Method of manufacturing a cured film and use thereof

Abstract

A method for producing a cured film having high film density, high film hardness, and high etching resistance. A method for producing a cured film, comprising (1) applying a composition (i) over a substrate; (2) forming a hydrocarbon-containing film from the composition (i); and (3) irradiating the hydrocarbon-containing film with plasma, an electron beam, and / or ions to form a cured film. Use of the cured film.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a cured film and its use. Background Technology

[0002] In semiconductor manufacturing, photoresist (hereinafter referred to as resist) is typically used for fine processing via photolithography. The fine processing steps include: forming a thin photoresist layer on a semiconductor substrate such as a silicon wafer; covering this layer with a mask pattern corresponding to the target device pattern; exposing the layer to active light such as ultraviolet light through the mask pattern; developing the exposed layer to obtain the photoresist pattern; and using the obtained photoresist pattern as a protective film for etching the substrate, thereby forming fine contours corresponding to the aforementioned pattern.

[0003] In semiconductor manufacturing, the area of ​​an IC chip is reduced by increasing the number of transistors per unit area, thereby continuously reducing the cost per transistor. However, this method attempts to achieve finer processing by shortening the wavelength of ultraviolet light irradiating the photoresist.

[0004] Using a single wavelength of ultraviolet light (e.g., a KrF light source at 248 nm) can lead to a reduction in the dimensional accuracy of the resist pattern due to the effect of standing waves. Therefore, methods for setting an underlying anti-reflective coating have been extensively studied to address this issue. Among the required characteristics of such an underlying anti-reflective coating, high anti-reflective performance is a prominent example.

[0005] To achieve further microfabrication, methods using ArF light sources (193nm) and EUV (13nm) have been extensively studied. However, in these cases, if the resist film thickness is too thick, the resist pattern may collapse or development residue may easily form. Therefore, there is a problem that sufficient protective film functionality cannot be obtained solely through resist.

[0006] Therefore, a method called multilayer is commonly used, which involves creating a new protective film under the photoresist, transferring the photoresist pattern onto the lower film, and using this lower film as a protective film to etch the substrate.

[0007] Various types of multilayer protective films exist, but amorphous carbon films can be used as protective films.

[0008] As a method to improve the function of a protective film by coating a solution and firing, coating a carbon film that can withstand general firing temperatures exceeding 450°C is one approach; for example, firing at 600°C can be used. Alternatively, the function of the protective film can be improved by increasing the carbon concentration in the liquid-solid material forming the carbon film, but this usually requires a trade-off with other properties such as solubility.

[0009] In this technological environment, Patent Document 1 describes a technique for manufacturing a cured film by irradiating a conductive polymer precursor such as polythiophene with plasma to polymerize it in order to obtain a film with excellent heat resistance and moisture resistance.

[0010] Patent Document 2 synthesizes a monocyclic hydrocarbon-bonded compound to achieve film-forming properties, solvent solubility, and heat resistance, providing it for use as a lower layer membrane, but does not describe plasma irradiation, electron beam irradiation, or ion irradiation during the membrane formation process.

[0011] Patent document 3 studies a method for forming a resist underlayer film with excellent etch resistance.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: Japanese Patent No. 5746670

[0015] Patent Document 2: WO2018 / 115043 International Publication

[0016] Patent Document 3: Japanese Patent Application Publication No. 2016-206676 Summary of the Invention

[0017] The problem the invention aims to solve

[0018] The inventor believes that there are more than one problem that requires improvement. Examples of these include:

[0019] The cured film has insufficient film density; the cured film has insufficient film hardness; and the intensity ratio R = I in Raman spectroscopy analysis cannot be obtained. D / I G The curing film has a thickness of 0.35 to 0.9; it is impossible to obtain a curing film with a hard structure such as diamond-like carbon structure; the film has insufficient etch resistance; it is impossible to obtain an insulating curing film; in the combination species used, the solute has insufficient solubility in the solvent; the composition has poor coatability; the film is oxidized during plasma or electron beam treatment; during plasma or electron beam treatment, the film disappears due to excessive dispersion of the solid components of the film.

[0020] The inventors focused on the possibility that the function of carbon films used as protective films in photolithography processes could be improved by increasing the film density. Therefore, it was considered useful to prepare carbon films containing a large amount of sp3 carbon, similar to diamond. Furthermore, the high solubility of this component was also considered advantageous.

[0021] As a result of their research, the inventors of this application have discovered a manufacturing method in which a high-density membrane with a large amount of sp3 carbon can be obtained by treating a membrane formed from a specific hydrocarbon-containing compound with energy such as plasma or an electron beam.

[0022] The present invention is made on the basis of the above-mentioned technical background and provides a method for manufacturing a cured film, comprising (1) applying a composition (i) on a substrate; (2) forming a hydrocarbon-containing film from the composition (i); and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and / or ions to form a cured film.

[0023] Methods for solving problems

[0024] The method for manufacturing a cured film according to the present invention comprises the following steps:

[0025] (1) Applying composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and / or ions to form a cured film; provided that composition (i) comprises (A) a hydrocarbon-containing compound and (B) a solvent; (A) the hydrocarbon-containing compound comprises a structural unit (A1) represented by the following formula (A1);

[0026]

[0027] Here, Ar 11 It was R 11 C that is replaced or not replaced 6-60 hydrocarbons (but Ar) 11 (Does not contain fused aromatic rings);

[0028] R 11 It is C 1-20 Straight-chain, branched, or cyclic alkyl, amino, or alkylamino groups;

[0029] R 12 For I, Br, or CN;

[0030] p 11 Numbers from 0 to 5, p 12 Numbers between 0 and 1, q 11 Numbers from 0 to 5, q 12 Numbers between 0 and 1, r 11 Numbers from 0 to 5, s 11 Numbers between 0 and 5;

[0031] p 11 q 11 and r 11 Not all values ​​are 0 at the same time in a structural unit.

[0032] In addition, this invention provides a carbon-cured film with a film density of 1.3–3.2 g / cm³. 3 The film hardness is 1.5–20 GPa; and / or the intensity ratio R = I in the G-band to D-band measurements using Raman spectroscopy (measurement at a laser wavelength of 514.5 nm). D / I G The value ranges from 0.35 to 0.90.

[0033] Furthermore, the present invention provides a method for manufacturing a resist layer on top of the aforementioned cured film. Furthermore, the present invention provides a method for manufacturing a resist pattern by exposing and developing the aforementioned resist layer. Furthermore, the present invention provides a method for manufacturing a device including any of the above methods.

[0034] The effects of the invention

[0035] By utilizing the method for manufacturing the cured film of the present invention, one or more of the following effects can be obtained.

[0036] It is possible to obtain cured films with high film density; it is possible to obtain cured films with high film hardness; it is possible to obtain films with an intensity ratio R = I in Raman spectroscopy analysis. D / I G The cured film has a thickness of 0.35–0.9. Cured films with a diamond-like carbon structure can be obtained; films with high corrosion resistance can be obtained; insulating cured films can be obtained; the solute in the composition has good solubility in the solvent; the composition has high coatability; it can prevent the film from oxidizing during plasma or electron beam treatment; and it prevents the film from disappearing due to excessive dispersion of the solid components during plasma or electron beam treatment.

[0037] Due to these advantageous properties, the cured film according to the present invention can be applied to the manufacturing process of precision devices, and is preferably applied to the manufacturing of semiconductors, more preferably to the manufacturing of DRAM and 3D NAND. The cured film of the present invention is also effective as a hard mask SOC (Spin on Carbon) and a core material SOC. Detailed Implementation

[0038] The embodiments of the present invention will be described in detail below.

[0039] definition

[0040] In this specification, unless otherwise stated, the definitions and examples provided in this paragraph shall be followed.

[0041] The singular form includes the plural form, and "a" or "that" means "at least one". The elements of a concept can be represented by multiple kinds, and when describing quantity (e.g., mass % or mole %), the quantity refers to the sum of multiple kinds.

[0042] "And / or" includes all combinations of elements, as well as individual uses.

[0043] When using "~" or "-" to indicate a numerical range, they include both endpoints, and the units are universal. For example, 5–25 mol% means above 5 mol% and below 25 mol%.

[0044] “C x-y “C” x -C y "and "C x Descriptions such as "" refer to the number of carbons in a molecule or substituent. For example, C 1～6 Alkyl refers to an alkyl chain with 1 or more but less than 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0045] If a polymer has multiple types of repeating units, these repeating units will copolymerize. These copolymerizations can be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, n, m, etc., as indicated in parentheses represent the number of repetitions.

[0046] Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius.

[0047] An additive refers to the compound itself that has this function (e.g., in the case of a base-generating agent, the compound that generates a base). In some embodiments, the compound is dissolved or dispersed in a solvent and added to the composition. As an embodiment of the invention, the composition of the invention preferably contains such a solvent as (B) solvent or other component.

[0048] The entire contents of International Publication No. WO2018 / 115043, International Patent Application No. PCT / EP2018 / 079621 filed on October 30, 2018, International Patent Application No. PCT / EP2018 / 085147 filed on December 17, 2018, and European Patent Application No. 18199921.3 filed on October 5, 2018, are incorporated herein by reference and inclusion in the present specification.

[0049] Composition

[0050] The method for manufacturing a cured film according to the present invention includes the following steps:

[0051] (1) Applying composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and / or ions to form a cured film.

[0052] Composition (i) contains (A) a hydrocarbon compound and (B) a solvent, wherein (A) the hydrocarbon compound contains a structural unit (A1) represented by formula (A1) described later. The hydrocarbon compound (A) may contain structural unit (A1) or other structural units. When (A) the hydrocarbon compound contains other structural units and (A) the hydrocarbon compound is a polymer, copolymerization of structural unit (A1) with other structural units is a preferred embodiment. As a preferred embodiment of the invention, the hydrocarbon compound (A) is substantially composed only of the constitutive unit (A1). However, end modification is permitted.

[0053] Here, the aforementioned hydrocarbon-containing film is preferably a resist underlayer film, more preferably a BARC (underlayer antireflective film) or SOC, and even more preferably a SOC. As one aspect of the present invention, SOC for hard masks and SOC for core materials can be cited as examples.

[0054] (A) Hydrocarbon compounds

[0055] The hydrocarbon compound according to the present invention (A) contains a structural unit (A1) represented by the following formula (A1).

[0056]

[0057] Ar 11 It was R 11 C that is replaced or not replaced 6-60 Hydrocarbons. But Ar 11 It does not contain fused aromatic rings. Ar is the preferred choice. 11 Examples include 9,9-diphenylfluorene, 9-phenylfluorene, phenyl, and C. 6-60 linear polystyrene and C 6-60 Branched polystyrene, which can be independently synthesized by R 11 Replaced or not replaced.

[0058] R 11 C 1-20 Straight-chain, branched, or cyclic alkyl, amino, or alkylamino groups. R 11 C is preferred 1-10 Straight-chain, branched, or cyclic alkyl groups, or alkylamino groups. R 11 More preferably C 1-3 straight-chain alkyl, C 1-3 Branched alkyl, cyclopentyl, cyclohexyl or dimethylamino.

[0059] (A) When a hydrocarbon compound has multiple structural units (A1), R 11 It can be used as a linker in Ar 11 Bonded between them. Replacing an Ar 11 R 11It can be one or more; one is preferred.

[0060] In a structural unit (A1), the groups within parentheses (e.g., p) 11 The group in parentheses can interact with R 11 Bonding. In this case, R 11 Ar serves as a linker 11 It bonds to this group.

[0061] Although not intended to limit the invention or to exceed its scope, Ar in the process of the invention 11 Embodiments containing naphthyl groups (e.g., naphthol) are prone to oxidation or difficult to rebuild the cured film based on plasma, electron beam and / or ion irradiation, and are therefore considered disadvantageous.

[0062] R 12 It is I, Br or CN; preferably I or Br, more preferably I.

[0063] p 11 The number is between 0 and 5. Here, as one embodiment of the invention, (A) the hydrocarbon compound may have only one of two (A1) as its structure. It can be in the form of: Ar 11 Both are phenyl groups, one Ar 11 p 11 =1, another Ar 11 p 11 =2. In this case, p as a whole 11 =1.5. Unless otherwise stated, the same applies to numbers in this specification.

[0064] p 11 Preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; even more preferably 1. 11 =0 is also a preferred embodiment of the present invention.

[0065] p 12 It is a number from 0 to 1; preferably 0 or 1; more preferably 1.

[0066] q 11 The number is between 0 and 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; and even more preferably 1. q 11 =0 is also a preferred embodiment of the present invention.

[0067] q 12 It is a number from 0 to 1; preferably 0 or 1; more preferably 1.

[0068] r 11 The number is between 0 and 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; and even more preferably 1.11 =0 is also a preferred embodiment of the present invention.

[0069] s 11 The number is between 0 and 5; preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; and even more preferably 1. 11 =0 is also a preferred embodiment of the present invention.

[0070] p 11 q 11 and r 11 Not all of them are 0 in a single structural unit.

[0071] The structural unit (A1) according to the invention can more specifically be a structural unit (A1-1), (A1-2) and / or (A1-3) represented by the following formulas (A1-1), (A1-2) and / or (A1-3). These will be described separately later.

[0072] In a preferred embodiment of the present invention, the structural unit (A1) is structural unit (A1-1).

[0073] The structural unit (A1-1) is represented by equation (A1-1).

[0074]

[0075] Ar 21 C 6-50 Aromatic hydrocarbons; preferably phenyl. Ar 21 The presence of phenyl ensures the solubility of (A) hydrocarbon compounds in the solvent, and the formation of thick films and other beneficial effects are expected.

[0076] R 21 R 22 and R 23 C independently 6-50 Aromatic hydrocarbons, hydrogen, or single bonds bonded to other structural units; preferably phenyl, hydrogen, or single bonds bonded to other structural units; more preferably phenyl or single bonds bonded to other structural units; even more preferably phenyl.

[0077] n 21 It is an integer that is either 0 or 1; preferably 0.

[0078] Ar 21 R 21 R 22 and R 23 It does not contain fused aromatic rings.

[0079] R 12 p 11 p 12 q 11q 12 r 11 and s 11 The definitions and preferred embodiments are the same as those described above.

[0080] Although not intended to limit the invention, specific examples of (A) hydrocarbon compounds having structural unit (A1-1) are listed below.

[0081]

[0082] In a more preferred embodiment of the present invention, the structural unit (A1-1) is structural unit (A1-1-1). The structural unit (A1-1-1) is represented by formula (A1-1-1).

[0083]

[0084] p 11 p 12 q 11 q 12 r 11 and s 11 The definition and preferred examples are the same as those described above, but the condition 1≤p is satisfied. 11 +q 11 +r 11 ≤4.

[0085] The structural unit (A1-2) is represented by equation (A1-2).

[0086]

[0087] L 31 and L 32 Each can be a single bond or a phenylene bond, respectively; a single bond is preferred.

[0088] n 31 n 32 m 31 and m 32 Each number is independently a number from 0 to 6; preferably an integer from 0 to 3. 31 +n 32 =5 or 6 is a preferred embodiment. L 31 When it is a single bond, m 31 =1. L 32 When it is a single bond, m 32 =1.

[0089] R 12 p 11 p 12 q 11 q 12 r 11 and s11 The definitions and implementation examples are the same as those described above.

[0090] While not intended to limit the invention, specific examples of (A) hydrocarbon compounds having structural units (A1-2) are listed below.

[0091]

[0092] The structural unit (A1-3) is represented by equation (A1-3).

[0093]

[0094] Ar 41 C 6-50 Aromatic hydrocarbons; preferably phenyl.

[0095] R 41 and R 42 C independently 1-10 Alkyl; preferably straight-chain C 1-6 alkyl.

[0096] R 41 and R 42 It can form hydrocarbon rings; preferably, it forms saturated hydrocarbon rings.

[0097] The carbon atom at position *41 is a quaternary carbon atom.

[0098] L 41 C 6-50 The arylene group, or a single bond bonded to other structural units; preferably phenylene or a single bond bonded to other structural units; more preferably a single bond bonded to other structural units.

[0099] R 12 p 11 p 12 q 11 q 12 r 11 and s 11 The definitions and preferred embodiments are independently the same as those described above.

[0100] While not intended to limit the invention, specific examples of (A) hydrocarbon compounds having structural units (A1-3) are listed below.

[0101]

[0102] When the hydrocarbon-containing compound (A) of the present invention is a polymer, as a preferred embodiment of the present invention, the aldehyde derivative used in the synthesis of the hydrocarbon-containing compound (A) is preferably 0 to 30 mol% (more preferably 0 to 15 mol%, further preferably 0 to 5 mol%, and even more preferably 0 mol%) based on the sum of all elements used in the synthesis. Formaldehyde is an example of such aldehyde derivative.

[0103] Using ketone derivatives instead of aldehyde derivatives is a preferred embodiment of the present invention.

[0104] The polymer synthesized in this way may have a main chain containing little or no secondary and tertiary carbon atoms. As a preferred embodiment of the invention, the aforementioned polymer is substantially free of secondary and tertiary carbon atoms in its main chain. While not bound by theory, this is expected to improve the heat resistance of the formed film while ensuring the solubility of the polymer. However, for end-modification, the inclusion of secondary and tertiary carbon atoms at the ends of the polymer is permissible.

[0105] In one embodiment of the present invention, the molecular weight of (A) the hydrocarbon-containing compound is 500 to 6,000, more preferably 500 to 4,000. When (A) the hydrocarbon-containing compound is a polymer, the weight-average molecular weight (Mw) is used as the molecular weight. In the present invention, Mw can be measured by gel permeation chromatography (GPC). In the same measurement, a GPC column at 40 degrees Celsius, a tetrahydrofuran elution solvent of 0.6 mL / min, and monodisperse polystyrene as the standard are preferred examples. The same applies below.

[0106] Based on composition (i), it is preferred that (A) contains 2 to 30% by mass of hydrocarbon compound, more preferably 5 to 30% by mass; further preferably 5 to 25% by mass; and even more preferably 10 to 25% by mass.

[0107] (B) Solvent

[0108] The composition (i) of the present invention comprises (B) a solvent. The (B) solvent is not particularly limited, as long as it can dissolve the components to be mixed. The (B) solvent preferably comprises an organic solvent, more preferably a hydrocarbon solvent, ether solvent, ester solvent, alcohol solvent, ketone solvent, or a mixture thereof.

[0109] Specific examples of solvents for (B) include water, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, trimethylbenzene, methanol, ethanol, n-propanol, isopropylbenzene Alcohols, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecane Alcohols, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzyl methanol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptahydrate-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, acetone, Methyl ethyl ketone, methyl n-acetone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentanone, ethyl n-butyl ketone, methyl n-hexanone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanedione, acetone-acetone, diacetone alcohol, acetophenone, anisole, diethyl ether, isopropyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-Epoxypropane, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, anisole, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate (n-butyl acetate, nBA), isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl acetate Cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate Ethyl lactate (EL), n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesulfonate lactone. These solvents can be used alone or in mixtures of two or more.

[0110] In a preferred embodiment of the invention, solvent (B) is composed essentially only of those selected from the specific examples described above. However, solvent (B) may contain small amounts of solvents for dissolving solid components of surfactants and additives.

[0111] As solvent (B), PGMEA, PGME, anisole, EL, nBA, DBE, or any mixture thereof are preferred; PGMEA, PGME, or mixtures thereof are more preferred; and PGMEA is even more preferred. When mixing two solvents, a mass ratio of the first solvent to the second solvent of 95:5 to 5:95 is preferred (more preferably 90:10 to 10:90, and even more preferably 80:20 to 20:80).

[0112] Regarding its relationship with other layers and films, one embodiment is that the solvent in (B) is substantially water-free. For example, the amount of water in the total amount of solvent in (B) is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0.001% by mass or less. It is also a preferred embodiment that the solvent in (B) is water-free (0% by mass).

[0113] Based on composition (i), the solvent (B) is preferably 60-98% by mass; more preferably 60-95% by mass; further preferably 70-95% by mass; and even more preferably 70-90% by mass.

[0114] (C) Surfactants

[0115] The composition (i) according to the invention may further contain (C) a surfactant.

[0116] The coating properties can be improved by including surfactants.

[0117] In this invention, (C) surfactant refers to the compound itself having the above-described function. This compound can be dissolved or dispersed in a solvent and included in the composition, but such a solvent is preferably included in the composition as (B) solvent or other component. The same applies below to various additives that may be contained in the composition.

[0118] Surfactants that can be used in this invention include (I) anionic surfactants, (II) cationic surfactants, or (III) nonionic surfactants. More specifically, preferred surfactants include (I) alkyl sulfonates, alkylbenzene sulfonic acids, and alkylbenzene sulfonates; (II) dodecylpyridine chloride and laurylmethyl ammonium chloride; and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene kyne glycol ether; fluorinated surfactants such as Fluorad (Sumitomo 3M), Megafac (DIC), Surflon (Asahi Glass); or organosiloxane surfactants (e.g., KP341, Shin-Etsu Chemical Co., Ltd.).

[0119] Based on (A) the hydrocarbon-containing compound, the surfactant (C) is preferably 0.01 to 10% by mass; more preferably 0.05 to 10% by mass; further preferably 0.05 to 5% by mass; and even more preferably 0.05 to 1% by mass.

[0120] (D) Additives

[0121] The composition (i) according to the invention may further contain additive (D). Additive (D) is a component different from (A), (B), and (C). Preferably, additive (D) includes a crosslinking agent, a high-carbon material, an acid generator, a free radical generator, a photopolymerization initiator, a substrate adhesion enhancer, or a mixture thereof. More preferably, additive (D) includes a crosslinking agent, an acid generator, a free radical generator, a photopolymerization initiator, a substrate adhesion enhancer, or a mixture thereof. Crosslinking agents are an example of a more preferred additive (D). As another embodiment of the invention, a high-carbon material is an example of additive (D).

[0122] The crosslinking agent is useful for the following purposes: improving film-forming properties when forming the hydrocarbon-containing film of the present invention, eliminating mixing with the upper film (e.g., the silicon-containing interlayer and photoresist), and eliminating the diffusion of low-molecular-weight components to the upper film, etc.

[0123] Examples of crosslinking agents include melamine compounds, guanidine compounds, urea compounds or urea compounds, epoxy compounds, thioepoxide compounds, isocyanate compounds, azide compounds, alkenyl ether compounds, and other compounds containing double bonds that are substituted with at least one group selected from hydroxymethyl, alkoxymethyl, or acylmethyl groups. These can also be used as additives or as side groups introduced into polymer side chains. Furthermore, hydroxyl-containing compounds can also be used as crosslinking agents.

[0124] Among the aforementioned compounds, examples of epoxy compounds include tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, compounds of hexamethylolmelamine with 1 to 6 hydroxymethyl groups methylated by methoxy groups, and mixtures thereof; hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds of hexamethylolmelamine with 1 to 6 hydroxymethyl groups methylated by acyloxy groups, and mixtures thereof. Examples of guanidine compounds include tetramethylolguanidine, tetramethoxymethylguanidine, compounds of tetramethylolguanidine with 1 to 4 hydroxymethyl groups methylated by methoxy groups, and mixtures thereof; tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds of tetramethylolguanidine with 1 to 4 hydroxymethyl groups methylated by acyloxy groups, and mixtures thereof. Examples of urea compounds include tetrahydroxymethyl urea, tetramethoxy urea, tetramethoxymethyl urea, compounds of tetrahydroxymethyl urea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, and compounds of tetrahydroxymethyl urea in which 1 to 4 hydroxymethyl groups are acyloxymethylated, or mixtures thereof. Examples of urea compounds include tetrahydroxymethyl urea, tetramethoxymethyl urea, compounds of tetrahydroxymethyl urea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea, etc.

[0125] Examples of compounds containing alkenyl ether groups include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0126] The molecular weight of the crosslinking agent is preferably 100-480, more preferably 200-400, and even more preferably 300-380.

[0127] While not intended to limit the invention, the following are specific examples of crosslinking agents.

[0128]

[0129] High-carbon materials are molecules with the most carbon atoms per molecule and are the solid components remaining in the hydrocarbon-containing film of this invention. Adding high-carbon materials can improve etching resistance. The high-carbon material itself does not necessarily need to form a film; it only needs to be able to form a hydrocarbon-containing film together with (A) the hydrocarbon compound.

[0130] While not intended to limit the invention, specific examples of high-carbon materials include isothrone purple, 2,7-bis(1-pyrene)-9,9'-spirobis[9H-fluorene], 9,9-bis[4-[bis(2-naphthyl)amino]phenyl]fluorene, 9,9-bis[4-[N-(1-naphthyl)anilino]phenyl]fluorene, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxydiimide, benzanthrone, perylene, benzene, 5,12-naphthoquinone, 6,13-pentabenzoquinone, and fullerene C. 60 C 60 MC 12 (C 60 (Condensed N-methylpyrrolidine)-mC 12 -phenyl), ICBA (indene-C 60 (Double adduct), N,2-diphenyl

[60] fullerene pyrrolidine, PCBM (methyl phenyl-C61-butyrate), PCBB (butyl phenyl-C61-butyrate), N-phenyl-2-hexyl

[60] fullerene pyrrolidine, etc.

[0131] In this invention, based on (A) the hydrocarbon-containing compound, (D) the additive is preferably 0.05 to 100% by mass; more preferably 0.05 to 25% by mass; further preferably 0.05 to 20% by mass; even more preferably 0.05 to 15% by mass; it should be noted that it is even more preferably 0.05 to 10% by mass.

[0132] Methods for manufacturing cured films

[0133] The method for manufacturing a cured film according to the present invention includes the following steps.

[0134] (1) Applying composition (i) over a substrate; (2) forming a hydrocarbon-containing film from composition (i); and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and / or ions to form a cured film.

[0135] In this invention, coating methods such as spin coaters and coating machines can be used as methods for applying composition (i). The composition (i) of this invention is advantageous for embedding patterns on a substrate. Preferably, the substrate and composition (i) are in direct contact with the upper part of the substrate, but coating can also be performed using other films.

[0136] As a method for forming a hydrocarbon-containing film from composition (i), examples include ultraviolet irradiation and / or heating, with heating being preferred.

[0137] Preferably, the ultraviolet irradiation conditions are: using ultraviolet light with a wavelength of 10–380 nm (more preferably 10–200 nm) at a frequency of 100–10,000 mJ / cm². 2 The cumulative amount of light irradiation is used for light irradiation.

[0138] Air is suitable as an atmosphere for ultraviolet irradiation and heating. The oxygen concentration can also be reduced to prevent oxidation of the composition (i) and / or the hydrocarbon-containing film of the present invention. For example, by injecting an inert gas (N2, Ar, He, or a mixture thereof) into the atmosphere, the oxygen concentration can be set to below 1,000 ppm (preferably below 100 ppm).

[0139] When forming a hydrocarbon-containing film by heating, the heating conditions can be appropriately selected from a range of heating temperature of 80–800°C (preferably 200–700°C, more preferably 300–600°C) and heating time of 30–180 seconds (preferably 30–120 seconds). Although not bound by theory, it is believed that high-temperature heating can effectively promote the crosslinking of groups that crosslink polymers, such as acetylene groups, which helps to increase the density of the cured film.

[0140] Heating can be performed in multiple steps (step-by-step baking). A hydrocarbon-containing film can be formed by heating alone, but it is preferred to combine it with ultraviolet irradiation.

[0141] Hydrocarbon-containing films are irradiated with plasma, electron beams, and / or ions to form cured films. Although not bound by theory, it is believed that these irradiations cause the chemical bonds in the hydrocarbon-containing film to dissociate and re-bond, and reconstruct into a cured film with a diamond-like carbon structure, thereby contributing to the increase in hardness and density.

[0142] As one embodiment of the present invention, it also includes irradiation with plasma, electron beam and / or ions immediately after coating composition (i) to form a cured film. That is, the present invention also includes embodiments in which the above-described steps (2) and (3) are performed almost simultaneously in one operation (step).

[0143] Plasma irradiation can be performed using known methods. For example, the literature described in patent No. 5746670 (patent document) and “Improvement of the wiggling profile of spin-on carbon hard mask by H2plasma treatment” (J.Vac.Sci.Technol.B26(1), Jan / Feb 2008, pp.67-71, non-patent document) can be cited.

[0144] The RF discharge power can be selected from 1,000 to 10,000 W, more preferably from 1,000 to 5,000 W.

[0145] Examples of suitable gaseous atmospheres include N2, NF3, H2, rare gases, and fluorocarbons; preferred examples include Ar, Ne, NF3, H2, CF4, CHF3, CH2F2, CH3F, C4F6, and C4F8. Two or more of these gases can be mixed. The use of an O2-free gaseous atmosphere also yields the desired effects of the invention, which is an advantage of this invention.

[0146] The duration can be selected from 10 to 240 seconds.

[0147] Pressure can be appropriately selected.

[0148] Electron beam irradiation can be performed using known methods. For example, the methods described in "Technology and Utilization of Electron Beam Irradiation Devices" (July 2012, SEI technical review, No. 181, pp. 50-57, non-patent literature) can be cited.

[0149] As an accelerating voltage, it can be selected from 2 to 200kV.

[0150] The exposure dose can be selected from 100 to 5,000 kGy.

[0151] Electron beam irradiation is preferably performed while heating is being carried out. In this case, the temperature can be selected from 80 to 800°C (preferably 200 to 700°C, more preferably 300 to 600°C).

[0152] Ion irradiation can be performed using well-known methods. For example, the method described in "Raman spectroscopy and microhardness of ion-implanted aC:H-films" (Ceramics Int. 26(1), 2000, pp. 29-32, non-patent literature) can be cited. A preferred embodiment of the ion irradiation of the present invention is ion implantation.

[0153] Examples of elements that can be used as irradiated ions include hydrogen, boron, carbon, nitrogen, and noble gases; preferred are boron, carbon, nitrogen, neon, and argon; further preferred are carbon and nitrogen. Two or more of these gases can be mixed for use.

[0154] The accelerating voltage can be selected from 3 to 1000 kV. More preferably, the accelerating voltage is 5 to 750 kV, and even more preferably, it is 10 to 500 kV.

[0155] Irradiation dose can be from 10 13 ~10 18 ion / cm 2 The preferred irradiation dose is 5 × 10⁻⁶. 13 ~5×10 17 ion / cm2 Further preferred is 10 14 ~10 17 ion / cm 2 .

[0156] Ion irradiation can also be performed simultaneously within the heating chamber. In this case, the temperature can be selected to be below 500°C. When heating after plasma irradiation and electron beam irradiation, the heating temperature can be appropriately selected from the range of 80–800°C (preferably 200–700°C, more preferably 300–600°C), and the heating time can be appropriately selected from the range of 30–180 seconds (preferably 30–120 seconds). Although not bound by theory, it is believed that dangling bonds can be bonded by heating at high temperatures after plasma and electron beam irradiation, and the density of the cured film can be increased.

[0157] As irradiation devices, Tactras Vigus, EB-ENGINE (Hamamatsu Photonics), and EXCEED2300AH (Nisshin Ionizer) can be used. The effects of the present invention can be achieved by selecting the device and setting the conditions.

[0158] As one embodiment of the present invention, the cured film formed in the aforementioned step (3) has the advantages of increasing the film density by 5 to 75% and / or increasing the film hardness by 50 to 500% compared with the hydrocarbon-containing film formed in step (2).

[0159] Furthermore, the intensity ratio R = I in the G band to D band of the cured film formed in process (3) was determined by Raman spectroscopy analysis (measurement at a laser wavelength of 514.5 nm). D / I G The value can range from 0.35 to 0.90. It is not bound by theory, but it is thought to possibly have a diamond-like carbon structure.

[0160] Furthermore, it is believed that the hydrocarbon-containing film formed in step (2) is easier to etch by 5 to 200% (preferably 5 to 100%, more preferably 5 to 50%, and even more preferably 10 to 50%) than the cured film formed in the aforementioned step (3) (the latter cured film has higher etch resistance).

[0161] The surface resistivity of the cured film formed in step (3) is preferably 10. 9 ~10 16 Ω□ (more preferably 10) 12 ~10 16 Ω□, further preferably 10 13 ~10 16 Ω□). That is, (A) the hydrocarbon-containing compound is not a conductive polymer precursor, and the cured film of the present invention is not a conductive polymer film.

[0162] As one embodiment of the present invention, a carbon-cured film having the following characteristics is provided.

[0163] The membrane density is 1.3–3.2 g / cm³. 3 ;

[0164] The membrane hardness is 1.5–20 GPa; and / or

[0165] In Raman spectroscopy analysis (measurement at a laser wavelength of 514.5 nm), the intensity ratio of the G band to the D band is R = I. D / I G The value ranges from 0.35 to 0.90.

[0166] Preferably, the carbon-cured film is formed by plasma, electron beam, and / or ion irradiation. More preferably, the surface resistivity of the film is 10⁻⁶. 9 ~10 16 Ω□ (Ohm square). Using the aforementioned composition (i) as the composition for forming such a carbon-cured film is a more preferred embodiment of the present invention.

[0167] As a known SOC membrane, it is described in "The Role of Underlayers in EUVL" (Journal of Photopolymer Science and Technology Vol.31, Number 2, pp.209-214, 2018), but its membrane density is only 1.05–1.32 g / cm³. 3 about.

[0168] The preferred film density of the cured film or carbon-containing cured film of the present invention is 1.3 to 3.2 g / cm³. 3 (More preferably 1.4–3.2 g / cm³) 3 A further preferred value is 1.5–2.8 g / cm³. 3 It is believed that a high film density of the cured film contributes to increased etching resistance. Furthermore, if the stress in the cured film is too high, the stress is applied to the substrate, which is considered detrimental.

[0169] The membrane density can be determined, for example, using the methods described in the examples, and can be appropriately combined with and adjusted from known methods.

[0170] The membrane of the present invention preferably has a hardness of 1.5 to 20 GPa (more preferably 1.7 GPa to 20 GPa, even more preferably 2.0 GPa to 15 GPa, and even more preferably 2.0 GPa to 10 GPa).

[0171] The membrane hardness can be determined, for example, by using the methods described in the examples, and can be appropriately combined with and adjusted from known methods.

[0172] The membrane of the present invention preferably exhibits an intensity ratio R = I between the G band and the D band in Raman spectroscopy analysis (measured with a laser wavelength of 514.5 nm). D / I G The value is 0.35 to 0.90 (more preferably 0.40 to 0.90, further preferably 0.40 to 0.80, and even more preferably 0.45 to 0.70).

[0173] Raman spectroscopy analysis can be performed using, for example, the methods described in the examples, and can be appropriately combined with and modified from known methods (e.g., Japanese Patent No. 3914179 (Patent Document)).

[0174] <Methods for manufacturing resist films and resist patterns>

[0175] A resist film can also be manufactured on top of the cured film produced by the method of the present invention.

[0176] The method for manufacturing the resist film of the present invention includes:

[0177] (4) Apply a photoresist composition over the aforementioned cured film;

[0178] (5) Heat the resist composition to form a resist layer.

[0179] Furthermore, the present invention can also manufacture resist patterns from the aforementioned resist film. A method for manufacturing the resist pattern of the present invention includes:

[0180] (6) Expose the photoresist layer;

[0181] Optionally, (7) the resist layer is exposed to heat; and

[0182] (8) Develop the resist layer.

[0183] For clarity, the numbers in parentheses indicate the order. For example, step (4) is performed before step (5).

[0184] The following describes one embodiment of the method for manufacturing the resist film and resist pattern of the present invention.

[0185] The resist composition is applied over a substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, and an ITO substrate, etc.) by a suitable method. Here, in this invention, "over" includes cases where it is formed directly over the substrate and cases where it is formed with other layers in between. For example, a planarization film or a resist underlayer film may be formed directly over the substrate, and the resist composition may be applied directly over it. There are no particular limitations on the application method, and coating methods using a spinner and a coating machine can be cited as examples. After coating, the resist layer is formed by heating. Heating (5) is performed, for example, by a hot plate. The heating temperature is preferably 60 to 140°C, more preferably 90 to 110°C. Here, the temperature refers to the heating atmosphere, such as the heating surface temperature of the hot plate. The heating time is preferably 30 to 900 seconds, more preferably 60 to 300 seconds. Heating is preferably performed in an atmospheric or nitrogen atmosphere.

[0186] The thickness of the resist layer can be appropriately selected according to the purpose. The thickness of the resist layer can be greater than 1 μm.

[0187] The photoresist layer is exposed using a prescribed mask. The wavelength of the light used for exposure is not particularly limited, but exposure with wavelengths of 190–440 nm (more preferably 240–370 nm) is preferred. Specifically, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), i-lines (wavelength 365 nm), h-lines (wavelength 405 nm), g-lines (436 nm), etc., can be used. Wavelengths of 240–440 nm are more preferred, 360–440 nm are even more preferred, and 365 nm is even more preferred. These wavelengths are allowed within ±1%.

[0188] After exposure, post-exposure heating (post-exposure baking, hereinafter sometimes referred to as PEB) may be optionally performed. (7) Heating is performed, for example, by a hot plate. The temperature of post-exposure heating is preferably 80 to 160°C, more preferably 105 to 115°C, and the heating time is 30 to 600 seconds, preferably 60 to 200 seconds. Heating is preferably performed in an atmospheric or nitrogen atmosphere.

[0189] After PEB, development is performed using a developing solution. As a developing method, conventional methods for developing photoresist can be used, such as spin-dip development, immersion development, and agitation immersion development. Furthermore, as a developing solution, an aqueous solution containing inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium silicate; organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol, and triethylamine; or quaternary amines such as tetramethylammonium hydroxide (TMAH) can be used; a 2.38% by mass TMAH aqueous solution is preferred. A surfactant may also be added to the developing solution. The temperature of the developing solution is preferably 5–50°C, more preferably 25–40°C, and the developing time is preferably 10–300 seconds, more preferably 30–60 seconds. After development, washing or rinsing with water may be performed if necessary.

[0190] As one embodiment of the present invention, various substrates serving as the base can be patterned using a manufactured resist pattern as a mask. The substrate can be processed directly using the resist pattern as a mask, or it can be processed via an intermediate layer. For example, a resist underlayer film can be patterned using the resist pattern as a mask, and the substrate can be patterned using the resist underlayer film pattern as a mask. Known methods can be used for processing, such as dry etching, wet etching, ion implantation, and metal plating. Electrodes can also be wired onto the patterned substrate.

[0191] substrate

[0192] In this invention, examples of substrates include semiconductor wafers, glass substrates for liquid crystal display devices, glass substrates for organic EL display devices, glass substrates for plasma displays, substrates for optical discs, substrates for magnetic disks, substrates for optical disc drives, glass substrates for photomasks, and substrates for solar cells. The substrate can be an unprocessed substrate (e.g., a bare wafer) or a processed substrate (e.g., a patterned substrate). The substrate can be constructed by stacking multiple layers. Preferably, the surface of the substrate is a semiconductor. The semiconductor can be composed of oxides, nitrides, metals, or any combination thereof. Furthermore, the substrate surface is preferably selected from the group consisting of Si, Ge, SiGe, Si3N4, TaN, SiO2, TiO2, Al2O3, SiON, HfO2, T2O5, HfSiO4, Y2O3, GaN, TiN, TaN, Si3N4, NbN, Cu, Ta, W, Hf, and Al.

[0193] Devices

[0194] Devices can be manufactured by further processing the substrate of the present invention. Examples of such devices include semiconductor devices, liquid crystal display devices, organic EL display devices, plasma display devices, and solar cell devices. Semiconductor devices are preferred. These processing methods can be used. After the device is formed, the substrate can be cut into chips as needed, connected to a lead frame, and encapsulated with resin. An example of such encapsulated products is a semiconductor.

[0195] The present invention will be illustrated by the following examples. It should be noted that the invention is not limited to these examples.

[0196] <Synthesis of P0>

[0197] Prepare a reactor equipped with a stirrer, Liebig condenser, heating device, nitrogen inlet pipe, and temperature control device. Add 200 parts of 9-fluorenone (Tokyo Chemical Industry), 2333 parts of 9,9-bis(4-hydroxyphenyl)fluorenene (Osaka Gas Chemicals), and 10430 parts of dichloromethane to the reactor, maintaining the temperature at 40°C under a nitrogen atmosphere with stirring. Then, slowly add 92 parts of trifluoromethanesulfonic acid (Mitsubishi Materials Electronics Chemical) and 6 parts of 3-mercaptopropionic acid (Tokyo Chemical Industry) dissolved in dichloromethane (200 parts) to the reactor, maintaining the temperature at 40°C with stirring, and allow the reaction to proceed for 4 hours. After the reaction is complete, allow the solution to return to room temperature, add water to the reaction solution, filter to remove excess 9,9-bis(4-hydroxyphenyl)fluorenene, and wash with dichloromethane. Remove trifluoromethanesulfonic acid by thoroughly washing the dichloromethane solution with water. Then, dichloromethane was removed by distillation at 40℃ and 10 mmHg to obtain P0 (2111 parts). When the molecular weight was determined by GPC (tetrahydrofuran), the number average molecular weight Mn = 533 Da, the weight average molecular weight Mw = 674 Da, and the molecular weight distribution (Mw / Mn) = 1.26.

[0198] <Synthesis Example 1: Synthesis of P1>

[0199] Prepare a reactor equipped with a stirrer, Liebig condenser, heating device, nitrogen inlet pipe, and temperature control device. Add PO (350 parts), potassium carbonate (562 parts), and acetone (1414 parts) to the reactor, maintaining the temperature at 56°C under a nitrogen atmosphere with stirring. Then, slowly add allyl bromide (500 parts, Tokyo Chemical Industry) to the reactor, maintaining the temperature at 56°C with stirring, and allow the reaction to proceed for 3 hours. After the reaction is complete, return the solution to room temperature, filter to remove excess potassium carbonate and salt, and wash the precipitate with acetone. Then, distill off the acetone at 40°C and 10 mmHg. Dissolve the resulting solid in ethyl acetate (3000 parts), and wash the ethyl acetate solution thoroughly with water to remove metallic impurities. Distill off the ethyl acetate at 40°C and 10 mmHg, and dissolve the resulting solid in acetone (600 parts). The acetone solution was then added to n-heptane (6000 parts), the solid was filtered, and dried at 100°C and 10 mmHg to obtain P1 (345 parts). When the molecular weight was determined by GPC (tetrahydrofuran), the number-average molecular weight Mn = 671 Da, the weight-average molecular weight Mw = 833 Da, and the molecular weight distribution (Mw / Mn) = 1.32.

[0200]

[0201] <Synthesis Example 2: Synthesis of P2>

[0202] Prepare a reactor equipped with a stirrer, Liebig condenser, heating device, nitrogen inlet pipe, and temperature control device. Add PO (200 parts), potassium carbonate (323 parts), and acetone (616 parts) to the reactor, maintaining the temperature at 56°C under a nitrogen atmosphere with stirring. Then, slowly add 3-bromo-1-propyne (278 parts) to the reactor, maintaining the temperature at 56°C with stirring, and allow the reaction to proceed for 3 hours. After the reaction is complete, allow the solution to return to room temperature, filter to remove excess potassium carbonate and salt, and wash the precipitate with acetone. Then, distill off the acetone at 40°C and 10 mmHg. Dissolve the resulting solid in ethyl acetate (820 parts), and wash the ethyl acetate solution thoroughly with water to remove metallic impurities. Distill off the ethyl acetate at 40°C and 10 mmHg, and then dissolve the resulting solid component (185 parts) in acetone (185 parts). Then, methanol (1850 parts) was added to the acetone solution, the solid was filtered, and dried at 100°C and 10 mmHg to obtain P2 (76 parts). When the molecular weight was determined by GPC (tetrahydrofuran), Mn = 789 Da, Mw = 1054 Da, and Mw / Mn = 1.34.

[0203]

[0204] Preparation Example 1 of Composition 1

[0205] P1 (13.9 parts) and Megafac R-41 (0.1 parts, DIC) were added to propylene glycol 1-monomethyl ether 2-acetic acid (PGMEA) (86 parts) and stirred at room temperature for 1 hour. The solute was visually confirmed to be completely dissolved.

[0206] Composition 1 was obtained by filtration using a 0.2 μm fluoropolymer filter (Merck Millipore, SLFG025NS).

[0207] Preparation Example 2 of Composition 2

[0208] Add P2 (11.9 parts) and Megafac R-41 (0.1 parts) to PGMEA (88 parts) and stir at room temperature for 1 hour. Visually confirm that the solutes are completely dissolved.

[0209] Composition 2 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0210] Preparation Example 3 of Composition 3

[0211] Add P3 (13.9 parts) and Megafac R-41 (0.1 parts) with the structure shown below to PGMEA (86 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0212] Composition 3 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0213]

[0214] Preparation Example 4 of Composition 4

[0215] Add P4 (14.9 parts) and Megafac R-41 (0.1 parts) with the structure shown below to PGMEA (85 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0216] Composition 4 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0217]

[0218] Preparation Example 5 of Composition 5

[0219] Add P5 (14.9 parts) and Megafac R-41 (0.1 parts) with the structure shown below to PGMEA (85 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0220] Composition 5 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0221]

[0222] Preparation Example 6 of Composition 6

[0223] Add P6 (13.9 parts) and Megafac R-41 (0.1 parts) with the structure shown below to PGMEA (86 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0224] Composition 6 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0225]

[0226] Preparation Example 7 of Composition 7

[0227] Add the above-described P0 (24.9 parts) and Megafac R-41 (0.1 parts) to PGMEA (75 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0228] Composition 7 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0229] Preparation Example 8 of Composition 8

[0230] Add P7 (12.9 parts), P8 (1 part), and Megafac R-41 (0.1 parts) of the structure shown below to PGMEA (87 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0231] Composition 8 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0232]

[0233] Preparation Example 9 of Composition 9

[0234] Add P2 (8.9 parts), P9 (5 parts) with the structure shown below, and Megafac R-41 (0.1 parts) to PGMEA (85 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0235] Composition 9 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0236]

[0237] Preparation Example 10 of Composition 10

[0238] Add P2 (2.9 parts) and Megafac R-41 (0.1 parts) to PGMEA (97 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0239] Composition 10 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0240] Preparation Example 11 of Composition 11

[0241] Add P2 (3.9 parts) and Megafac R-41 (0.1 parts) to PGMEA (96 parts) and stir at room temperature for 1 hour. Visually confirm that the solute has completely dissolved.

[0242] Composition 11 was obtained by filtration using a 0.2 μm fluoropolymer filter.

[0243] Formation of hydrocarbon-containing films

[0244] Using a CLEAN TRACK ACT 12 (Tokyo Electron), each composition was coated onto a bare silicon wafer at 1,500 rpm. The wafer was then baked at 250°C for 60 seconds in an air atmosphere, followed by a further baking at 450°C for 120 seconds in a nitrogen atmosphere. This yielded a hydrocarbon-containing film from the composition.

[0245] Formation of the cured film (in the case of plasma treatment)

[0246] The wafer with the aforementioned hydrocarbon-containing film was subjected to plasma treatment for 2 minutes using a Tactras Vigus (Tokyo Electron).

[0247] Formation of the cured film (in the case of electron beam treatment)

[0248] The wafer with the aforementioned hydrocarbon-containing film was heated to 400°C using an EB-ENGINE (Hamamatsu Photonics) and simultaneously irradiated with a 1 mgy electron beam.

[0249] Formation of the cured film (in the case of ion irradiation treatment)

[0250] The wafer with the aforementioned hydrocarbon-containing film formed was subjected to an accelerating voltage of 10 kV for 10 seconds. 16 ion / cm 2 Carbon ion irradiation.

[0251] Measurement of film thickness

[0252] A wafer cross-section was fabricated, and SEM images were obtained using a JSM-7100F (Japan Electronics) to determine the film thickness.

[0253] Measurement of membrane density

[0254] The film density was calculated by fitting a simulated curve of cathode (Cu), power (45kV×200mA), resolution range (0.2 to 3.0°), and measurement step (0.002°) to the obtained X-ray reflectance curve through high-resolution X-ray reflectance measurement.

[0255] Measurement of membrane hardness

[0256] The film hardness was calculated using an ENT-2100 indentation hardness tester (Elionix) with an indentation load of 10 μN, 100 measurements, and a step interval of 100 ms.

[0257] I D / I G Measurement

[0258] Ig in Raman spectroscopy was determined using a triple Raman laser spectrometer (RAMANORT 64000, Horiba Jobin Yvon) at a laser wavelength of 514.5 nm. D / I G .

[0259] The Gaussian function will be used to find the area between approximately 900 and 1800 cm⁻¹. 1 The broad peak at that location is divided into 1590cm- 1 The nearby G-zone, and 1350cm- 1 Nearby D-belt, 1100cm- 1 Calculate the intensity of the D and G bands in the vicinity. Then calculate I. D / I G .

[0260] Etching resistance determination

[0261] Dry etching for 30 seconds was performed using an etching apparatus NE-5000N (ULVAC) at a chamber pressure of 0.17 mT, an RF power of 200 W, and gas flow rates of CF4 (50 sccm), Ar (35 sccm), and O2 (4 sccm).

[0262] According to the above-mentioned "Measurement of Film Thickness", measure the film thickness before and after etching, calculate the difference between the two, and calculate the reduction in film thickness per unit time.

[0263] Evaluation results

[0264] The evaluation results are recorded in Table 1 below.

[0265] Table 1

[0266]

[0267] In the table above,

[0268] For compositions 1 to 9, "before treatment" means the result of the evaluation of the hydrocarbon-containing film before plasma treatment, and "after treatment" means the result of the evaluation of the cured film after plasma treatment.

[0269] For composition 10, "before treatment" means the result of the evaluation of the hydrocarbon-containing film before electron beam irradiation, and "after treatment" means the result of the evaluation of the cured film after electron beam irradiation.

[0270] For composition 11, "before treatment" means the result of the evaluation of the hydrocarbon-containing film before ion irradiation, and "after treatment" means the result of the evaluation of the cured film after ion line irradiation.

[0271] Comparative example: Evaluation of the etch resistance of hydrocarbon-containing films

[0272] The etch resistance of the hydrocarbon-containing film of composition 2 before plasma treatment was measured in the same manner as described above. The etch resistance was 204 nm / min.

[0273] If we compare the etch resistance of the hydrocarbon-containing film (before plasma treatment) and the cured film (after plasma treatment) obtained from composition 2, the former is etched about 24% more easily.

Claims

1. A method for manufacturing a resist layer over a cured film, comprising the following steps: (1) Apply composition (i) above the substrate; (2) Forming a hydrocarbon-containing film from composition (i) by heating; and (3) Irradiate the hydrocarbon-containing film with plasma, electron beam and / or ions to form a cured film; The condition is that the composition (i) contains (A) a hydrocarbon compound and (B) a solvent; (A) The hydrocarbon compound contains a structural unit (A1-1) represented by the following formula (A1-1); in, Ar 21 C 6-50 Aromatic hydrocarbons, R 21 R 22 and R 23 C independently 6-50 Aromatic hydrocarbons, hydrogen, or single bonds bonded to other structural units, n 21 Integers that are either 0 or 1; Among them, Ar 21 R 21 R 22 and R 23 It does not contain fused aromatic rings. R 12 Is it I, Br, or CN? p 11 Numbers from 0 to 5, p 12 Numbers between 0 and 1, q 11 0, r 11 Numbers from 0 to 5, s 11 Numbers between 0 and 5; p 11 q 11 and r 11 Not all values ​​are 0 simultaneously in a single structural unit; In the Raman spectroscopy analysis of the cured film formed in step (3), the intensity ratio R = I of the G band and D band measured at a laser wavelength of 514.5 nm. D / I G The value ranges from 0.35 to 0.

90.

2. The method for manufacturing a resist layer according to claim 1, wherein, (A) The molecular weight of the hydrocarbon-containing compound is 500 to 6,000.

3. The method for manufacturing a resist layer according to claim 1 or 2, wherein, The aforementioned composition (i) further contains (C) a surfactant or (D) an additive; Among them, (D) additives include crosslinking agents, high-carbon materials, acid generators, free radical generators, photopolymerization initiators, substrate adhesion enhancers, or mixtures thereof.

4. The method for manufacturing a resist layer according to claim 1 or 2, wherein, The solvents mentioned in (B) above include organic solvents; The organic solvent includes hydrocarbon solvents, ether solvents, ester solvents, alcohol solvents, ketone solvents, or mixtures thereof.

5. The method for manufacturing a resist layer according to claim 1 or 2, wherein, Based on composition (i), (A) contains 2-30% by mass of hydrocarbon compounds. Based on composition (i), the content of solvent (B) is 60-98% by mass; Based on (A) hydrocarbon compounds, the content of (C) surfactants is 0.01–10% by mass; or Based on (A) hydrocarbon compounds, the content of (D) additives is 0.05–100% by mass.

6. The method for manufacturing a resist layer according to claim 1 or 2, characterized in that, The aforementioned hydrocarbon-containing compound (A) is a polymer, and the aldehyde derivative used in the synthesis of the aforementioned polymer is 0–30 mol% of the total amount of all elements used in the synthesis.

7. The method for manufacturing a resist layer according to claim 6, wherein, The aforementioned polymers contain virtually no secondary or tertiary carbon atoms in their main chain.

8. The method for manufacturing a resist layer according to claim 1 or 2, wherein, In the aforementioned process (3), plasma irradiation is used. The atmosphere is N2, NF3, H2, fluorocarbons, rare gases, or any mixture of these gases, or The RF discharge power is 1,000 to 10,000 W.

9. The method for manufacturing a resist layer according to claim 1 or 2, wherein, In the aforementioned process (3), irradiation is performed using an electron beam. The accelerating voltage is 2kV to 200kV, or The radiation dose ranges from 100 kGy to 5,000 kGy.

10. The method for manufacturing a resist layer according to claim 1 or 2, wherein, In the aforementioned process (3), ion irradiation is performed. The elements irradiated with the ions are hydrogen, boron, carbon, nitrogen, noble gases, or any mixture of these elements. The accelerating voltage is 3–1000 kV, or The irradiation dose is 10 13 ~10 18 ion / cm 2 .

11. The method for manufacturing a resist layer according to claim 1 or 2, wherein, Compared with the hydrocarbon-containing film formed in step (2), the film density of the cured film formed in the aforementioned step (3) increases by 5 to 75%, or the film hardness increases by 50 to 500%.

12. The method for manufacturing a resist layer according to claim 1 or 2, wherein, The hydrocarbon-containing film formed in step (2) is 5-200% more easily etched than the cured film formed in step (3); or The surface resistivity of the cured film formed in step (3) is 10. 9 ~10 16 Ω.

13. The method for manufacturing a resist layer according to claim 1 or 2, wherein, The heating conditions in the aforementioned process (2) are 80 to 800°C and last for 30 to 180 seconds.

14. The method for manufacturing a resist layer according to claim 1 or 2, wherein the film density of the cured film is 1.3 to 3.2 g / cm³. 3 ;or The hardness of the cured film is 1.5–20 GPa.

15. A method for manufacturing a resist pattern by exposing and developing the resist layer according to any one of claims 1 to 14.

16. A method for manufacturing a device, comprising the method according to any one of claims 1 to 15.

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