insoluble, confirming that they are not useful as semiconductor manufacturing compositions.

[0390] In this way, when a composition for manufacturing a semiconductor that satisfies the requirements of this embodiment is used, better solubility can be imparted compared to a composition for manufacturing a semiconductor of a comparative example that does not satisfy these requirements. As long as the requirements of this embodiment are satisfied, compositions other than those for manufacturing a semiconductor described in the examples also show the same effect.

[0391] (2) Solubility Test 2 Solubility evaluation of the metal compound (A-1) and the photoacid generator (C-1) was performed using the solvents of Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-2. Specifically, the metal compound (A-1) and the photoacid generator (C-1) were added to the solvent so that the concentrations of both were 10 wt % or 5 wt % relative to 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 % relative to 100 wt % of the final semiconductor manufacturing composition. The composition was stirred at room temperature for 24 hours to obtain a semiconductor manufacturing composition. The state of the semiconductor manufacturing composition after stirring was visually confirmed and evaluated according to the following criteria (where the semiconductor manufacturing composition is 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)

[0392] Table 2 below shows that the semiconductor manufacturing compositions prepared in Examples 2-1 to 2-9 had superior solubility for metal compounds and photoacid generators compared to the semiconductor manufacturing compositions of Comparative Examples 2-1 and 2-2. This is presumably due to the high solubility of compound (B1) contained in solvent (B). Furthermore, semiconductor manufacturing 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.

[0393] The semiconductor manufacturing composition of the present invention has excellent solubility in 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 can improve the coating performance of photoresist films, photoresist underlayer films, and photoresist overlayer films. 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 compositional content of the organic solvent, and the semiconductor manufacturing composition of the present invention satisfies this requirement. As long as the requirements of this embodiment are met, the same effects can be achieved with compositions other than those described in the examples.

[0394]

[0395] 4: Evaluation of In-Wafer Uniformity The metal compound (A-1) described above was mixed with a solvent (Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-2 shown in Table 1) to prepare a mixture with a metal compound concentration of 5 wt % relative to 100 wt % of the final semiconductor manufacturing composition. Next, an acid generator (C-1) was mixed with the mixture, and the acid generator concentration was adjusted to 1 wt %. Furthermore, 500 ppm of a nonionic surfactant, FTX-218 (polyoxyethylene alkyl ether, manufactured by NEOS Corporation), relative to the weight of the metal compound, was added to the mixture to obtain a semiconductor manufacturing composition for measuring in-wafer uniformity. The prepared semiconductor manufacturing composition was then spin-coated onto a silicon wafer at 1500 rpm to form a coating film, and the coating film was pre-baked at 110°C for 90 seconds to form a resist film. The thickness of the obtained resist film was measured at 49 points in the diameter direction of the silicon wafer, and the film thickness unevenness 3σ was calculated from the obtained measurement results using the following formula, and the in-plane uniformity was evaluated according to the following criteria. The in-plane uniformity was evaluated as follows. The results are shown in Table 3. 3σ (%) = 3 × film thickness standard deviation (nm) at 49 points / average film thickness (nm) × 100 Rating S: 3σ < 1% Rating A: 1% ≦ 3σ < 2% Rating C: 3σ ≧ 2%

[0396] The film thickness of the coating film formed from the composition for manufacturing a semiconductor was measured using a film thickness measurement system (device name "F50-UV", manufactured by Filmetrics, Inc.) in a constant temperature and humidity chamber at a temperature of 23°C and a humidity of 50% (relative humidity).

[0397]

[0398] The in-plane uniformity evaluation results in Table 3 reveal that the compositions for manufacturing semiconductors containing the solvents prepared in Examples 2-1 to 2-9 in Table 1 had superior in-plane uniformity when forming resist films compared to Comparative Examples 2-1 and 2-2. It is presumed that solvent (B) containing compound (B1) has high solubility, making it less likely for defects to occur in the coating film and improving the in-plane uniformity of the formed film. In particular, compositions for manufacturing semiconductors in which solvent (B) contains 3-HBM as solvent (B2) exhibit high in-plane uniformity and are preferably used.

[0399] 5. Evaluation of Metal Compound Concentration Reduction Ability The above-described metal compound (A-1) and a solvent (Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-2 shown in Table 1) were mixed to prepare a mixture with a desired metal compound concentration. Next, an acid generator (C-1) was mixed with the mixture, and the acid generator was adjusted so that the concentration of the acid generator (C-1) relative to the metal compound was 20%. Furthermore, 500 ppm of a nonionic surfactant, FTX-218 (polyoxyethylene alkyl ether, manufactured by NEOS Corporation), relative to the weight of the metal compound, was added to the mixture to prepare a semiconductor manufacturing composition. The prepared semiconductor manufacturing composition was then spin-coated on a silicon wafer at 1500 rpm to form a coating, which was then prebaked at 110°C for 90 seconds to form a 20 nm thick resist film. The metal compound concentration reduction ability was evaluated as follows, based on the metal compound concentration relative to 100 wt % of the semiconductor manufacturing composition when forming a 20 nm thick resist film. The evaluation results are shown in Table 4. Evaluation S: The concentration of the metal compound (A-1) when formed to a thickness of 20 nm is less than 1.2 wt%. Evaluation A: The concentration of the metal compound (A-1) when formed to a thickness of 20 nm is 1.2 wt% or less than 1.3 wt%. Evaluation C: The concentration of the metal compound (A-1) when formed to a thickness of 20 nm is 1.3 wt% or more.

[0400]

[0401] From the evaluation results of metal compound concentration reduction in Table 4, it was found that the semiconductor manufacturing compositions containing the solvents prepared in Examples 2-1 to 2-9 in Table 1 were able to reduce the concentration of metal compounds when forming a resist film compared to Comparative Examples 2-1 and 2-2. Specifically, in the semiconductor manufacturing compositions of the Comparative Examples, unless the concentration of the metal compound (A-1) was relatively high, the solution viscosity was difficult to increase and the solidification rate of the composition upon drying of the coating film was slow, resulting in a large amount of composition scattering during spinning and making it impossible to form a target film thickness. In contrast, the semiconductor manufacturing compositions of the Examples were likely to have a high solution viscosity even without increasing the concentration of the metal compound (A-1), and the solidification rate of the composition upon drying of the coating film was fast, suppressing the scattering of the composition during spinning. In other words, in the semiconductor manufacturing compositions of the Examples, the concentration of the metal compound (A-1) could be reduced to obtain a resist film of the desired thickness. In particular, a composition for manufacturing a semiconductor in which the solvent (B) contains α-MBM as the solvent (B2) has a large reduction in the concentration of metal compounds and is therefore preferably used.

[0402] Metal compounds and metalloid compounds are often produced from rare metals, which are rare and expensive substances on Earth. Therefore, reducing the concentration of metal compounds in resist compositions and underlayer film compositions is of great industrial significance, and Examples 2-1 to 2-9 can be said to be excellent compositions for manufacturing semiconductors.

[0403] According to the present invention, it is possible to provide a composition for semiconductor manufacturing that can increase the solubility of a metal compound or semi-metal compound in a solvent and the in-plane uniformity of a formed film, and further, can reduce the amount of the compound used, as well as a film formation method using the composition for semiconductor manufacturing.

Claims

1. A composition for manufacturing a semiconductor, comprising (A) a metal compound or semi-metal compound and (B) a solvent containing (B1) a compound represented by the following general formula (b-1), wherein the content of an active ingredient in the composition for manufacturing a semiconductor is 45 mass% or less based on the total mass of the composition for manufacturing a semiconductor. [In the above formula (b-1), R １ is an alkyl group having 1 to 10 carbon atoms.

2. The composition for manufacturing a semiconductor according to claim 1, further comprising at least one additive (C) selected from the group consisting of a photosensitizer and an acid generator.

3. R ​​in the general formula (b-1) １ 2. The composition for manufacturing a semiconductor 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.

4. The composition for manufacturing a semiconductor according to claim 1, wherein the solvent (B) includes, 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.

5. The composition for manufacturing a semiconductor according to claim 4, wherein the solvent (B2) contains 100 mass % or less based on the total amount (100 mass %) of the compound (B1).

6. The composition for manufacturing a semiconductor according to claim 5, wherein the solvent (B2) is contained in an amount of 0.0001 mass % or more based on the total amount (100 mass %) of the compound (B1).

7. The composition for manufacturing a semiconductor according to claim 1, wherein the metal atom or metalloid atom contained in the compound (A) is an atom of an element belonging to any one of Groups 3 to 16, Periods 3 to 7 of the periodic table.

8. The composition for manufacturing a semiconductor according to claim 1, wherein the metal atom or semi-metal atom contained in said compound (A) is an atom of any one of titanium, zirconium, hafnium, tantalum, tungsten, zinc, germanium, tin and tellurium.

9. The semiconductor manufacturing composition according to claim 1, wherein the compound (A) contains a halogen ligand, a hydroxo ligand, a carboxy ligand, an alkoxy ligand, a carboxylate ligand, an alkyl ligand, or an amide ligand as a ligand that bonds to a metal atom or a metalloid atom of the compound (A).

10. A film forming method comprising: step (1): applying the composition for semiconductor manufacturing according to any one of claims 1 to 9 onto a substrate to form a coating film; step (2): performing a heat treatment after step (1); and step (3): forming a resist pattern.

11. The composition for manufacturing a semiconductor according to any one of claims 1 to 9, which is a resist composition.

12. The composition for manufacturing a semiconductor according to any one of claims 1 to 9, wherein the composition for manufacturing a semiconductor is a resist auxiliary film composition.

13. The composition for manufacturing a semiconductor according to claim 12, wherein the resist auxiliary film is a resist underlayer film or a resist intermediate layer film.

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