TWI869396B - Method for manufacturing hardened film and its application - Google Patents

Abstract

The present invention provides a method for producing a hardened film having high film density, high film hardness and high etching resistance. The solution is a method comprising: (1) applying (i) a composition onto a substrate; (2) forming a hydrocarbon-containing film from (i) the composition; and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and/or ions to produce the hardened film. A use of the hardened film.

Description

Method for manufacturing hardened film and its application

The present invention relates to a method for manufacturing a hardened film and its use.

In the semiconductor manufacturing process, micro-machining is generally performed. Micro-machining is achieved through lithography using photoresist (hereinafter referred to as anti-etching agent). The steps of micro-machining include the following: forming a thin photoresist layer on a semiconductor substrate such as a silicon wafer, covering the layer with a mask pattern corresponding to the pattern of the target device, exposing the layer through the mask pattern using active light such as ultraviolet light, and developing the exposed layer to obtain a photoresist pattern, using the obtained photoresist pattern as a protective film to etch the substrate, thereby forming fine bumps corresponding to the above pattern. In semiconductor manufacturing, the area of IC chips is reduced by increasing the number of transistors per unit area, thereby continuously reducing the cost per unit transistor. However, this method attempts to achieve finer processes by shortening the wavelength of ultraviolet light irradiating the photoresist.

The use of single-wavelength ultraviolet light (for example, KrF light source 248nm) causes the problem of reduced dimensional accuracy of the anti-etching agent pattern due to the influence of the resident wavelength. Therefore, in order to solve this problem, the method of setting a lower anti-reflection film is widely discussed. As for the characteristics required for such an underlying anti-reflection film, a high anti-reflection effect can be listed. In order to achieve further fine processing, the method of using ArF light source (193nm) or EUV (13nm) is widely discussed. In this case, if the film thickness of the anti-etching agent is too thick, the anti-etching agent pattern collapses or it is easy to produce development residues. Therefore, there is a problem that the function of a sufficient protective film cannot be obtained with the anti-etching agent alone. Therefore, a multi-layer method is generally popular, in which a new protective film is made under the photoresist, the photoresist pattern is transferred to the lower film, and the lower film is used as a protective film to etch the substrate.

There are various types of multi-layer protective films, and an amorphous carbon film is sometimes used as the protective film.

As for the method of applying and firing the solution to improve the function of the protective film of the carbon film, there are examples of applying a carbon film that can withstand firing at 450°C, which is higher than the general firing temperature, and firing at, for example, 600°C. In addition, by increasing the carbon concentration in the solid matter of the carbon film forming solution, the function of the protective film can be improved, but this is generally compromised with other properties such as solubility.

In such a technical situation, Patent Document 1 discusses a technology for obtaining a film with excellent heat resistance and moisture resistance, which is to produce a hardened film by subjecting a conductive polymer precursor such as polythiophene to plasma irradiation to polymerization. Patent Document 2 provides a method for synthesizing a compound with a monocyclic hydrocarbon bonded thereto as an underlayer film in order to achieve film forming properties, solubility in solvents, and heat resistance, but does not describe plasma irradiation or electron beam or ion irradiation during the film formation process. Patent Document 3 discusses a method for forming an anti-etching agent underlayer film with excellent etching resistance. [Prior Technical Documents] [Patent Documents]

Patent document 1: Japanese Patent No. 5746670 Patent document 2: International Publication No. WO2018/115043 Patent document 3: Japanese Patent No. 2016-206676

[The problem that the invention wants to solve]

The inventors of the present invention believe that there are at least one problem that needs to be improved. For example, the following can be listed. The film density of the cured film is insufficient; the film hardness of the cured film is insufficient; it is impossible to obtain a cured film with an intensity ratio R= _ID / _IG of 0.35~0.9 in Raman spectroscopy analysis; it is impossible to obtain a cured film with a strong structure such as a diamond-like carbon structure; the etching resistance of the film is insufficient; it is impossible to obtain an insulating cured film; in the composition used, the solubility of the solute in the solvent is insufficient; the coating property of the composition is low; the film is oxidized during the plasma or electron beam treatment process; the solid components of the film are excessively scattered during the plasma or electron beam treatment process and the film disappears. The inventors of the present invention focused on the possibility that the function of the carbon film used as a protective film in the lithography step can be improved by increasing the film density. Therefore, it is believed that it is useful to make a carbon film with a high sp3 carbon content, similar to diamond. In addition, it is believed that it is useful for such a component to have high solubility at the same time. As a result of the discussion, the inventors of the present case discovered a manufacturing method that can obtain a film with a high sp3 carbon content and a high density by treating a film formed by a specific hydrocarbon-containing compound with energy such as plasma or electron beam. The present invention is made based on the above-mentioned technical background and provides a method: (1) applying (i) a composition onto a substrate; (2) forming a hydrocarbon-containing film from (i) the composition; and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and/or ions to form a cured film. [Means for Solving the Problem]

The method for producing a cured film according to the present invention comprises the following steps: (1) applying (i) a composition onto a substrate; (2) forming a hydrocarbon-containing film from (i) the composition; and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and/or ions to form a cured film; wherein (i) the composition comprises (A) a hydrocarbon-containing compound and (B) a solvent; (A) the hydrocarbon-containing compound comprises a constituent unit (A1) represented by the following formula (A1); Herein, Ar ₁₁ is a C _6-60 alkyl group which is substituted or unsubstituted by R ₁₁ (wherein Ar ₁₁ does not contain a condensed aromatic ring); R ₁₁ is a C _1-20 linear, branched or cyclic alkyl group, an amine group, or an alkylamine group; R ₁₂ is I, Br or CN; p ₁₁ is a number from 0 to 5, p ₁₂ is a number from 0 to 1, q ₁₁ is a number from 0 to 5, q ₁₂ is a number from 0 to 1, r ₁₁ is a number from 0 to 5, and s ₁₁ is a number from 0 to 5; p ₁₁ , q ₁₁ and r ₁₁ are not simultaneously 0 in one constituent unit.

The present invention also provides a carbon-containing hardened film, wherein the film density is 1.3-3.2 g/cm ³ ; the film hardness is 1.5-20 GPa; and the intensity ratio R= _ID / _IG of the G band to the D band in Raman spectroscopy (measured at a laser wavelength of 514.5 nm) is 0.35-0.90.

Furthermore, the present invention provides a method for manufacturing an anti-corrosion agent layer on the above-mentioned cured film. Furthermore, the present invention provides a method for exposing and developing the above-mentioned anti-corrosion agent layer to manufacture an anti-corrosion agent pattern. Furthermore, the present invention provides a method for manufacturing a device comprising any of the above-mentioned methods. [Effect of the invention]

By using the method for producing a cured film of the present invention, one or more of the following effects can be expected. A cured film with high film density can be obtained; a cured film with high film hardness can be obtained; a cured film with an intensity ratio R= _ID / _IG of 0.35 to 0.9 in Raman spectroscopy analysis can be obtained; a cured film with a diamond-like carbon structure can be obtained; a film with high etching resistance can be obtained; an insulating cured film can be obtained; in the composition used, the solute has good solubility in the solvent; the composition has high coating properties; oxidation of the film can be prevented during plasma or electron beam treatment; and disappearance of the film due to excessive scattering of the solid components of the film can be prevented during plasma or electron beam treatment. Due to the advantageous properties, the hardened film of the present invention can be applied to the manufacturing steps of fine devices, preferably to semiconductors, and more preferably to the manufacturing of DRAM or 3D NAND. The hardened film of the present invention is also effective as a hard mask SOC (Spin on carbon) or a core material SOC.

[Form used to implement the invention]

The embodiments of the present invention will be described in detail as follows.

[Definition] In this specification, unless otherwise specified or mentioned, the definitions and examples described in this paragraph shall apply. The singular includes the plural, and "1" and "the" mean "at least 1". An element of a certain concept can be expressed in multiple ways. When its amount (for example, mass % or mole %) is recorded, its amount means the sum of such multiple ways. "And or" includes all combinations of elements and also includes the use of monomers. When "~" or "-" is used to indicate a numerical range, both endpoints are included and the units are common. For example, 5~25 mole % means more than 5 mole % and less than 25 mole %. "C _{x -y} ", "C _x ~C _y " and "C _x " refer to the number of carbons in a molecule or substituent. For example, C _1~6 alkyl means an alkyl chain having 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, the repeating units are copolymerized. The copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, grafting copolymerization, or any of the above. When a polymer or resin is represented by a structural formula, n, m, etc. recorded in parentheses represent the number of repeats. The unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius. An additive refers to the compound itself that has the function (for example, if it is an alkali generator, it is the compound itself that generates the alkali). The compound can also be dissolved or dispersed in a solvent and added to the composition. In one aspect of the present invention, such a solvent is preferably contained in the composition of the present invention as (B) solvent or other component.

Herein, all the contents described in 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 by reference as a part of this specification.

[Composition] The method for producing a cured film of the present invention comprises the following steps; (1) applying (i) composition onto a substrate; (2) forming a hydrocarbon-containing film from (i) composition; and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and/or ions to form a cured film. (i) composition comprises (A) a hydrocarbon-containing compound and (B) a solvent, wherein (A) the hydrocarbon-containing compound comprises a constituent unit (A1) represented by formula (A1) described below. (A) The hydrocarbon-containing compound only needs to comprise the constituent unit (A1), and may comprise other constituent units. When (A) the hydrocarbon-containing compound comprises other constituent units, and (A) the hydrocarbon-containing compound is a polymer, a suitable embodiment is copolymerization of the constituent unit (A1) and the other constituent units. In one preferred aspect of the present invention, the alkyl compound (A) is substantially composed of only the constituent unit (A1). However, modification of the terminal is permitted. Here, the alkyl film is preferably an anti-corrosion agent lower layer film, more preferably a BARC (lower layer anti-reflection film) or SOC, and further preferably SOC. In one aspect of the present invention, the following can be cited: SOC for hard mask, SOC for core material.

[(A) Hydrocarbon-Containing Compound] The (A) hydrocarbon-containing compound of the present invention comprises a constituent unit (A1) represented by the following formula (A1).

Ar ₁₁ is a C _6-60 alkyl group which may be substituted or unsubstituted by R _11. Ar ₁₁ does not contain a condensed aromatic ring. Suitable Ar ₁₁ includes: 9,9-diphenylfluorene, 9-phenylfluorene, phenyl, C _6-60 straight chain polyphenylene and C _6-60 branched polyphenylene, which may be independently substituted or unsubstituted by R _11. R ₁₁ is a C _1-20 straight chain, branched or cyclic alkyl group, amino group or alkylamino group. R ₁₁ is suitably a C _1-10 straight chain, branched or cyclic alkyl group or alkylamino group. R ₁₁ is more suitably a C _1-3 straight chain alkyl group, a C _1-3 branched alkyl group, a cyclopentyl group, a cyclohexyl group or a dimethylamino group. When the (A) alkyl-containing compound has a plurality of constituent units (A1), R ₁₁ may be bonded to Ar ₁₁ via a linker. The number of R ₁₁ replacing one Ar ₁₁ may be one or more; preferably one. In one constituent unit (A1), a group enclosed by parentheses (e.g., a group enclosed by parentheses together with p ₁₁ ) may be bonded to R _11. In this case, R ₁₁ acts as a linker to bond the group to Ar ₁₁ via a linker. Although not intended to limit the present invention and outside the scope of the present invention, it is considered disadvantageous that Ar ₁₁ includes a naphthyl group (e.g., naphthol) because it is easily oxidized in the steps of the present invention and the reconstruction of the cured film by irradiation with plasma, electron beam and/or ions is difficult.

R ₁₂ is I, Br or CN; preferably I or Br, and more preferably I. p ₁₁ is a number from 0 to 5. Here, in one aspect of the present invention, the alkyl-containing compound (A) may be a compound having two types of (A1) in the form of only one of each. Ar ₁₁ is a phenyl group, and may be in a form where p ₁₁ = 1 for one Ar ₁₁ and p ₁₁ = 2 for the other Ar _11. In this case, p ₁₁ = 1.5 as a whole. In this specification, unless otherwise specified, the numbers are the same. p ₁₁ is suitably 0, 1, 2 or 3; more suitably 0, 1 or 2; and further suitably 1. p ₁₁ = 0 is also a suitable aspect of the present invention. p ₁₂ is a number from 0 to 1; preferably 0 or 1; and more preferably 1. q ₁₁ is a number from 0 to 5; suitably, it is 0, 1, 2 or 3; more suitably, it is 0, 1 or 2; further suitably, it is 1. q ₁₁ = 0 is also a suitable form of the present invention. q ₁₂ is a number from 0 to 1; preferably, it is 0 or 1; more preferably, it is 1. r ₁₁ is a number from 0 to 5; suitably, it is 0, 1, 2 or 3; more suitably, it is 0, 1 or 2; further suitably, it is 1. r ₁₁ = 0 is also a suitable form of the present invention. s ₁₁ is a number from 0 to 5; suitably, it is 0, 1, 2 or 3; more suitably, it is 0, 1 or 2; further suitably, it is 1. s ₁₁ = 0 is also a suitable form of the present invention. p ₁₁ , q ₁₁ , and r ₁₁ will not become 0 at the same time in one constituent unit.

The constituent unit (A1) of the present invention may more specifically be the constituent units (A1-1), (A1-2) and or (A1-3) represented by the following formulas (A1-1), (A1-2) and or (A1-3). Each will be described later. In a suitable embodiment of the present invention, the constituent unit (A1) is the constituent unit (A1-1).

The constituent unit (A1-1) is represented by formula (A1-1).

Ar ₂₁ is a C _6-50 aromatic hydrocarbon; preferably, it is a phenyl group. Since Ar ₂₁ is a phenyl group, the solubility of the hydrocarbon-containing compound (A) in the solvent can be ensured, and advantageous effects such as the ability to form a thick film can be expected. R ₂₁ , R ₂₂ and R ₂₃ are each independently a C _6-50 aromatic hydrocarbon, hydrogen, or a single bond bonded to another constituent unit; preferably, it is a phenyl group, hydrogen, or a single bond bonded to another constituent unit; more preferably, it is a phenyl group or a single bond bonded to another constituent unit; further preferably, it is a phenyl group. n ₂₁ is an integer of 0 or 1; preferably, it is 0. Ar ₂₁ , R ₂₁ , R ₂₂ and R ₂₃ do not contain a condensed aromatic ring. The definitions and suitable examples of R ₁₂ , p ₁₁ , p ₁₂ , q ₁₁ , q ₁₂ , r ₁₁ and s ₁₁ are independently the same as those described above.

Although not intended to limit the present invention, specific examples of the hydrocarbon-containing compound (A) having the constituent unit (A1-1) are listed below.

In a further suitable aspect of the present invention, the constituent unit (A1-1) is a constituent unit (A1-1-1). The constituent unit (A1-1-1) is represented by the formula (A1-1-1). The definitions and suitable examples of p ₁₁ , p ₁₂ , q ₁₁ , q ₁₂ , r ₁₁ and s ₁₁ are the same as those described above, respectively and independently. However, 1≦p ₁₁ +q ₁₁ +r ₁₁ ≦4 is satisfied.

The constituent unit (A1-2) is represented by formula (A1-2). L ₃₁ and L ₃₂ are each independently a single bond or a phenylene group; suitably, they are single bonds. n ₃₁ , n ₃₂ , m ₃₁ and m ₃₂ are each independently a number of 0 to 6; suitably, they are integers of 0 to 3. n ₃₁ + n ₃₂ = 5 or 6 is a suitable embodiment. When L ₃₁ is a single bond, m ₃₁ = 1. When L ₃₂ is a single bond, m ₃₂ = 1. The definitions and suitable examples of R ₁₂ , p ₁₁ , p ₁₂ , q ₁₁ , q ₁₂ , r ₁₁ and s ₁₁ are independently the same as those described above.

Although not intended to limit the present invention, specific examples of the hydrocarbon-containing compound (A) having the constituent unit (A1-2) are listed below.

The constituent unit (A1-3) is represented by formula (A1-3). Ar ₄₁ is a C _6-50 aromatic hydrocarbon; preferably a phenyl group. R ₄₁ and R ₄₂ are each independently a C _1-10 alkyl group; preferably a linear C _1-6 alkyl group. R ₄₁ and R ₄₂ may form a cyclic hydrocarbon; preferably a saturated cyclic hydrocarbon group. The carbon atom at the position of *41 is a quaternary carbon atom. L ₄₁ is a C _6-50 aryl group, or a single bond to another constituent unit; preferably a phenyl group or a single bond to another constituent unit; more preferably a single bond to another constituent unit. The definitions and suitable examples of R ₁₂ , p ₁₁ , p ₁₂ , q ₁₁ , q ₁₂ , r ₁₁ and s ₁₁ are independently the same as described above.

Although not intended to limit the present invention, specific examples of the hydrocarbon-containing compound (A) having the constituent unit (A1-3) are listed below.

When the (A) alkyl compound of the present invention is a polymer, as a suitable aspect of the present invention, the aldehyde derivative used when the (A) alkyl compound is synthesized is suitably 0-30 mol% (more suitably 0-15 mol%, further suitably 0-5 mol%, and further suitably 0 mol%) based on the sum of all the elements used in the synthesis. As an example of the aldehyde derivative, formaldehyde can be cited. It is a suitable aspect of the present invention to use a ketone derivative instead of an aldehyde derivative. The polymer synthesized in this way may have the characteristics of not containing secondary carbon atoms and tertiary carbon atoms in the main chain, or having very few such atoms. As a suitable aspect of the present invention, the aforementioned polymer substantially does not contain secondary carbon atoms and tertiary carbon atoms in its main chain. Although not limited by theory, it is expected that the heat resistance of the formed film can be improved while ensuring the solubility of the polymer. However, it is allowed to contain secondary carbon atoms and tertiary carbon atoms at the terminal of the polymer as terminal modification.

In one embodiment of the present invention, the molecular weight of the alkyl compound (A) is 500-6,000, preferably 500-4,000. When the alkyl compound (A) is a polymer, the molecular weight is the weight average molecular weight (Mw). In the present invention, Mw can be measured by gel permeation chromatography (GPC). For the same measurement, the GPC column is used at 40 degrees Celsius, the elution solvent is tetrahydrofuran at 0.6 mL/min, and monodisperse polystyrene is used as the standard. The following is the same. Based on the composition (i), the amount of the hydrocarbon-containing compound (A) is preferably 2-30% by mass, more preferably 5-30% by mass, more preferably 5-25% by mass, and even more preferably 10-25% by mass.

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

Specific examples of the (B) solvent include water, n-pentane, isopentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-pentylnaphthalene, trimethylbenzene, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol. , dibutyl alcohol, tertiary butyl alcohol, n-pentanol, isopentanol, 2-methylbutanol, dipentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, dihexanol, 2-ethylbutanol, diheptanol, heptanol-3, n-octanol, 2-ethylhexanol, dioctanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, diundecyl alcohol, trimethylnonanol, ditetradecyl alcohol, diheptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexane Alcohol, benzyl alcohol, phenyl methyl carbinol, diacetone alcohol, cresol, ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, Methyl-n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanedione, acetone acetone, diacetone alcohol, acetophenone, fenchone, ethyl ether, isopropyl ether, n-butyl ether (di-n-butyl ether, DBE), n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, di ... Alkane, dimethyl alkyl, 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, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol 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, normal-butyl acetate (normal-butyl acetate) acetate), nBA), isobutyl acetate, dibutyl acetate, n-amyl acetate, diamyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetylacetate, ethyl acetylacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetic acid glycol, 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-amyl 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, cyclobutane sulfone, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more. It is a suitable embodiment of the present invention that the (B) solvent is substantially composed of only those selected from the above specific examples. However, a small amount of a solvent for dissolving the solid component of the surfactant or additive is allowed to be contained in the (B) solvent.

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

In terms of the relationship with other layers or films, it is also an aspect that the (B) solvent does not substantially contain water. For example, the amount of water in the (B) solvent as a whole is preferably 0.1 mass % or less, more preferably 0.01 mass % or less, and further preferably 0.001 mass % or less. It is also an appropriate aspect that the (B) solvent does not contain water (0 mass %).

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

[(C) Surfactant] The composition (i) of the present invention may further include a (C) surfactant. By including a surfactant, the coating properties can be improved. In the present invention, the so-called (C) surfactant refers to the compound itself having the above-mentioned function. The compound may be dissolved or dispersed in a solvent and contained in the composition, but such a solvent is preferably contained in the composition as a (B) solvent or other component. Hereinafter, the various additives that can be contained in the composition are also considered the same. As for the surfactant that can be used in the present invention, there can be listed: (I) anionic surfactants, (II) cationic surfactants, or (III) non-ionic surfactants. More specifically, preferred are (I) alkyl sulfonates, alkylbenzene sulfonic acids, and alkyl benzene sulfonates, (II) lauryl pyridinium chloride and lauryl ammonium chloride, and (III) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene acetylenic glycol ether, fluorine-containing surfactants such as Fluorad (Sumitomo 3M), Megafac (DIC), Sulflon (Asahi Glass), or organosiloxane surfactants (such as KP341, Shin-Etsu Chemical Co., Ltd.).

Based on the (A) hydrocarbon-containing compound, the (C) surfactant is preferably in an amount of 0.01 to 10% by mass; more preferably 0.05 to 10% by mass; further preferably 0.05 to 5% by mass; and further preferably 0.05 to 1% by mass.

[(D) Additive] The composition (i) of the present invention may further include an additive (D). The additive (D) is a component different from (A), (B) and (C). Preferably, the 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, the additive (D) includes a crosslinking agent, an acid generator, a free radical generator, a photopolymerization initiator, a substrate adhesion enhancer or a mixture thereof. As a more preferred additive (D), a crosslinking agent can be listed. As another aspect of the present invention, as the additive (D), a high carbon material can be listed.

The crosslinking agent is useful for improving the film-forming property of the hydrocarbon-containing film according to the present invention, eliminating intermixing with the upper film (such as the silicon-containing intermediate layer and the anti-etching agent), and eliminating the diffusion of low molecular components into the upper film.

As for the crosslinking agent, there can be listed: melamine compounds, guanamine compounds, glycoluril compounds or urea compounds substituted with at least one group selected from hydroxymethyl, alkoxymethyl, acyloxymethyl, epoxy compounds, thioepoxy compounds, isocyanate compounds, aziridine compounds, compounds containing double bonds such as alkenyl ether groups. These can be used as additives, but can also be introduced into the polymer side chain as pendant groups. In addition, compounds containing hydroxyl groups can also be used as crosslinking agents. Among the aforementioned compounds, examples of epoxy compounds include tris(2,3-epoxypropyl)isocyanate, trihydroxymethylmethane triglycidyl ether, trihydroxymethylpropane triglycidyl ether, trihydroxyethylethane triglycidyl ether, etc. Specific examples of melamine compounds include hexahydroxymethylmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 hydroxymethyl groups of hexahydroxymethylmelamine are methoxymethylated, and a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound in which 1 to 6 hydroxymethyl groups of hexahydroxymethylmelamine are acyloxymethylated, and a mixture thereof. As for guanamine compounds, there are tetrahydroxymethylguanamine, tetramethoxymethylguanamine, compounds of tetrahydroxymethylguanamine in which 1 to 4 hydroxymethyl groups are methoxymethylated, and mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds of tetrahydroxymethylguanamine in which 1 to 4 hydroxymethyl groups are acyloxymethylated, and mixtures thereof. As for glycoluril compounds, there are tetrahydroxymethyl glycoluril, tetramethoxyglycouril, tetramethoxymethyl glycoluril, compounds of tetrahydroxymethyl glycoluril in which 1 to 4 hydroxymethyl groups are methoxymethylated, and mixtures thereof, compounds of tetrahydroxymethyl glycoluril in which 1 to 4 hydroxymethyl groups are acyloxymethylated, and mixtures thereof. As for urea compounds, there are tetrahydroxymethyl urea, tetramethoxymethyl urea, compounds of tetrahydroxymethyl urea in which 1 to 4 hydroxymethyl groups are methoxymethylated, and mixtures thereof, and tetramethoxyethyl urea, etc. As for the compounds containing alkenyl ether groups, the following can be cited: ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,4-butylene glycol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trihydroxymethylpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trihydroxymethylpropane trivinyl ether, etc. The molecular weight of the crosslinking agent is preferably 100-480, more preferably 200-400, and further preferably 300-380.

Although not intended to limit the present invention, specific examples of the crosslinking agent include the following.

The high-carbon material is a molecule containing more carbon atoms per molecule and is a solid component remaining in the hydrocarbon-containing film according to the present invention. By adding the high-carbon material, the etching resistance can be improved. The high-carbon material itself does not need to be able to form a film, and it only needs to be able to form a hydrocarbon-containing film together with the (A) hydrocarbon-containing compound.

Although the present invention is not intended to be limiting, specific examples of high-carbon materials include isoviolanthrone, 2,7-di(1-pyrene)-9,9'-spiro[9H-fluorene], 9,9-bis[4-[di(2-naphthyl)amino]phenyl]fluorene, 9,9-bis[4-[N-(1-naphthyl)anilino]phenyl]fluorene, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid diimide, benzanthrone, perylene, coronene, 5,12-naphthacenequinone, 6,13-pentacenedione, fullerene C ₆₀ , C ₆₀ MC ₁₂ (C _{The following} are the main materials: N-methylpyrrolidine (m-C ₁₂ -phenyl), ICBA (indene-C ₆₀ bisadduct), N,2-diphenyl[60]fulleropyrrolidine), PCBM (Phenyl-C ₆₁ -Butyric-Acid-Methyl Ester _{), PCBB (Phenyl-C 61 -Butyric -} Acid-Butyl Ester), and N-phenyl-2-hexyl[60]fulleropyrrolidine _.

In the present invention, based on the (A) alkyl compound, the (D) additive is preferably 0.05-100 mass %; more preferably 0.05-25 mass %; further preferably 0.05-20 mass %; further preferably 0.05-15 mass %; and further preferably 0.05-10 mass %.

[Method for producing a cured film] The method for producing a cured film of the present invention comprises the following steps. (1) applying (i) composition onto a substrate; (2) forming a hydrocarbon-containing film from (i) composition; and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and/or ions to form a cured film.

As a method for applying the composition (i) in the present invention, coating methods such as a spinner and a coating machine can be cited. The composition (i) according to the present invention is advantageous for patterns embedded in a substrate. The so-called upper part of the substrate is preferably a substrate that is directly in contact with the composition (i), but it can also be coated through other films. As for the method of forming a hydrocarbon-containing film from the composition (i), ultraviolet irradiation and/or heating can be cited, and heating can be cited as appropriate.

Preferably, the ultraviolet irradiation condition is to irradiate with ultraviolet light having a wavelength of 10 to 380 nm (more preferably 10 to 200 nm) at a cumulative irradiation dose of 100 to 10,000 mJ/cm ² .

Air is suitable as the environment for UV irradiation or heating. In order to prevent oxidation of the composition (i) and/or the alkali-containing film of the present invention, the oxygen concentration can also be reduced. For example, the oxygen concentration can be made below 1,000 ppm (suitably below 100 ppm) by injecting an inert gas (N2, Ar, He or a mixture thereof) into the environment.

When a hydrocarbon-containing film is formed by heating, the heating conditions are preferably selected from the range of 80 to 800°C (preferably 200 to 700°C, more preferably 300 to 600°C) and the heating time from 30 to 180 seconds (preferably 30 to 120 seconds). Although not limited by theory, it is believed that by heating at a high temperature, crosslinking based on groups such as acetylene groups that crosslink polymers with each other can be well performed, which can contribute to the high density of the cured film. Heating can also be performed in multiple steps (stage baking). A hydrocarbon-containing film can be formed by heating alone, but a combination with ultraviolet irradiation is also suitable.

The hydrocarbon-containing film is irradiated with plasma, electron beam and/or ions to form a hardened film. Although not limited by theory, it is believed that the chemical bonding dissociation and rebonding of the hydrocarbon-containing film due to such irradiation reconstruct the film in the form of a hardened film having a diamond-like carbon structure, thereby contributing to an increase in hardness and density. As one aspect of the present invention, it also includes irradiating with plasma, electron beam and/or ions immediately after applying the composition (i) to form a hardened film. That is, the aspect in which the above steps (2) and (3) are performed approximately simultaneously in one operation (step) is also included in the present invention.

Plasma irradiation can be performed by a known method. For example, methods described in Japanese Patent No. 5746670 (patent document) and "Improvement of the wiggling profile of spin-on carbon hard mask by H ₂ plasma treatment" (J. Vac. Sci. Technol. B 26 (1), Jan/Feb 2008, p67-71, non-patent document) can be cited. RF discharge power can be selected from 1,000 to 10,000 W, more preferably 1,000 to 5,000 W. As for the gas environment, _N2 , _NF3 , _H2 , rare gases, fluorocarbons can be listed; more preferably, Ar, Ne, _NF3 , _H2 , _CF4 , CHF3, _CH2F2 , _CH3F , _C4F6 , _{C4F8 ,} etc. can be listed. Two _or more of these gases can be mixed for use. The effect of the present invention can be expected even when using a gas environment that does _not contain _O2 . The time can be _selected from 10 to 240 seconds. The pressure can be appropriately selected.

Electron beam irradiation can be performed by a known method. For example, the method described in "Technology and Utilization of Electron Beam Irradiation Device" (July 2012, SEI Technical Review No. 181, p50-57, non-patent document) can be cited. As for the accelerating voltage, it can be selected from 2 to 200 kV. The irradiation dose can be selected from 100 to 5,000 kGy. It is suitable to perform electron beam irradiation while heating. At this time, the temperature can be selected from 80 to 800°C (preferably 200 to 700°C, and more preferably 300 to 600°C). Ion irradiation can be performed by a known method. For example, the method described in "Raman spectroscopy and microhardness of ion-implanted aC:H-films" (Ceramics Int.26(1), 2000, p29-32, non-patent document) can be cited. One suitable aspect of the ion irradiation of the present invention is ion implantation. As for the type of element of the ion to be irradiated, it can be listed: hydrogen, boron, carbon, nitrogen, and rare gases; suitably, it can be listed: boron, carbon, nitrogen, neon, argon, etc.; more suitably, it can be listed: carbon, nitrogen, etc. These gases can also be used in combination of two or more. As for the accelerating voltage, it can be selected from 3~1000kV. The accelerating voltage is more preferably 5 to 750 kV, and more preferably 10 to 500 kV. The irradiation dose can be selected from 10 ¹³ to 10 ¹⁸ ion/cm ² . The irradiation dose is more preferably 5×10 ¹³ to 5×10 ¹⁷ ion/cm ² , and more preferably 10 ¹⁴ to 10 ¹⁷ ion/cm ² . Ion irradiation can also be performed while heating the chamber of the device. In this case, the temperature can be selected to be 500°C or less. When heating is performed after plasma irradiation and electron beam irradiation, the heating conditions are preferably selected from the range of 80 to 800°C (preferably 200 to 700°C, more preferably 300 to 600°C) and the heating time from 30 to 180 seconds (preferably 30 to 120 seconds). Although not limited by theory, it is believed that high-temperature heating after plasma and electron beam irradiation can contribute to the high density of the cured film by bonding the suspended bonds.

As the irradiation device, Tactras Vigus, EB-ENGINE (Hamamatsu Photonics), EXCEED2300AH (Nissin Ion Machine) can be used. The device can be selected and the conditions can be set so that the effect of the present invention can be achieved.

According to one aspect of the present invention, the cured film formed in the aforementioned step (3) can have a favorable effect of increasing the film density by 5 to 75% and increasing the film hardness by 50 to 500% compared to the hydrocarbon-containing film formed in the step (2). In addition, the cured film formed in the step (3) may have an intensity ratio R = _ID / _IG of 0.35 to 0.90 between the G band and the D band in Raman spectroscopy (measured at a laser wavelength of 514.5 nm). Although not limited by theory, it is considered that it may have a diamond-like carbon structure. Furthermore, it is considered that the hydroxyl-containing film formed in step (2) is more easily etched by 5 to 200% (preferably 5 to 100%, more preferably 5 to 50%, and further preferably 10 to 50%) than the cured film formed in the aforementioned step (3) (the latter cured film has higher etching resistance). Preferably, the surface resistivity of the cured film formed in step (3) is 10 ⁹ to 10 ¹⁶ Ω□ (preferably 10 ¹² to 10 ¹⁶ Ω□, and further preferably 10 ¹³ to 10 ¹⁶ Ω□). That is, the hydroxyl-containing compound (A) is not a conductive polymer precursor, and the cured film of the present invention is not a conductive polymer film.

According to one aspect of the present invention, a carbon-containing cured film having the following characteristics is provided. The film density is 1.3 to 3.2 g/cm ³ ; the film hardness is 1.5 to 20 GPa; and or in Raman spectroscopy (measured at a laser wavelength of 514.5 nm), the intensity ratio of the G band to the D band R = _ID / _IG is 0.35 to 0.90. Preferably, the carbon-containing cured film is formed by plasma, electron beam and/or ion irradiation. More preferably, the film has a surface resistivity of 10 ⁹ to 10 ¹⁶ Ω□ (Ohm square). As a composition for forming such a carbon-containing cured film, using the above-mentioned (i) composition is a more suitable aspect of the present invention.

As for the film known as SOC, "The Role of Underlayers in EUVL" (Journal of Photopolymer Science and Technology Vol.31, Number 2, p209-214, 2018) describes it, but the film density is only about 1.05~1.32g/cm3. According to the cured film of the present invention, the carbon-containing cured film preferably has a film density of 1.3~3.2g/ ^cm3 (more preferably 1.4~3.2g/ ^cm3 , and further preferably 1.5~2.8g/ ^cm3 ). It is believed that the ^high film density of the cured film contributes to the improvement of etching resistance. In addition, it is believed that if the stress of the cured film is too strong, the substrate is pressed and it is not good. The film density can be measured using, for example, the method described in the examples, and can be adjusted by appropriately combining known methods.

The film of the present invention preferably has a film hardness of 1.5 to 20 GPa (more preferably 1.7 to 20 GPa, further preferably 2.0 to 15 GPa, further preferably 2.0 to 10 GPa). The film hardness can be measured using, for example, the method described in the embodiment, and can be adjusted by appropriately combining known methods.

The film of the present invention preferably has an intensity ratio R= _ID / _IG of 0.35 to 0.90 (more preferably 0.40 to 0.90, further preferably 0.40 to 0.80, further preferably 0.45 to 0.70) between the G band and the D band in Raman spectroscopy (measured at a laser wavelength of 514.5 nm). Raman spectroscopy can be performed using, for example, the method described in the embodiments, and can be adjusted by appropriately combining it with a known method (for example, Japanese Patent No. 3914179 (patent document)).

<Method for producing anti-corrosion film and anti-corrosion pattern> An anti-corrosion film can also be produced on top of the cured film produced by the method of the present invention. The method for producing the anti-corrosion film of the present invention comprises the following steps: (4) applying an anti-corrosion composition on top of the aforementioned cured film; (5) heating the anti-corrosion composition to form an anti-corrosion layer. Furthermore, the present invention can also produce an anti-corrosion pattern from the aforementioned anti-corrosion film. The method of making the resist pattern of the present invention comprises the following steps: (6) exposing the resist layer; optionally (7) heating the resist layer after exposure; and (8) developing the resist layer. If recorded for clarity, the numbers in () refer to the order. For example, step (4) is performed before step (5).

The following is an explanation of one aspect of the method for manufacturing an anti-etching film and an anti-etching pattern according to the present invention. The anti-etching agent composition is applied to the top of 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 an appropriate method. Here, in the present invention, the so-called top includes the case where it is formed directly above and the case where it is formed through other layers. For example, a planarization film or an anti-etching agent lower layer film can be formed directly above the substrate, and the anti-etching agent composition is applied directly above it. The application method is not particularly limited, but for example, a method of coating by a spinner or a coating machine can be cited. After coating, the anti-corrosion agent layer is formed by heating. The heating in (5) is performed, for example, by a hot plate. The heating temperature is preferably 60 to 140°C, more preferably 90 to 110°C. The temperature here is the heating environment, for example, the heating surface temperature of the hot plate. The heating time is preferably 30 to 900 seconds, more preferably 60 to 300 seconds. The heating is preferably performed in an atmosphere or nitrogen gas environment.

The thickness of the anti-etching agent layer is selected according to the purpose, and the thickness of the anti-etching agent layer may be greater than 1 μm.

The resist layer is exposed through a prescribed mask. The wavelength of light that can be used for exposure is not particularly limited, but exposure is preferably performed using light with a wavelength of 190 to 440 nm (more preferably 240 to 370 nm). Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (436 nm), etc. can be used. The wavelength is more preferably 240 to 440 nm, more preferably 360 to 440 nm, and even more preferably 365 nm. The wavelengths are within a range of ±1%.

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

After PEB, a developer is used for development. As for the developing method, methods that can be used in the development of photoresists in the past, such as paddle development, immersion development, and swing immersion development, can be used. In addition, as for the developer, an aqueous solution containing inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylamine ethanol, triethylamine, and tetramethylammonium hydroxide (TMAH) and the like can be used, preferably a 2.38 mass% TMAH aqueous solution. A surfactant can also be further added to the developer. The temperature of the developer 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 developing, water washing or rinsing can be performed as needed.

In one aspect of the present invention, the manufactured resist pattern can be used as a mask to pattern various substrates that serve as a base. The substrate can be processed directly using the resist pattern as a mask, or it can be processed through an intermediate layer. For example, the resist lower film can be patterned using the resist pattern as a mask, and the substrate can be patterned using the resist lower film pattern as a mask. For processing, known methods can be used, such as dry etching, wet etching, ion implantation, metal plating, etc. Electrodes can also be wired on the patterned substrate.

[Substrate] In the present invention, the substrate includes: semiconductor wafers, glass substrates for liquid crystal display devices, glass substrates for organic EL display devices, glass substrates for plasma displays, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, glass substrates for masks, and substrates for solar cells. The substrate may be a non-processed substrate (e.g., a bare wafer) or a processed substrate (e.g., a patterned substrate). The substrate may also be formed by laminating multiple layers. Preferably, the surface of the substrate is a semiconductor. The semiconductor may also be formed by any of oxides, nitrides, metals, or any combination thereof. Furthermore, it is preferred that the surface of the substrate is _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.

[Device] Device can be manufactured by further processing the substrate according to the present invention. As for the device, there can be listed: semiconductor element, liquid crystal display element, organic EL display element, plasma display element, solar cell element. The so-called device is preferably a semiconductor. Such processing can use a known method. After the device is formed, the substrate can be cut into chips as needed, connected to the lead frame, and packaged with resin. One example of the packaged is a semiconductor.

If the present invention is described using examples, it is as follows. In addition, the aspects of the present invention are not limited to these examples.

<Synthesis of P0> A reactor equipped with a stirrer, Liebig condenser, heating device, nitrogen inlet pipe and temperature control device was prepared. 9-Fluorone (200 parts, Tokyo Chemical Industry), 9,9-bis(4-hydroxyphenyl)fluorene (2333 parts, Osaka Gas Chemicals) and dichloromethane (10430 parts) were added to the reactor and kept at 40°C under nitrogen atmosphere while stirring. Then, trifluoromethanesulfonic acid (92 parts, Mitsubishi Materials Electronic Chemicals) and 3-hydroxypropionic acid (6 parts, Tokyo Chemical Industry) dissolved in dichloromethane (200 parts) were slowly added to the reactor and kept at 40°C with stirring for 4 hours. After the reaction is completed, the solution is returned to room temperature, water is added to the reaction solution, and the excess 9,9-bis(4-hydroxyphenyl)fluorene is removed by filtration, and then washed with dichloromethane. The dichloromethane solution is washed with sufficient water to remove trifluoromethanesulfonic acid. Thereafter, dichloromethane is distilled off at 40°C and 10 mmHg to obtain P0 (2111 parts). If the molecular weight is measured by GPC (tetrahydrofuran), the coefficient average molecular weight Mn = 533 Da, the weight average molecular weight Mw = 674 Da, and the molecular weight distribution (Mw/Mn) = 1.26.

<Synthesis Example 1: Synthesis of P1> Prepare a reactor equipped with a stirrer, Liebig condenser, heating device, nitrogen inlet pipe and temperature control device. Add P0 (350 parts), potassium carbonate (562 parts) and acetone (1414 parts) to the reactor, and keep it at 56°C while stirring in a nitrogen atmosphere. Then, slowly add allyl bromide (500 parts, Tokyo Chemical Industry) to the reactor, keep it at 56°C and stir, and let it react for 3 hours. After the reaction is completed, return the solution to room temperature, remove excess potassium carbonate and salt by filtration, and wash the precipitate with acetone. Then, distill off the acetone at 40°C and 10 mmHg. The obtained solid was dissolved in ethyl acetate (3000 parts), and the ethyl acetate solution was fully washed with water to remove metal impurities. After diluting the ethyl acetate at 40°C and 10 mmHg, the obtained solid content was dissolved in acetone (600 parts). Thereafter, the acetone solution was placed in n-heptane (6000 parts), the solid was filtered, and dried at 100°C and 10 mmHg to obtain P1 (345 parts). If the molecular weight is measured by GPC (tetrahydrofuran), the coefficient average molecular weight Mn = 671 Da, the weight average molecular weight Mw = 833 Da, and the molecular weight distribution (Mw/Mn) = 1.32.

<Synthesis Example 2: Synthesis of P2> Prepare a reactor equipped with a stirrer, Liebig condenser, heating device, nitrogen inlet pipe and temperature control device. Add P0 (200 parts), potassium carbonate (323 parts) and acetone (616 parts) to the reactor, and keep it at 56°C while stirring in a nitrogen environment. Then, slowly add 3-bromo-1-propyne (278 parts) to the reactor, keep it at 56°C and stir it for 3 hours. After the reaction is completed, return the solution to room temperature, remove excess potassium carbonate and salt by filtration, and wash the precipitate with acetone. Then, dilute the acetone at 40°C and 10 mmHg. The obtained solid was dissolved in ethyl acetate (820 parts), and the ethyl acetate solution was fully washed with water to remove metal impurities. After diluting the ethyl acetate at 40°C and 10 mmHg, the obtained solid content (185 parts) was dissolved in acetone (185 parts). Thereafter, methanol (1850 parts) was placed in 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 measured by GPC (tetrahydrofuran), it was Mn=789Da, Mw=1,054Da, and Mw/Mn=1.34.

[Preparation Example 1 of Composition 1] P1 (13.9 parts) and Megafac R-41 (0.1 parts, DIC Corporation) were added to propylene glycol 1-monomethyl ether 2-acetate (PGMEA) (86 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2μm fluororesin filter (Merck Millipore, SLFG025NS) to obtain Composition 1.

[Preparation Example 2 of Composition 2] P2 (11.9 parts) and Megafac R-41 (0.1 parts) were added to PGMEA (88 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2μm fluororesin filter to obtain Composition 2.

[Preparation Example 3 of Composition 3] P3 (13.9 parts) and Megafac R-41 (0.1 parts) having the structure shown below were added to PGMEA (86 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2 μm fluororesin filter to obtain Composition 3. P3

[Preparation Example 4 of Composition 4] P4 (14.9 parts) and Megafac R-41 (0.1 parts) having the structure shown below were added to PGMEA (85 parts) and stirred at room temperature for 1 hour. The solute was visually confirmed to be completely dissolved. The mixture was filtered using a 0.2 μm fluororesin filter to obtain Composition 4. P4

[Preparation Example 5 of Composition 5] P5 (14.9 parts) and Megafac R-41 (0.1 parts) having the structure shown below were added to PGMEA (85 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2 μm fluororesin filter to obtain Composition 5. P5

[Preparation Example 6 of Composition 6] P6 (13.9 parts) and Megafac R-41 (0.1 parts) having the structure shown below were added to PGMEA (86 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2 μm fluororesin filter to obtain Composition 6. P6

[Preparation Example 7 of Composition 7] The above-mentioned P0 (24.9 parts) and Megafac R-41 (0.1 parts) were added to PGMEA (75 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2μm fluororesin filter to obtain Composition 7.

[Preparation Example 8 of Composition 8] P7 (12.9 parts) having the structure shown below, P8 (1 part) having the structure shown below, and Megafac R-41 (0.1 part) were added to PGMEA (87 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2 μm fluororesin filter to obtain Composition 8. P7 P8

[Preparation Example 9 of Composition 9] P2 (8.9 parts), P9 (5 parts) having the structure shown below, and Megafac R-41 (0.1 parts) were added to PGMEA (85 parts) and stirred at room temperature for 1 hour. The solute was visually confirmed to be completely dissolved. The mixture was filtered using a 0.2 μm fluororesin filter to obtain Composition 9. P9

[Preparation Example 10 of Composition 10] P2 (2.9 parts) and Megafac R-41 (0.1 parts) were added to PGMEA (97 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2μm fluororesin filter to obtain Composition 10.

[Preparation Example 11 of Composition 11] P2 (3.9 parts) and Megafac R-41 (0.1 parts) were added to PGMEA (96 parts) and stirred at room temperature for 1 hour. Visually confirm that the solute is completely dissolved. Filter using a 0.2μm fluororesin filter to obtain Composition 11.

[Formation of hydrocarbon-containing film] Each composition was applied to a Si bare wafer at 1,500 rpm using CLEAN TRACK ACT 12 (Tokyo Electron). The wafer was baked at 250°C for 60 seconds in an air environment, and further baked at 450°C for 120 seconds in a nitrogen environment. A hydrocarbon-containing film was obtained from the composition.

[Formation of hardened film (in the case of plasma treatment)] The wafer on which the above-mentioned hydrocarbon-containing film was formed was subjected to plasma treatment for 2 minutes using Tactras Vigus (Tokyo Electron).

[Formation of Cured Film (Electron Beam Treatment)] While heating the wafer with the alkali-containing film to 400°C using EB-ENGINE (Hamamatsu Photonics), 1MGy of electron beam irradiation was performed.

[Formation of Cured Film (In the Case of Ion Irradiation Treatment)] The wafer on which the above-mentioned alkene-containing film was formed was irradiated with carbon ions at 10 ¹⁶ ions/cm ² at an accelerating voltage of 10 kV.

[Film thickness measurement] The wafer cross section was made and the film thickness was measured by obtaining SEM photographs using JSM-7100F (JEOL).

[Film density measurement] The film density was calculated by fitting the obtained X-ray reflectivity curve with the curve simulated in the high-resolution X-ray reflectivity measurement using the fully automatic multi-purpose X-ray diffraction device SmartLab (Rigaku) with the cathode: Cu, output: 45kV×200mA, resolution range: 0.2~3.0°, and measurement step (step) 0.002°.

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

[Determination of _ID / _IG ] The _ID / _IG in Raman spectroscopic analysis was measured using a triple laser Raman spectrometer RAMANOR T64000 (HORIBA Jobin Yvon) with a laser wavelength of 514.5nm. The peak that appeared in the width of about 900~1800cm ^-1 was separated into three bands using a Gaussian function: the G band near 1590cm ^-1 , the D band near 1350cm ^-1 , and the band near 1100cm ^-1 . The intensities of the D band and the G band were calculated. _ID / _IG was calculated in this way.

[Measurement of etching resistance] Dry etching was performed using an etching apparatus NE-5000N (ULVAC) at a chamber pressure of 0.17 mT, an RF power of 200 W, a gas flow rate of CF ₄ (50 sccm), Ar (35 sccm), and O ₂ (4 sccm), for 30 seconds. The film thickness before etching and the film thickness after etching were measured as described in the above "Measurement of film thickness", and the difference between the former and the latter was obtained, and the film thickness reduction per unit time was calculated.

[Evaluation Results] The evaluation results are listed in Table 1 below. [Table 1] Film thickness(nm) Film density (g/cm ³ ) Film hardness (GPa) _ID / _IG Etching resistance (nm/min) Before treatment After treatment Before treatment After treatment Before treatment After treatment After treatment After treatment Composition 1 224 75 1.2 1.4 1.1 2.7 0.62 172 Composition 2 236 85 1.2 1.5 0.8 2.8 0.58 164 Composition 3 223 94 1.2 1.6 0.8 3.0 0.50 153 Composition 4 212 98 1.2 1.6 1.0 3.0 0.52 149 Composition 5 216 77 1.2 1.5 0.8 2.7 0.51 150 Composition 6 213 92 1.2 1.6 0.8 3.0 0.49 149 Composition 7 232 83 1.2 1.2 0.9 2.5 0.71 164 Composition 8 243 88 1.2 1.2 0.9 2.6 0.85 149 Composition 9 238 97 1.2 1.6 0.9 2.7 0.84 132 Composition 10 53 42 1.2 1.4 1.1 1.9 0.75 183 Composition 11 71 60 1.2 1.3 1.0 4.5 0.54 168 In the above table, for compositions 1 to 9, "before treatment" means the results of evaluating the hydrocarbon-containing film before plasma treatment, and "after treatment" means the results of evaluating the cured film after plasma treatment. For composition 10, "before treatment" means the results of evaluating the hydrocarbon-containing film before electron beam irradiation, and "after treatment" means the results of evaluating the cured film after electron beam irradiation. For composition 11, "before treatment" means the results of evaluating the hydrocarbon-containing film before ion irradiation, and "after treatment" means the results of evaluating the cured film after ion beam irradiation.

[Comparative example, evaluation of etching resistance of hydrocarbon-containing film] The etching resistance of the hydrocarbon-containing film of composition 2 before plasma treatment was measured in the same manner as above. The etching resistance was 204nm/min. When the etching resistance of the hydrocarbon-containing film obtained from composition 2 (before plasma treatment) and the cured film (after plasma treatment) was compared, the former was easily etched by about 24%.

without.

without.

without.

Claims (16)

A method for producing an anti-etching agent layer on a cured film comprises the following steps: (1) applying (i) a composition on a substrate; (2) forming a hydrocarbon-containing film from (i) the composition by heating; and (3) irradiating the hydrocarbon-containing film with plasma, electron beam and/or ions to form a cured film; wherein (i) the composition comprises (A) a hydrocarbon-containing compound and (B) a solvent; (A) the hydrocarbon-containing compound comprises a constituent unit (A1-1) represented by the following formula (A1-1);

Herein, Ar ₂₁ is a C _6-50 aromatic hydrocarbon, R ₂₁ , R ₂₂ and R ₂₃ are each independently a C _6-50 aromatic hydrocarbon, hydrogen, or a single bond to another constituent unit, n ₂₁ is an integer of 0 or 1; Herein, Ar ₂₁ , R ₂₁ , R ₂₂ and R ₂₃ do not contain a condensed aromatic ring, R ₁₂ is I, Br or CN; p ₁₁ is a number from 0 to 5, p ₁₂ is a number from 0 to 1, q _{11 is 0, r 11 is} a number from 0 to 5, s ₁₁ is a number from 0 to 5; p ₁₁ , q ₁₁ and r 11 are integers of 0 to 5. ₁₁ will not become 0 simultaneously within one constituent unit; in the Raman spectroscopic analysis (laser wavelength 514.5nm) of the cured film formed in step (3), the intensity ratio of the G band to the D band R = _ID / _IG is 0.35~0.90. The method of claim 1, wherein the molecular weight of the hydrocarbon-containing compound (A) is 500-6,000. The method of claim 1 or 2, wherein the (i) composition further comprises (C) a surfactant or (D) an additive; herein, the (D) additive comprises 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. The method of claim 1 or 2, wherein (B) the solvent comprises an organic solvent; herein, the organic solvent comprises a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or a mixture thereof. The method of claim 1 or 2, wherein, based on the composition (i), the content of the hydrocarbon-containing compound (A) is 2-30% by mass; based on the composition (i), the content of the solvent (B) is 60-98% by mass; based on the hydrocarbon-containing compound (A), the content of the surfactant (C) is 0.01-10% by mass; or based on the hydrocarbon-containing compound (A), the content of the additive (D) is 0.05-100% by mass. As in the method of claim 1 or 2, wherein (A) the hydrocarbon-containing compound is a polymer, and the aldehyde derivative used in the synthesis of the polymer is 0-30 mol% based on the sum of all elements used in the synthesis. The method of claim 6, wherein the polymer does not substantially contain secondary carbon atoms and tertiary carbon atoms in its main chain. The method of claim 1 or 2, wherein in step (3) plasma is irradiated; the environment is _N2 , _NF3 , _H2 , fluorocarbon, rare gas, or a mixture of any of these, or the RF discharge power is 1,000-10,000W. The method of claim 1 or 2, wherein in step (3), electron beam irradiation is performed; the accelerating voltage is 2kV~200kV, or the irradiation dose is 100kGy~5,000kGy. The method of claim 1 or 2, wherein in step (3), ions are irradiated; the element type of the ions irradiated is hydrogen, boron, carbon, nitrogen, a rare gas, or a mixture of any of these, the accelerating voltage is 3-1000 kV, or the irradiation dose is 10 ¹³ -10 ¹⁸ ion/cm ² . As in the method of claim 1 or 2, the hardened film formed in step (3) has a film density increased by 5 to 75%, or a film hardness increased by 50 to 500%, compared to the hydrocarbon-containing film formed in step (2). The method of claim 1 or 2, wherein the hydrocarbon-containing film formed in step (2) is 5-200% easier to etch 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□. The method of claim 1 or 2, wherein the heating in step (2) is performed at 80-800°C for 30-180 seconds. The method of claim 1 or 2, wherein the film density of the cured film is 1.3-3.2 g/cm ³ ; or the film hardness of the cured film is 1.5-20 GPa. A method for manufacturing an anti-etching agent pattern, comprising: exposing the anti-etching agent layer as described in any one of claims 1 to 14; and developing the exposed anti-etching agent layer to obtain the anti-etching agent pattern. A method for manufacturing a device, comprising the method of any one of claims 1 to 15.