Diluent composition and method for manufacturing semiconductor device using same

Abstract

The present invention provides a diluent composition containing a solvent (B) containing a compound (B1) represented by general formula (b-1) (in formula (b-1), R0 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, and R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a thinner composition and a method for manufacturing a semiconductor device using the thinner composition, and in particular to a thinner composition for removing a photoresist film or a photoresist underlayer film. Background Art

[0002] When manufacturing semiconductor elements or liquid crystal elements, fine processing using photolithography using photoresist materials is performed. In the photolithography process, a photosensitive resin composition is applied to a wafer, and after the designed pattern is transferred, a fine circuit pattern such as a semiconductor integrated circuit is produced through an etching process. This includes methods of producing the desired fine circuit pattern through coating, exposure, development, etching and stripping processes. In particular, when manufacturing semiconductor elements, in recent years, with the high integration and high speed of LSI, the pattern size is required to be further refined. In order to cope with the refinement of such pattern dimensions, the light source for lithography used in forming the resist pattern is being shortened from KrF excimer laser (248nm) to ArF excimer laser (193nm) and EUV (extreme ultraviolet light) light source (13.5nm), and is therefore sensitive to pollution sources. Therefore, the residues and contaminants of the photoresist, BARC, SOC or SOG applied to the substrate in the coating process may become a contamination source in the exposure process, so they need to be removed in advance. In this case, a thinner composition can be used in the EBR (edge ​​bead removing) process.

[0003] In addition, photoresists or their lower films that use short-wavelength light sources have recently been applied, so the amount of photoresists or their lower films used has a greater impact on the manufacturing cost of integrated circuits. Therefore, in order to save costs, it is necessary to reduce the amount of photoresists or their lower films used. For this purpose, the RRC (reducing resist comsumption) process is applied. In this process, before applying the photoresist or its lower film, a diluent composition is applied to the surface of the substrate to perform a pre-wetting treatment to wet the surface of the substrate. Even if there is only a small amount of photoresist or its lower film, the photoresist can be evenly applied to the entire surface of the substrate.

[0004] Currently, although various diluent compositions for use in the EBR process or the RRC process have been developed, a diluent composition that can achieve these processes at a high level has not yet been developed.

[0005] Prior art literature Patent Literature Patent Document 1: Japanese Patent Application Publication No. 2001-188359 Patent Document 2: Japanese Patent Application Publication No. 2005-227770 Patent Document 3: Japanese Patent Application Publication No. 2015-232708 Summary of the invention

[0006] Problems to be solved by the invention Thus, the thinner composition used in manufacturing various devices such as the EBR process or the RRC process can be fully applied to the EBR process of various photoresists or their underlying films, and in order to reduce the manufacturing cost, it is necessary to develop a thinner composition with high RRC efficiency.

[0007] Technical solutions to solve problems The inventors of the present invention have conducted intensive studies to solve the above technical problems and have found that the above technical problems can be solved by using a diluent composition containing a solvent containing a compound having a specific structure. That is, the present invention is as follows.

[0008] <1> A diluent composition comprising a solvent (B) containing a compound (B1) represented by the following general formula (b-1).

[0009]

[0010] [In the above formula (b-1), R 0 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0011] <2> The thinner composition according to <1> above, wherein the solvent (B) does not contain methyl 2-methoxyisobutyrate (MBM), methyl 2-formyloxyisobutyrate (FBM), and methyl 2-acetoxyisobutyrate (ABM).

[0012] <3> The diluent composition according to <1> or <2> above, wherein R in the general formula (b-1) 0 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, formyl, acetyl, propionyl or benzoyl.

[0013] <4> The diluent composition according to any one of <1> to <3> above, wherein R in the general formula (b-1) 1 It is a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.

[0014] <5> The diluent composition according to any one of <1> to <4>, wherein the solvent (B) contains a compound represented by the following general formula (b-2) as a solvent (B2) other than the compound (B1).

[0015]

[0016] [In the above formula (b-2), R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0017] <6> The diluent composition according to <5> above, wherein the solvent (B) contains at least one selected from methyl α-hydroxyisobutyrate and α-hydroxyisobutyric acid as the solvent (B2).

[0018] <7> The thinner composition according to <5> or <6>, comprising less than 100% by mass of the solvent (B2) based on the total amount (100% by mass) of the thinner composition.

[0019] <8> The diluent composition according to <5> or <6>, comprising 100% by mass or less of the solvent (B2) based on the total amount (100% by mass) of the compound (B1).

[0020] <9> A method for manufacturing a semiconductor device, comprising the step of applying the thinner composition according to any one of <1> to <8> above on a substrate before applying a photoresist film material or a photoresist underlayer film material on the substrate.

[0021] <10> A method for manufacturing a semiconductor device, comprising the step of applying the thinner composition according to any one of <1> to <8> above on the substrate after applying a photoresist film material or a photoresist underlayer film material on the substrate and before an exposure step.

[0022] <11> A method for manufacturing a semiconductor device, comprising: a step of forming a photoresist film or a photoresist underlayer film on a substrate; and a step of removing the photoresist film or the photoresist underlayer film using the thinner composition described in any one of <1> to <8> above.

[0023] <12> A method for manufacturing a semiconductor device as described in <11> above, wherein the thinner composition is brought into contact with an edge and / or back surface of the substrate on which the photoresist film or photoresist underlayer film is formed, thereby removing the photoresist film or photoresist underlayer film.

[0024] <13> A method for manufacturing a semiconductor device as described in <12> above, wherein the photoresist film or photoresist underlayer film is removed by spraying the thinner composition onto an edge and / or back surface of the substrate while rotating the substrate on which the photoresist film or photoresist underlayer film is formed.

[0025] <14> The method for manufacturing a semiconductor device as described in any one of <11> to <13> above, further comprising a step of drying the thinner composition remaining on the substrate after the step of removing the photoresist film or the photoresist underlayer film.

[0026] <15> A method for manufacturing a semiconductor device as described in any one of <11> to <14> above, which further includes the steps of soft-baking the photoresist film, locally exposing the soft-baked photoresist film using a mask, and developing the exposed photoresist film using a developer to form a photoresist pattern.

[0027] <16> A method for manufacturing a semiconductor device as described in any one of <11> to <15> above, wherein, when a photoresist film or a photoresist underlayer film is formed on the edge and / or back side of the above-mentioned substrate, the method further includes a step of removing the photoresist film or the photoresist underlayer film on the edge and / or back side of the above-mentioned substrate after the above-mentioned photoresist film or the photoresist underlayer film is formed on the above-mentioned substrate.

[0028] <17> A solvent composition comprising a solvent (B) containing a compound (B1) represented by the following general formula (b-1).

[0029]

[0030] [In the above formula (b-1), R 0 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0031] <18> The solvent composition according to <17>, wherein the solvent (B) does not contain methyl 2-methoxyisobutyrate (MBM), methyl 2-formyloxyisobutyrate (FBM), and methyl 2-acetoxyisobutyrate (ABM).

[0032] <19> The solvent composition according to <17> or <18>, wherein the solvent (B) contains a compound represented by the following general formula (b-2) as a solvent (B2) other than the compound (B1).

[0033]

[0034] [In the above formula (b-2), R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0035] <20> The solvent composition according to <19>, comprising less than 100% by mass and 0.0001% by mass or more of the solvent (B2) based on the total amount (100% by mass) of the solvent composition.

[0036] Effects of the Invention According to a preferred embodiment of the present invention, the thinner composition can realize substrate processing suitable for manufacturing various devices (particularly semiconductor devices) and removal of a photoresist or its underlying film. DETAILED DESCRIPTION

[0037] [Diluent composition] The diluent composition of the present invention contains a solvent (B) (hereinafter also referred to as “component (B)”) containing a compound (B1) represented by the general formula (b-1).

[0038] <Component (B): Solvent> The diluent composition according to one embodiment of the present invention contains a solvent (B) containing a compound (B1) represented by the following general formula (b-1).

[0039] The compound (B1) may be used alone or in combination of two or more.

[0040]

[0041] In the above formula (b-1), R 0 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0042] In one embodiment of the present invention, R in the general formula (b-1) is 0 Preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, formyl, acetyl, propionyl or benzoyl, more preferably methyl, acetyl or formyl.

[0043] In one embodiment of the present invention, R in the general formula (b-1) is 1 It is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group, and more preferably a methyl group, an isopropyl group, an n-butyl group or an isobutyl group.

[0044] Among them, in one embodiment of the present invention, from the viewpoint of EBR performance or reprocessing performance and the viewpoint of in-plane uniformity of a coating film obtained by using it as a pre-wetting liquid, it is preferred that the solvent (B) does not contain methyl 2-methoxyisobutyrate (MBM), methyl 2-formyloxyisobutyrate (FBM) and methyl 2-acetoxyisobutyrate (ABM).

[0045] In the diluent composition of one embodiment of the present invention, the solvent (B) preferably contains a compound represented by the following general formula (b-2) as a solvent (B2) other than the compound (B1).

[0046]

[0047] In the above formula (b-2), R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group may be a linear alkyl group or a branched alkyl group.

[0048] As able to act as R 1 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl.

[0049] Among these, in one embodiment of the present invention, R in the above general formula (b-2) 1 Preferred is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.

[0050] In particular, it is preferred that the solvent (B) contain, as the solvent (B2), one or more selected from methyl 2-hydroxyisobutyrate (HBM) and 2-hydroxyisobutyric acid.

[0051] In the diluent composition of one embodiment of the present invention, examples of the solvent (B2) include: lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, and 2-heptanone; polyols 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 ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the above polyols or the above compounds having an ester bond, or monophenyl ether. bonds; cyclic ethers such as dioxane; esters other than compound (B1) such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl β-methoxyisobutyrate, methyl methoxypropionate, ethyl ethoxypropionate, methyl β-formyloxyisobutyrate; aromatic organic solvents such as anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc.; dimethyl sulfoxide (DMSO), etc.

[0052] These solvents (B2) may be used alone or in combination of two or more.

[0053] Among them, from the viewpoint of being able to realize not only the EBR process but also the RRC process at the same time, in the thinner composition of the present invention, the content ratio of the compound (B1) in the component (B) is preferably 20 to 100 mass %, more preferably 30 to 100 mass %, further preferably 50 to 100 mass %, further preferably 60 to 100 mass %, and particularly preferably 70 to 100 mass % relative to the total amount (100 mass %) of the component (B) contained in the thinner composition.

[0054] In addition, in the thinner composition of one embodiment of the present invention, the content of the compound (B1) is preferably 66.67% by mass or more, based on the total amount (100% by mass) of the solvent (B), from the viewpoint of RRC performance; more preferably 80% by mass or more, from the viewpoint of EBR performance; further preferably 90% by mass or more, from the viewpoint of reprocessing performance; further preferably 99% by mass or more, from the viewpoint of in-plane uniformity of a coating film obtained by using the composition as a pre-wetting liquid; and particularly preferably 99.9% by mass or more, from the viewpoint of suppressing defects of a coating film obtained by using the composition as a pre-wetting liquid.

[0055] In addition, in the component (B) used in one embodiment of the present invention, as a solvent (B2), methyl 3-hydroxyisobutyrate is preferably contained from the viewpoints of excellent solubility of the acid generator, EBR performance and reprocessing performance, excellent in-plane uniformity of the coating film obtained by using it as a pre-wetting liquid, and improved production yield of semiconductor devices. From the viewpoints of small contact angle and RRC performance, methyl 3-hydroxyisobutyrate is preferably contained. In addition, the mixing method of methyl 3-hydroxyisobutyrate is not particularly limited, and methyl 3-hydroxyisobutyrate can be contained by any method of adding methyl 3-hydroxyisobutyrate to compound (B1), generating or mixing as a by-product in the production process of compound (B1) and mixing.

[0056] The content of the solvent (B2) is not particularly limited, but is preferably less than 100% by mass, more preferably 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 1% by mass or less, further preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, based on the total amount (100% by mass) of the thinner composition, from the viewpoint of improving productivity by shortening the drying time of the thinner composition. From the viewpoint of excellent in-plane uniformity of the coating film obtained by using it as a pre-wetting liquid and improving the production yield of semiconductor devices, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.01% by mass or more.

[0057] The content of the solvent (B2) is preferably 100% by mass or less, more preferably 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, 1% by mass or less, further preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, based on the total amount (100% by mass) of the compound (B1), from the viewpoint of improving productivity by shortening the drying time of the thinner composition. From the viewpoint of excellent in-plane uniformity of a coating film obtained by using the solvent (B2) as a pre-wetting liquid and improving the production yield of semiconductor devices, the content is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.01% by mass or more.

[0058] In the thinner composition of the present invention, the content of component (B) can be appropriately set according to the application, and 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 thinner composition. In addition, the upper limit of the content of component (B) can be appropriately set, and can be 99% by mass or less, 98% by mass or less, 96% by mass or less, 93% by mass or less, 91% by mass or less, 86% by mass or less, 81% by mass or less, 76% by mass or less, 71% by mass or less, 66% by mass or less, or 61% by mass or less, based on the total amount (100% by mass) of the thinner composition.

[0059] The content of the component (B) can be appropriately selected from the respective options of the upper limit and the lower limit described above, and can be specified in any combination.

[0060] In addition, the thinner composition of the present invention may contain other components in addition to the above-mentioned component (B) depending on the application. As other components, for example, one or more selected from surfactants and antioxidants can be listed. Among them, the content of each of these other components can be appropriately selected according to the type of component, and is preferably 0.000000001 to 1 mass part, more preferably 0.000001 to 0.1 mass part, and further preferably 0.00001 to 0.001 mass part relative to 1 mass part of component (B) contained in the thinner composition.

[0061] The surfactant used in one embodiment of the present invention is not particularly limited, and compounds known in the art can be used. Preferably, ethylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol dipropyl ether, etc. are listed. These can be used alone, or two or more can be used in combination.

[0062] The antioxidant used in one embodiment of the present invention is not particularly limited, and compounds known in the art can be used, including tocopherol antioxidants, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfur antioxidants, benzotriazole antioxidants, benzophenone antioxidants, hydroxylamine antioxidants, salicylate antioxidants, triazine antioxidants, etc.

[0063] ・Tocopherol antioxidant Tocopherol compounds are usually vitamin E, which is also a chemical substance of natural origin. Therefore, they are highly safe and have a low environmental load. In addition, since they are oil-soluble and liquid at room temperature, they are also excellent in compatibility with diluent compositions and resistance to precipitation.

[0064] As tocopherol compounds, for example, tocopherol and its derivatives, tocotrienol and its derivatives can be cited. Tocopherol or tocotrienol is known to have natural compounds (d-form), non-natural compounds (l-form), racemic forms (dl-form) as equal mixtures thereof, etc. Considering that there are also substances that can be used as food additives, natural compounds (d-form) or racemic forms (dl-form) are preferred.

[0065] Specific examples of tocopherol include d-α-tocopherol, dl-α-tocopherol, d-β-tocopherol, dl-β-tocopherol, d-γ-tocopherol, dl-γ-tocopherol, d-δ-tocopherol, and dl-δ-tocopherol.

[0066] Specific examples of tocotrienol include d-α-tocotrienol, dl-α-tocotrienol, d-β-tocotrienol, dl-β-tocotrienol, d-γ-tocotrienol, dl-γ-tocotrienol, d-δ-tocotrienol, and dl-δ-tocotrienol.

[0067] Specific examples of the tocopherol derivatives include acetate, nicotinate, linoleate, succinate, etc. of the above-mentioned tocopherols. Specific examples of the tocotrienol derivatives include acetate, etc. of the above-mentioned tocotrienols.

[0068] ・Phenolic antioxidants Examples of the phenolic antioxidant include hindered phenolic antioxidants. Examples of the hindered phenolic antioxidant include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-nonylphenol, 2,2'-isobutylene-bis-(4,6-dimethyl-phenol), 4,4'-butylene-bis-(2-tert-butyl-5-methylphenol), 2,2'-thio- Bis-(6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'-thiodiethylbis-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)phenol, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 4,4'-butylenebis-(6-tert-butyl-3-methylphenol), 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol), butylhydroxyanisole, and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure may also be used.

[0069] In addition, examples of the phenolic antioxidant include butylated hydroxytoluene (BHT) and hydroquinone in addition to the above-mentioned hindered phenolic antioxidants.

[0070] ・Hindered amine antioxidants Examples of hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl) yl)amino-N-(2,2,6,6-tetramethyl-4-piperidinyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) (1,2,3,4-butanetetracarboxylate, poly{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexa Methyl{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidinyl)imino}, hexamethylene{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2 ,2,6,6-tetramethylpiperidine polycondensate and N,N′-4,7-tetra-[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, etc. In addition, oligomer and polymer compounds having a hindered amine structure can also be used.

[0071] ・Phosphorus antioxidants Examples of the phosphorus-based antioxidant include tris(isodecyl) phosphite, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, 4,4'-isopropylidene diphenol alkyl phosphite, trisnonylphenyl phosphite, tris(dinonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(biphenyl) phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) Pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra(tridecyl)-4,4'-butylenebis(3-methyl-6-tert-butylphenol) diphosphite, hexa(tridecyl)-1,1,3-tri(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphite, sodium bis(4-tert-butylphenyl)phosphite, sodium 2,2-methylene-bis(4,6-di-tert-butylphenyl)phosphite, 1,3-bis(diphenoxyphosphinooxy)-benzene, tris(2-ethylhexyl)phosphite, triisodecylphosphite, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. In addition, oligomer-type and polymer-type compounds having a phosphite structure may also be used.

[0072] ・Sulfur antioxidants Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, 3,3'-didodecylthiodipropionate, 3,3'-dioctadecylthiodipropionate, and 3,3'-ditetradecylthiodipropionate. In addition, oligomer and polymer compounds having a thioether structure may also be used.

[0073] ・Benzotriazole antioxidants As the benzotriazole antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure and the like can be used.

[0074] ・Benzophenone antioxidant Examples of benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and 2-hydroxy-4-chlorobenzophenone. In addition, oligomeric and polymeric compounds having a benzophenone structure may also be used.

[0075] ・Hydroxyamine antioxidant Examples of the hydroxylamine antioxidant include hydroxylamine, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine phosphate, hydroxylamine hydrochloride, hydroxylamine citrate, and hydroxylamine oxalate.

[0076] ・Salicylate antioxidants Examples of salicylate antioxidants include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer and polymer compounds having a salicylate structure may also be used.

[0077] ・Triazine antioxidants Examples of the triazine antioxidant include 2,4-bis(allyl)-6-(2-hydroxyphenyl)-1,3,5-triazine, etc. In addition, oligomer and polymer compounds having a triazine structure may also be used.

[0078] Such a thinner composition of the present invention has excellent solubility for various photoresist films, photoresist lower layer films (films coated on the lower layer of the photoresist such as lower anti-reflection plate (BARC) or spin-coated carbon film) or photoresist upper layer films (upper anti-reflection film (TARC)), and can improve not only the EBR characteristics, reprocessing characteristics and coating performance of the photoresist film, photoresist lower layer film or photoresist upper layer film, but also excellent RRC characteristics. In particular, in the case of photoresists for g-rays, i-rays, KrF, ArF, EUV or EB, since the basic structures of the photoresists are different, it is necessary to adjust the composition content of the organic solvent in order to improve the solubility and coating properties of all of them, but the thinner composition of the present invention meets this condition.

[0079] <Method for manufacturing semiconductor device> One embodiment of the present invention is a method for manufacturing a semiconductor device using the thinner composition of the present invention.

[0080] More specifically, one embodiment of the method for manufacturing a semiconductor device of the present invention includes a step of coating the thinner composition of the present invention on the substrate before coating the photoresist film material, the photoresist upper film material or the photoresist lower film material on the substrate.

[0081] In addition, another embodiment of the method for manufacturing a semiconductor device of the present invention includes the step of applying the thinner composition of the present invention on the substrate after applying a photoresist film material or a photoresist underlayer film material on the substrate and before an exposure step.

[0082] Furthermore, another embodiment of the method for manufacturing a semiconductor device of the present invention includes a process of forming a photoresist film or a photoresist underlayer film on a substrate; and a process of removing the above-mentioned photoresist film or the photoresist underlayer film using the above-mentioned diluent composition of the present invention.

[0083] In this embodiment, it is preferable that the thinner composition is brought into contact with the edge and / or the back surface of the substrate on which the photoresist film or the photoresist underlayer film is formed to remove the photoresist film or the photoresist underlayer film.

[0084] In addition, in this embodiment, it is also preferred to rotate the substrate on which the photoresist film or photoresist underlayer film is formed while spraying the thinner composition onto the edge and / or back surface of the substrate to remove the photoresist film or photoresist underlayer film.

[0085] In addition, an embodiment further comprising the step of drying the thinner composition remaining on the substrate after the step of removing the photoresist film or the photoresist underlayer film is also preferred.

[0086] In addition, a method is also preferred which further includes the steps of soft-baking the photoresist film, partially exposing the soft-baked photoresist film using a mask, and developing the exposed photoresist film with a developer to form a photoresist pattern.

[0087] Furthermore, in the case where a photoresist film or a photoresist underlayer film is formed on the edge and / or back side of the above-mentioned substrate, it is also preferred that the method further includes a process of removing the photoresist film or the photoresist underlayer film on the edge and / or back side of the above-mentioned substrate after forming the above-mentioned photoresist film or the photoresist underlayer film on the above-mentioned substrate.

[0088] After the substrate is treated with the thinner composition, a photoresist or a photoresist underlayer film is coated, so that the substrate can be coated with a small amount of photoresist or photoresist underlayer film, thereby improving process cost and productivity.

[0089] The method for manufacturing a semiconductor device of the present invention may include the steps of coating a photoresist or a photoresist underlayer film after treating the substrate with the thinner composition, and further treating the substrate with the thinner composition before an exposure step.

[0090] In the above step, by further treating the substrate with the thinner composition, it is possible to quickly and efficiently remove unnecessary photoresist or photoresist underlayer film applied on the peripheral portion or rear portion of the substrate before the exposure step.

[0091] Example The present invention is described below using examples, but the present invention is not limited to these examples. The measured values ​​in the examples were measured using the following methods or devices.

[0092] (1) Content ratio of the structural unit of the resin use 13 C-NMR (model "JNM-ECA500, manufactured by JEOL Ltd., 125 MHz), using deuterated chloroform as solvent, 13 The quantitative mode of C was integrated 1024 times to measure the content ratio of the structural unit of the resin.

[0093] (2) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resin The Mw and Mn of the resin were measured by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard substance.

[0094] ・Device name: LaChrom series manufactured by Hitachi ・Detector: RI detector L-2490 ・Column: 2 pieces of TSKgelGMHHR-M manufactured by Tosoh Corporation + guard column HHR-H ・Solvent: THF (contains stabilizer) ・Flow rate 1mL / min ・Column temperature: 40℃ Then, the ratio of Mw to Mn (Mw / Mn) of the obtained resin was calculated as the value of the molecular weight distribution of the resin.

[0095] The solvents used in the following Examples and Comparative Examples are as follows.

[0096] <Ingredients (B1)> ・ABM: 2-acetoxyisobutyric acid methyl ester. In the above general formula (b-1), R 0 is acetyl and R1 A compound containing methyl.

[0097] ・iPAIB: 2-acetoxyisobutyric acid isopropyl ester. In the above general formula (b-1), R 0 is acetyl and R 1 It is an isopropyl compound.

[0098] <Ingredient (B2)> ・PGMEA: Propylene glycol monomethyl ether acetate ・HBM: 2-Hydroxyisobutyric Acid Methyl Ester The resins used in the following Examples and Comparative Examples are as follows.

[0099] (i) Cresol novolac resin EP4080G (manufactured by Asahi Organic Materials Co., Ltd.) (ii) Copolymer having structural units of hydroxystyrene / tert-butyl acrylate / styrene = 3 / 1 / 1 (molar ratio) (manufactured by Maruzen Petrochemical Co., Ltd., Mw = 12,000) (iii) A copolymer having structural units of MADM (2-methyl-2-adamantyl methacrylate) / GBLM (α-methacryloyloxy-γ-butyrolactone) = 25 / 75 (molar ratio) (Mn = 3770) (iv) XBisN-1: 13-(biphenyl-4-yl)-13H-dibenzoxanthene-3,10-diol (synthesized according to WO2013 / 024778) The acid generators used in the following Examples and Comparative Examples are as follows.

[0100] ・Acid generator (i): WPAG336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・Acid generator (ii): WPAG145 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・Acid generator (iii): Triphenylsulfonium nonafluorobutane butanesulfonate (manufactured by Sigma-Aldrich) ・Acid generator (iv): TPS-C1 (manufactured by Heraeus) ・Acid generator (v): TPS-N3 (manufactured by Heraeus) ・Acid generator (vi): DTBPIO-C1 (manufactured by Heraeus) ・Acid generator (vii): MDT (manufactured by Heraeus) [Solubility evaluation] Examples 1a to 4a, 1b to 7b, Comparative Examples 1a to 4a, 1b to 7b In the examples, methyl 2-acetoxyisobutyrate (ABM) was used as the solvent, and in the comparative examples, propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent. Solubility evaluations were performed on the resins (i) to (iv) and the acid generators (i) to (vii) shown in Tables 1 and 2.

[0101] The resin was added to the solvent so that the resin concentration became (i) 30 wt %, (ii) 35 wt %, (iii) 15 wt %, or (iv) 25 wt %, and the state after stirring at room temperature for 24 hours was evaluated by visual inspection according to the following criteria.

[0102] Evaluation A: Dissolution (visual inspection confirmed clear solution); Evaluation C: Insoluble (a turbid solution was confirmed by visual observation).

[0103] Regarding the acid generators (i) to (vii), the acid generators were added to the solvent so that the concentration of the acid generator became 10 wt %, and the state after stirring at room temperature for 1 hour was evaluated by visual observation according to the following criteria.

[0104] Evaluation A: Dissolution (visual inspection confirmed clear solution); Evaluation C: Insoluble (a turbid solution was confirmed by visual observation).

[0105] The results are shown in Tables 1 and 2.

[0106] [Table 1]

[0107] [Table 2]

[0108] When the thinner composition of the present invention is used, it can be confirmed that the solubility in both the resins (i) to (iv) and the acid generators (i) to (vii) is excellent, and it is particularly useful as a thinner composition for EBR applications and reprocessing applications. On the other hand, when the thinner composition of the comparative example is used, it can be confirmed that the solubility in the resins (i) to (iv) and the acid generators (i) to (vii) is partially insoluble, and it is not useful as a thinner composition.

[0109] Thus, when the thinner composition that satisfies the conditions of the present embodiment is used, good solubility can be imparted compared to the thinner composition of the comparative example that does not satisfy the conditions. As long as the conditions of the present embodiment described above are satisfied, the thinner composition other than that described in the examples also exhibits the same effect.

[0110] [Solubility evaluation] The diluent compositions of Examples A1-1 to 2-3 and Comparative Examples A1-1 to 2-1 were prepared using the solvents shown in Tables 3 and 4. The solubility of these diluent compositions in the resins (i) to (iv) and the acid generators (i) to (ii) shown in Tables 3 and 4 was evaluated.

[0111] <Solvent> ABM: 2-acetoxyisobutyric acid methyl ester (synthesized according to WO2020 / 004466) iPAIB: 2-acetoxyisobutyric acid isopropyl ester (synthesized according to WO2020 / 004466) HBM: 2-Hydroxyisobutyric acid methyl ester (manufactured by Mitsubishi Gas Chemical Co., Ltd.) PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) <Resin> (i) Cresol novolac resin EP4080G (manufactured by Asahi Organic Materials Co., Ltd.) (ii) Copolymer having structural units of hydroxystyrene / tert-butyl acrylate / styrene = 3 / 1 / 1 (molar ratio) (manufactured by Maruzen Petrochemical Co., Ltd., Mw = 12,000) (iii) A copolymer having structural units of MADM (2-methyl-2-adamantyl methacrylate) / GBLM (α-methacryloyloxy-γ-butyrolactone) = 25 / 75 (molar ratio) (Mn = 3770) (iv) XBisN-1: 13-(biphenyl-4-yl)-13H-dibenzoxanthene-3,10-diol (synthesized according to WO2013 / 024778) <Acid Generator> (i): WPAG336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (ii): WPAG145 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) A resin was added to the diluent composition shown in Tables 3 and 4 so that the resin concentration was (i) 30 wt%, (ii) 35 wt%, (iii) 15 wt%, or (iv) 25 wt%, and an acid generator was added so that the concentration of the acid generator shown in Tables 3 and 4 was 1 wt%. The state after stirring at room temperature for 24 hours was evaluated by visual observation according to the following criteria.

[0112] Evaluation S: dissolution (visual inspection to confirm clear solution); Evaluation A: substantially dissolved (visual inspection confirmed a substantially clear solution); Evaluation C: Insoluble (a turbid solution was confirmed by visual observation).

[0113] The results are shown in Tables 3 and 4.

[0114] [Table 3]

[0115] [Table 4]

[0116] As can be seen from Table 3, the diluent compositions prepared in Examples A1-1 to A1-3 are superior in solubility in the resin and the acid generator as compared with the diluent composition of Comparative Example A1-1.

[0117] As can be seen from Table 4, the diluent compositions prepared in Examples A2-1 to A2-3 are superior in solubility in the resin and the acid generator as compared with the diluent composition of Comparative Example A2-1.

[0118] The thinner composition of the present invention has excellent solubility for various photoresist films, lower layers of photoresists (films coated on the lower layer of photoresists such as lower anti-reflection plates (BARC) or spin-coated carbon films) or upper layers of photoresists (upper anti-reflection films (TARC)), and can not only improve the EBR characteristics, reprocessing characteristics, and coating performance of photoresist films, lower layers of photoresists, or upper layers of photoresists, but also has excellent RRC characteristics. In particular, in the case of photoresists for g-rays, i-rays, KrF, ArF, EUV, or EB, due to the different basic structures of the photoresists, in order to improve their solubility and coating properties, it is necessary to adjust the composition content of the organic solvent, but the thinner composition of the present invention meets this condition. As long as the above-mentioned conditions of this embodiment are met, the same effect is also exhibited in the case other than the thinner composition described in the examples.

Claims

1. A diluent composition, characterized in that: A solvent B containing a compound B1 represented by the following general formula (b-1), In the general formula (b-1), R 0 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

2. The thinner composition according to claim 1, characterized in that: The solvent B does not contain 2-methoxyisobutyric acid methyl ester MBM, 2-formyloxyisobutyric acid methyl ester FBM and 2-acetoxyisobutyric acid methyl ester ABM.

3. The thinner composition according to claim 1 or 2, characterized in that: In the general formula (b-1), R 0 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, formyl, acetyl, propionyl or benzoyl.

4. The thinner composition according to any one of claims 1 to 3, characterized in that: In the general formula (b-1), R 1 It is a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.

5. The thinner composition according to any one of claims 1 to 4, characterized in that: The solvent B contains, as a solvent B2 other than the compound B1, a compound represented by the following general formula (b-2): In the general formula (b-2), R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

6. The diluent composition according to claim 5, characterized in that: The solvent B contains, as the solvent B2, at least one selected from the group consisting of methyl α-hydroxyisobutyrate and α-hydroxyisobutyric acid.

7. The thinner composition according to claim 5 or 6, characterized in that: The solvent B2 is contained in an amount of less than 100% by mass based on 100% by mass of the total amount of the diluent composition.

8. The thinner composition according to claim 5 or 6, characterized in that: The solvent B2 is contained in an amount of 100% by mass or less based on 100% by mass of the total amount of the compound B1.

9. A method for manufacturing a semiconductor device, characterized in that: The method comprises the step of applying the thinner composition according to any one of claims 1 to 8 on the substrate before applying a photoresist film material or a photoresist underlayer film material on the substrate.

10. A method for manufacturing a semiconductor device, characterized in that: The method comprises the step of applying the thinner composition according to any one of claims 1 to 8 on the substrate after applying a photoresist film material or a photoresist underlayer film material on the substrate and before an exposure step.

11. A method for manufacturing a semiconductor device, characterized in that: include: A process of forming a photoresist film or a photoresist underlayer film on a substrate; and A step of removing the photoresist film or the photoresist underlayer film using the thinner composition according to any one of claims 1 to 8.

12. The method for manufacturing a semiconductor device according to claim 11, wherein: The thinner composition is brought into contact with the edge and / or the back surface of the substrate on which the photoresist film or the photoresist underlayer film is formed, thereby removing the photoresist film or the photoresist underlayer film.

13. The method for manufacturing a semiconductor device according to claim 12, wherein: The photoresist film or the photoresist underlayer film is removed by spraying the thinner composition toward the edge and / or the back surface of the substrate while rotating the substrate on which the photoresist film or the photoresist underlayer film is formed.

14. The method for manufacturing a semiconductor device according to any one of claims 11 to 13, wherein: The method further includes drying the thinner composition remaining on the substrate after removing the photoresist film or the photoresist underlayer film.

15. The method for manufacturing a semiconductor device according to any one of claims 11 to 14, characterized in that: The method further includes the steps of soft-baking the photoresist film, partially exposing the soft-baked photoresist film using a mask, and developing the exposed photoresist film using a developer to form a photoresist pattern.

16. The method for manufacturing a semiconductor device according to any one of claims 11 to 15, wherein: In the case where a photoresist film or a photoresist underlayer film is formed on the edge and / or back side of the substrate, the process also includes removing the photoresist film or the photoresist underlayer film on the edge and / or back side of the substrate after forming the photoresist film or the photoresist underlayer film on the substrate.

17. A solvent composition, characterized in that: A solvent B containing a compound B1 represented by the following general formula (b-1), In the general formula (b-1), R 0 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

18. The solvent composition according to claim 17, characterized in that: The solvent B does not contain 2-methoxyisobutyric acid methyl ester MBM, 2-formyloxyisobutyric acid methyl ester FBM and 2-acetoxyisobutyric acid methyl ester ABM.

19. The solvent composition according to claim 17 or 18, characterized in that: The solvent B contains, as a solvent B2 other than the compound B1, a compound represented by the following general formula (b-2): In the general formula (b-2), R 1 It is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

20. The solvent composition according to claim 19, characterized in that: The solvent B2 is contained in an amount of less than 100% by mass and not less than 0.0001% by mass based on 100% by mass of the total amount of the solvent composition.

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