JP2018140972A - Vinyl derivative and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel vinyl derivative and a composition comprising the same, to provide a carbon-containing film-forming composition that has heat resistance and capability of forming a uniform film and a method for producing a carbon-containing film using the same, and to provide a method for producing a device using the carbon-containing film.SOLUTION: There are provided a novel vinyl derivative and use thereof and a composition using the vinyl derivative and a method for producing a carbon-containing film and a method for producing a semiconductor.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a novel vinyl derivative and an electronic material or a lithographic material containing the derivative. The present invention also relates to a composition containing the vinyl derivative, a method for producing a carbon-containing film using the composition, and a method for producing a semiconductor.

In the process of manufacturing a device such as a semiconductor, fine processing by a lithography technique using a photoresist is generally performed. In the microfabrication process, a thin photoresist layer is formed on a semiconductor substrate such as a silicon wafer, and the layer is covered with a mask pattern corresponding to a target device pattern. Exposure to actinic light, development of the exposed layer to obtain a photoresist pattern, and etching the substrate using the resulting photoresist pattern as a protective film, thereby providing a fine pattern corresponding to the above-mentioned pattern Unevenness is formed. In recent years, it has been demanded to form another layer on a substrate processed so as to form fine unevenness by high integration and three-dimensional semiconductor and to repeat the processing.
A photoresist layer or other film can be applied to such a substrate in a solution state and cured by radiation or heating to form a film. Photoresist layers and other films are laminated in such a precise environment, and characteristics such as film forming properties and non-mixing with other layers are required.

In such a technical background, an attempt is made to form a resist layer by applying a specific resist composition to a bare wafer and crosslinking it by direct or indirect sensitivity to radiation (see FIG. Patent Document 1). In another attempt, a vinyl ether compound having a specific fluorene skeleton was synthesized, but only Tg and solubility were confirmed (Patent Document 2).

International Publication WO2006 / 132139 JP 2014-166888 A

  The present inventor has conducted extensive research on the assumption that a compound that is heat resistant and capable of forming a uniform film is useful as a compound that can be used for a carbon-containing film in a lithography process. Further, if the carbon-containing film can be cured by a predetermined radiation, it is considered that the damage to the other organic layers can be avoided and useful for the lamination process. In addition, the inventors pay attention to the fact that when a film is formed on a non-flat substrate such as a processed substrate (for example, a stepped substrate), the flatness of the film surface is lowered due to the influence of the structure of the substrate, We conducted intensive research.

The vinyl according to the present invention is represented by the following formula (1).
{Where,
Each ring A is independently a C _6-14 aromatic hydrocarbon ring or a C _6-14 saturated hydrocarbon ring;
Each X is independently a C _6-14 aromatic hydrocarbon ring, a C _6-14 saturated hydrocarbon ring or C _1-4 alkyl;
Each R ₁ is independently hydrogen or C _1-4 alkyl;
n is any integer from 0 to 13,
L is each independently a C _1-4 alkylene, a linker unit represented by the following formulas (2), (3), (4), or a combination thereof, and the number of linker units in one L is Each independently 1 to 4,
Each R ₂ is independently hydrogen or C _1-4 alkyl;
Each R ₃ is independently hydrogen or C _1-4 alkyl. }

The composition according to the present invention comprises the vinyl derivative according to the present invention and an organic solvent. The carbon-containing film-forming composition according to the present invention comprises the composition according to the present invention.
The method for producing a carbon-containing film according to the present invention comprises applying the composition according to the present invention upward on a substrate and curing the composition. The upward direction includes a case where layers are stacked in contact with each other and a case where layers are stacked via other layers.

  Further, the method for producing a semiconductor according to the present invention comprises producing a carbon-containing film according to the present invention, laminating a photoresist composition in an upward or downward direction of the carbon-containing film, curing the photoresist composition, and Forming a resist layer, exposing the substrate coated with the photoresist layer, developing the exposed substrate to form a resist pattern, etching using the resist pattern as a mask, and processing the substrate. It becomes. The downward direction includes a case where the layers are stacked in contact with each other and a case where the layers are stacked via other layers.

  The inventors of the present invention have a saturated hydrocarbon ring rather than an aromatic hydrocarbon ring as the central skeleton of the vinyl derivative, which can easily reflow during film formation and improve flatness when embedded in a stepped substrate or the like. I found it possible. Moreover, it discovered that the film | membrane produced using the vinyl derivative of this invention was not easily received by the solvent at the time of laminating | stacking an adjacent layer. Further, the present composition was useful in the lamination process, such as being capable of crosslinking by irradiation with predetermined radiation and avoiding damage to other layers.

Sectional view of the SiO ₂ steps wafers used in Examples. Sectional view of the SiO ₂ steps wafers carbon-containing film is formed.

The above summary and the following details are intended to illustrate the present invention and not to limit the claimed invention.
In the present specification, when a numerical range is indicated using-, unless specifically limited and mentioned, these include both end points, and the unit is common. For example, 5-25 mol% means 5 mol% or more and 25 mol% or less.
In the present specification, descriptions such as “C _xy ”, “C _{x ˜C y} ”, and “C _x ” mean the number of carbons in the molecule or substituent. For example, C _1-6 alkyl means an alkyl chain having 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).
In this specification, when a polymer has a plurality of types of repeating units, these repeating units are copolymerized. Unless particularly limited and mentioned, these copolymers may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof.
In this specification, unless otherwise specified, the unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

Vinyl derivative The vinyl derivative in the present invention is represented by the following formula (1).
Each ring A is independently a C _6-14 aromatic hydrocarbon ring or a C _6-14 saturated hydrocarbon ring. Preferably the two rings A are the same. Ring A is preferably a _C6-10 aromatic hydrocarbon ring or a _C6-12 saturated hydrocarbon ring, and more preferably phenyl or cyclohexyl.
X are each independently _{C having 6 to 14} aromatic hydrocarbon _{ring, C having 6 to 14} saturated hydrocarbon ring or _{C 1 to 4} alkyl. Preferably the two X are the same. X is preferably a C _6-10 aromatic hydrocarbon ring, a C _6-12 saturated hydrocarbon ring, a straight chain C _1-4 alkyl, or a branched C _1-4 alkyl, more preferably phenyl, cyclohexyl, Methyl, ethyl, propyl, isopropyl or t-butyl, more preferably phenyl or cyclohexyl. Although not intended to limit the present invention, it is considered that the presence of X can suppress a phenomenon such as the compound being sublimated during film formation.
Each R ₁ is independently hydrogen or C _1-4 alkyl. Preferably two R ₁ are the same. R ₁ is preferably hydrogen, methyl, ethyl, propyl, isopropyl or t-butyl, more preferably hydrogen or methyl, and even more preferably hydrogen.
n is any integer of 0-13. N is preferably 1 to 12, more preferably 1 to 7, and even more preferably 1 or 7. Although not intended to limit the present invention, it is considered that the central skeleton between the rings A is a saturated hydrocarbon ring, which contributes to the ease of reflow and the speed of curing by exposure.

Each L is independently a C _1-4 alkylene, a linker unit of the following formulas (2), (3), (4), or a linker represented by a combination thereof.
The number of linker units possessed by one L is 1 to 4 independently. Preferably the two L are the same. The number of linker units that one L has is preferably 1 to 3, more preferably 1 to 2, and further preferably 2. The C _1-4 alkylene of the linker unit is preferably methylene or ethylene, more preferably methylene. The linker of formula (4) and the like are preferably bonded at the para position.
Each R ₂ is independently hydrogen or C _1-4 alkyl. R ₂ is preferably hydrogen, methyl, ethyl, propyl, isopropyl or t-butyl, more preferably hydrogen or methyl, and even more preferably hydrogen.
Each R ₃ is independently hydrogen or C _1-4 alkyl. R ₃ is preferably hydrogen, methyl, ethyl, propyl, isopropyl or t-butyl, more preferably hydrogen or methyl, and even more preferably hydrogen.

From the viewpoint of ease of synthesis, the compound of the present invention preferably has a symmetrical structure. In this specification, the left-right symmetry means that it is left-right symmetric about the central skeleton sandwiched between the rings A as shown in the following figure.

For example, in the following compound, in formula (1), ring A is phenyl, X is phenyl, R ₁ is hydrogen, and n is 7 (the central skeleton is cyclododecyl). One L is a linker represented by a combination of methylene and two linker units of the formula (4). Two L's are the same. In one linker, methylene and the formula (4) are arranged in this order from the central skeleton to the vinyl. R ₃ is hydrogen.

The vinyl derivative of formula (1) is preferably represented by formula (5) or formula (6).
In formulas (5) and (6), the definitions and preferred embodiments of X, n, L, and R ₁ are each independently the same as in the above formula (1). Naturally, since R ₂ and R ₃ are contained in L, in formulas (5) and (6), the definitions and preferred embodiments of R ₂ and R ₃ are independently the above formulas (1) and (3). The same.
In a preferred embodiment of the vinyl derivatives of formulas (1), (5) and (6), X is a C _6-10 aromatic hydrocarbon or C _6-10 saturated hydrocarbon ring, R ₁ is hydrogen or methyl Yes, n is an integer of 1 to 7, the number of linker units in one L is 1 or 2, R ₂ is hydrogen or methyl, and R ₃ is hydrogen. In a more preferred embodiment, X is phenyl or cycloalkyl, R ₁ is hydrogen, n is 1 or 7, one L has 2 linker units, and R ₂ is hydrogen , R ₃ is hydrogen.
One L has two linker units and is represented by a combination of methylene and formula (4), formulas (2) and (3), methylene and formula (2), and formulas (3) and (4). This is one preferred embodiment. One L has two linker units, and one of the more preferable embodiments is represented by a combination of methylene and formula (4), and formulas (2) and (3).

For illustrative purposes, specific examples of vinyl derivatives of formula (1) are shown below, but are not intended to limit the invention.

Synthesis Method of Vinyl Derivative of the Present Invention The vinyl derivative of the present invention can be synthesized, for example, by adding a vinyl group to a precursor having hydroxyl.
When the vinyl derivative in which ring A is a saturated hydrocarbon ring is synthesized, a saturated hydrocarbon ring can be obtained from an aromatic hydrocarbon ring. “Efficient and Practical Area Hydrogenation by Heterogeneous Catalysts under Mild CONDITIONS,” Tomohiro Maekawa et al. Chem. Eur. J. et al. A synthetic method such as 2009, p6953 can be used. The above Br can be changed to I, Cl or the like.

Electronic Material, Lithographic Material The present invention provides an electronic material comprising the vinyl derivative. In this specification, the electronic material means a material necessary for manufacturing a device or module for an electronic apparatus. Materials necessary for manufacturing include both materials that remain in and constitute devices and modules, and materials that are used in the manufacturing process but are removed but not left.
The present invention also provides a lithography material comprising the above electronic material. This can also be said to be a lithography material made of the vinyl derivative. In this specification, the lithography material means a material used in a lithography process, and is not limited to a material whose solubility changes upon exposure, such as a photoresist. Preferably, the lithographic material of the present specification is a semiconductor lithographic material, and is a material used in a semiconductor manufacturing process (more preferably, a resist pattern forming process).

Composition The present invention provides a composition comprising the vinyl derivative and an organic solvent. The composition is preferably an electronic material composition, more preferably a lithographic composition, and even more preferably a semiconductor lithographic composition.
The present invention also provides a carbon-containing film-forming composition comprising the above composition. The carbon-containing film-forming composition is preferably a carbon-containing underlayer film-forming composition. The carbon-containing film-forming composition preferably has photosensitivity, and a photosensitive carbon-containing film-forming composition or a photosensitive carbon-containing underlayer film-forming composition is a preferred embodiment of the present invention.

Organic solvent The composition of the present invention comprises an organic solvent, and the organic solvent may be one organic solvent or a mixture of a plurality of organic solvents.
Examples of the organic solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane and methyl. Aliphatic hydrocarbon solvents such as cyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene, i-butyl benzene, triethyl benzene, di-i-propyl benzene Aromatic hydrocarbon solvents such as n-amylnaphthalene and trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pen Nord, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n -Octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-hepta Such as decyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl carbinol, diacetone alcohol, cresol Alcohol solvents; ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2- Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone , Methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methyl Ketone solvents such as lohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide 1,2-propylene oxide, 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 dibuty 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 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 Ether solvents such as butyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, acetic acid Methyl cyclohexyl, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl acetate , Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl 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, acetic acid Dipropylene glycol monoethyl ether, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate ( EL), γ-butyrolactone, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propi Ester solvents such as lenglycol 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 and other nitrogen-containing solvents; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1, A sulfur-containing solvent such as 3-propane sultone can be used. Alternatively, a mixture of these can be used.

In particular, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2-acetate, propylene Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, butyl lactate, benzyl alcohol, butyl carbitol acetate, ethyl 3-ethoxypropionate, or a mixture thereof can be used for the storage stability of the solution. This is preferable.
From the viewpoint of solubility of the solute, cyclopentanone, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, ethyl lactate, butyl lactate, benzyl alcohol, butyl carbitol acetate, ethyl 3-ethoxypropionate, or Of these, a mixture of two types is preferred. The two kinds of mixtures are preferably a mixture having a mass ratio of 10:90 to 90:10, more preferably a mixture having a ratio of 25:75 to 75:25.

The amount occupied by the vinyl derivative is preferably from 1 to 15% by mass, more preferably from 1 to 8% by mass, and even more preferably from 1 to 6% by mass, relative to the entire composition.
As long as it is represented by the formula (1), the vinyl derivative is not limited to a single compound, and may be a combination of a plurality of derivatives. For example, the following two compounds may both be included in the composition as the same vinyl derivative. In a preferred embodiment, one or two vinyl derivatives of the present invention are included in the composition.

  The amount occupied by one or more organic solvents (or the sum in the case of a plurality of organic solvents) is preferably 75 to 99% by mass, more preferably 75 to 98% by mass, compared to the entire composition. More preferably, it is 80-98 mass%. The amount of water in the composition is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. In relation to other layers and films, the composition preferably does not contain water, and it is an embodiment of the present invention that the amount of water in the composition is 0.00% by mass.

The number of atoms contained in one or more solid components in the composition preferably satisfies the following formula (7).
1.5 ≦ {total number of atoms / (C number−O number)} ≦ 3.5 (7)
The C number is the number of carbon atoms in the total number of atoms. The O number is the number of oxygen atoms in the total number of atoms.
The said solid component means the component which remains in a film | membrane when a film | membrane is formed from this composition. Solutes that volatilize with the solvent when forming a film with Bake or the like are not included in the solid component.
The number of atoms contained in one or more solid components in the composition of the present invention can be determined by a known calculation method. It can be calculated as an Ohnishi parameter. In the case of a polymer, a weight average molecular weight may be used.
Preferably, formula (7) is formula (7) ′ or formula (7) ″.
1.5 ≦ {total number of atoms / (C number−O number)} ≦ 3.0 (III) ′
1.8 ≦ {total number of atoms / (C number−O number)} ≦ 2.7 (III) ″
By preparing the composition so as to satisfy the above formula, a carbon-containing film with better etching resistance can be obtained. It is possible to adjust the numerical value of the above formula by adding not only the above-mentioned vinyl derivative but also a high carbon material (described later). In the formation of the present carbon-containing film, a mode in which the high carbon material is present without being polymerized in the composition at a point before being cured by irradiation or irradiation after heating is preferable.

Crosslinking agent In this specification, the crosslinking agent means a chemical substance that links molecules and changes physical and chemical properties (hereinafter referred to as a crosslinking component). The crosslinking agent in the present specification does not include a solvent (excluding these when the crosslinking component is liquid from the beginning). Hereinafter, the same applies to the agent added in the composition of the present invention.
Compared with the entire composition, the amount occupied by the crosslinking agent (or the sum in the case of plural compositions) is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass, More preferably, it is 0.2-1 mass%. In calculating the amount occupied, when a solid crosslinking agent is dissolved in a solvent and added to the composition, such a solvent is calculated as a solvent, not a crosslinking agent.

  In the cross-linking agent according to the present composition, it is not necessary that all molecules of the cross-linking agent are used for linking molecules. It may also contribute to adhesion enhancement, surface modification, or flatness improvement. As an embodiment in which a cross-linking agent is added in order to obtain these performances, it is preferable that the amount occupied by the cross-linking agent (the sum in a plurality of cases) is 5 to 25% by mass as compared with the entire composition. It is mentioned as a more preferable aspect that it is 15-20 mass%.

The crosslinking agent according to the present composition is preferably represented by the following formula (8).
The P ring is a phenyl having a hydroxyl.
Y is C _1-6 alkyl, C _6-14 aryl, C _6-12 cycloalkyl, C _7-20 aralkyl, C _7-20 alkyl substituted aralkyl, C _7-20 cycloalkyl substituted alkyl cycloalkyl, or two P A direct bond that connects the rings. More preferably Y is methyl, _C2-3 straight chain alkyl, _C2-5 branched alkyl, _C14-16 aralkyl, _C10-12 alkyl substituted aralkyl, or a direct bond connecting two P rings. More preferably Y is a direct bond connecting _{methyl, C 2 to 3} branched _{alkyl, C 11} alkyl-substituted aralkyl, or two P rings.
Each R ₄ is independently hydrogen, methyl, ethyl, phenyl, methylol, C _1-3 alkoxymethyl or C _6-12 cycloalkyl. More preferably, each R ₄ is independently hydrogen, methyl, phenyl, methylol or methoxymethyl. More preferably, each R ₄ is independently hydrogen, methylol or methoxymethyl.
Each R ₅ is independently hydrogen or C _1-3 alkyl. More preferably R ₅ is hydrogen or methyl.
m is 1, 2, 3 or 4. Preferably m is 1, 2 or 3.
m ′ is 0 or 1. Preferably m ′ is 1.

For example, in the following compound (8), Y is a direct bond connecting two P rings, R ₄ is methoxymethyl, R ₅ is methyl, m is 2 and m ′ is 1. is there.
For example, the following compounds, in Formula (8), Y is C ₂ branched alkyl linking the three P ring, R ₄ is methylol, R ₅ is hydrogen, m is 3, m 'is 1 It is.

For illustration, specific examples of the crosslinking agent of formula (8) are shown below, but are not intended to limit the present invention.
As long as it is represented by Formula (8), the crosslinking agent of Formula (8) is not limited to a single compound, and may be a combination of a plurality of compounds.

  Since the vinyl derivative according to the present invention can be self-crosslinked by radiation, there is an advantage in the lamination process that less crosslinking agent is required. Although it can be selected depending on the apparatus and process conditions, when the amount of the crosslinking agent is reduced, the concentration of the crosslinking agent is preferably 0 to 1,000 ppm as compared with the present carbon-containing underlayer film forming composition. More preferably, it is 0 to 500 ppm. From the viewpoint of process management, the crosslinking is performed only by self-crosslinking of the acrylate derivative of the formula (I), and no crosslinking agent is added (the amount of the crosslinking agent is smaller than that of the present carbon-containing underlayer film forming composition). 0 ppm) is also an embodiment of the present invention.

High carbon material The composition may further comprise a high carbon material. The high carbon material is a compound having a large number of carbon atoms, and can be used to adjust {total number of atoms / (C number−O number)} within the range of the formula (7) by being added to the present composition. For example, the following materials can be used as the high carbon material.
The proportion of the same high carbon material (or the sum in the case of plural materials) in the total mass of the composition is preferably 0.02 to 5 mass%, more preferably 0.05 to 2 mass%, and 0 More preferably, it is 1 to 0.5% by mass. The composition can include one or more high carbon materials. The composition preferably comprises a single high carbon material.

The high carbon material is preferably represented by any of the following formulas (9), (10), or (11). Each will be described later.

The high carbon material represented by the formula (9) is as follows.
Ar ₁ is a direct bond, C _1-6 alkyl, C _6-12 cycloalkyl or C _6-14 aryl. Preferably Ar ₁ is a direct bond, C _1-6 alkyl or phenyl, more preferably a direct bond, straight chain C ₃ alkyl, straight chain C ₆ alkyl, tertiary butyl or phenyl, even more preferably direct. A bond or phenyl.
Ar ₂ is C _1-6 alkyl, C _6-12 cycloalkyl or C _6-14 aryl. Preferably Ar ₂ is isopropyl, tertiary butyl, C ₆ cycloalkyl, phenyl, naphthyl, phenanthryl or biphenyl, more preferably phenyl.
R ₆ and R ₇ are each independently C _1-6 alkyl, hydroxy, halogen or cyano. Preferably, R ₁ and R ₂ are each independently methyl, ethyl, propyl, isopropyl, tertiary butyl, hydroxy, fluorine, chlorine or cyano, more preferably methyl, hydroxy, fluorine or chlorine.
R ₈ is hydrogen, C _1-6 alkyl or C _6-14 aryl. Preferably R ₈ is hydrogen, C _1-6 alkyl or phenyl, more preferably hydrogen, methyl, ethyl, straight chain C ₅ alkyl, tertiary butyl or phenyl, more preferably hydrogen or phenyl, more More preferred is hydrogen.
When Ar ₂ is C _1-6 alkyl or C _6-14 aryl and R ₈ is C _1-6 alkyl or C _6-14 aryl, Ar ₂ and R ₈ are combined to form a hydrocarbon ring, or Do not form.
r and s are each independently 0, 1, 2, 3, 4 or 5. Preferably, r and s are each independently 0 or 1, and more preferably, r and s are each independently 0.
At least one of the C _1, C ₂ and C ₃ rings surrounded by a broken line is an aromatic hydrocarbon ring condensed with the adjacent aromatic hydrocarbon ring P _1, and the number of carbon atoms in the aromatic hydrocarbon ring is aromatic. C _10-14 including carbon of hydrocarbon ring P ₁ is preferable, and C ₁₀ is more preferable.
At least one of the C _4, C _5, and C ₆ rings surrounded by a broken line is an aromatic hydrocarbon ring condensed with the adjacent aromatic hydrocarbon ring P _2, and the number of carbon atoms of the aromatic hydrocarbon ring is aromatic. C _10-14 including carbon of hydrocarbon ring P ₂ is preferable, and C ₁₀ is more preferable.
In the formula (9), the bonding positions of R ₆ , R ₇ and OH are not limited.
For example, the following compound can take the following structure in Formula (9). The aromatic hydrocarbon ring P ₁ and the aromatic hydrocarbon ring C ₃ are condensed to form a naphthyl ring, and OH is bonded to the aromatic hydrocarbon ring C ₃ . Ar ₁ is a direct bond, Ar ₂ and R ₈ are phenyl, and A ₂ and R ₈ are bonded to form a hydrocarbon ring (fluorene).

Specifically, the high carbon material represented by the formula (9) is represented by the following formula.
In the formulas (9) -1, (9) -2 and (9) -3, the definitions of Ar ₁ , Ar ₂ , R ₆ , R ₇ , R ₈ , r and s are the same as described above. These preferred examples are the same as described above independently. Among the high carbon materials of the formula (9), the high carbon material represented by the formula (9) -1 is more preferable.
This composition can contain the high carbon material represented by single or several Formula (9). Use alone is preferred. For example, the following two compounds may be included in the composition as the same high-carbon material.

For illustration, specific examples of the high carbon material represented by the formula (9) are shown below, but are not intended to limit the present invention.

The high carbon material represented by the formula (10) is the following polymer.
R ₉ is hydrogen, C _1-6 alkyl, halogen or cyano. Preferably, R ₉ is hydrogen, methyl, ethyl, propyl, isopropyl, tertiary butyl, fluorine, chlorine or cyano, more preferably R ₉ is hydrogen, methyl, fluorine or chlorine, particularly preferably R ₉ is Hydrogen.
R ₁₀ is C _1-6 alkyl, halogen or cyano. Preferably, R ₁₀ is methyl, ethyl, propyl, isopropyl, tertiary butyl, fluorine, chlorine or cyano, more preferably R ₁₀ is methyl, fluorine or chlorine.
p is 0, 1, 2, 3, 4 or 5, preferably p is 0 or 1, and particularly preferably p is 0.
The high carbon material represented by the formula (10) is a polymer having a repeating unit surrounded by parentheses of the formula (10). In the high carbon material represented by the formula (10), individual R ₉ and R ₁₀ may be the same or different individually.
The weight average molecular weight (Mw) of the high carbon material represented by the formula (10) is preferably 5,000 to 50,000, more preferably 8,000 to 40,000.
In the present specification, the weight average molecular weight can be measured by gel permeation chromatography (GPC). In this measurement, it is a preferred example to use a GPC column at 40 degrees Celsius, an elution solvent tetrahydrofuran at 0.6 mL / min, and monodisperse polystyrene as a standard.

The high carbon material represented by the formula (11) is as follows.
Z is C _1-6 alkyl, C _6-60 aryl, C _6-12 cycloalkyl, C _7-20 aralkyl, C _7-20 alkyl substituted aralkyl, or C _7-20 cycloalkyl substituted alkyl cycloalkyl. Preferably Z is methyl, _C2-4 straight chain alkyl, _C6-50 aryl, _C6-10 cycloalkyl, _C12-18 aralkyl or _C9-14 alkyl substituted aralkyl. More preferably Z is methyl, C _2-3 branched alkyl, C _12-54 aryl, cyclohexyl, C ₁₅ aralkyl or C ₁₁ alkyl substituted aralkyl. More preferably Z is _{methyl, C 2 to 3} branched alkyl, _{fluorenyl, C 54} aryl, _{cyclohexyl, C 15} aralkyl, or _{C 11} alkyl-substituted aralkyl. Even more preferably Z is fluorenyl, C ₁₅ aralkyl or C ₁₁ alkyl substituted aralkyl.
L ′ is independently a direct bond or —O—CH ₂ —CH ₂ —. Preferably L ′ is a direct bond.
Each R ₁₁ is independently hydrogen, methyl, ethyl, phenyl or C _6-12 cycloalkyl. Preferably R ₁₁ is hydrogen, methyl, phenyl or C _6-7 cycloalkyl. More preferably R ₁₁ is hydrogen or phenyl.
Each R ₁₂ is independently hydrogen, methyl, ethyl, phenyl or C _6-12 cycloalkyl. Preferably R ₁₂ is hydrogen, methyl, phenyl or C _6-7 cycloalkyl. More preferably R ₁₂ is hydrogen or phenyl.
q is 1, 2, 3 or 4. Preferably q is 2, 3 or 4. More preferably q is 2 or 3.

For example, the following compound can take the following structure in Formula (11).
Z is fluorene and connects two phenyl rings as a linker. L ′ is a direct bond, R ₁₁ is hydrogen, R ₁₂ is hydrogen, and q is 2.
For example, the following compound can take the following structures in Formula (11).
Z is a C ₁₁ alkyl substituted aralkyl (C ₃ alkyl substituted phenyl C ₂ alkyl), which connects three phenyl rings as a linker. L ′ is a direct bond, R ₁₁ is hydrogen, R ₁₂ is hydrogen, and q is 3.
This composition can contain the high carbon material represented by single or several Formula (11). Use alone is preferred.

For the sake of explanation, specific examples of the high carbon material represented by the formula (11) are shown below, but are not intended to limit the present invention.

Solid component other than vinyl derivative of formula (1), cross-linking agent of formula (8), and high carbon material In addition, a solid component that forms a film may be further included. Such a solid component may be a monomer or a polymer. When forming into a film, these solid components may be copolymerized with the vinyl derivative of the formula (1), may be polymerized separately, or these states may be mixed.
The composition may further contain a surfactant, a photopolymerization initiator, a crosslinking agent other than the crosslinking agent represented by the formula (8), an acid generator, a radical generator, a substrate adhesion enhancer, or a mixture thereof. . The substrate adhesion enhancing agent is different from the crosslinking agent represented by the formula (8).

Surfactants Surfactants are useful for suppressing the occurrence of pinholes and installations and improving the coating properties and solubility. The amount of the surfactant in the present composition is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, relative to the entire present composition. Further, the amount of the surfactant is preferably 0.005 to 10% by mass, more preferably 0.05 to 5% by mass, compared with the vinyl derivative of the formula (1) in the present composition. More preferably, it is 0.05-1 mass%.
Surfactants include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether. Alkyl allyl ether compounds, polyoxyethylene / polyoxypropylene block copolymer compounds, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate and sorbitan tristearate and other sorbitan fatty acid ester compounds, polyoxyethylene sorbitan Monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene Polyoxyethylene sorbitan fatty acid ester compounds such as sorbitan monostearate and polyoxyethylene sorbitan tristearate and the like. Also, trade names F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, R-08, R-30, R-2011 (produced by Dainippon Ink Co., Ltd.), Fluorosurfactants such as Fluorad FC430, FC431 (Sumitomo 3M Co., Ltd.), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Examples thereof include organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and F-563 (DIC Corporation).

Photopolymerization initiator The photopolymerization initiator is a compound that is modified by receiving light to polymerize or polymerize a solid component of the composition, or to trigger the polymerization. Radical photopolymerization initiator (alkylphenone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, intramolecular hydrogen abstraction photopolymerization initiator, oxime ester photopolymerization initiator, photopolymerization initiator blend), cation And a photopolymerization initiator. A radical photopolymerization initiator that receives light to generate radicals is suitable for the present composition. As the photopolymerization initiator, a known polymerization initiator can be used. For example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone 2-hydroxy-2-methyl-1-phenyl-propan-1-one, iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate, 2- [2-oxo 2-phenylacetoxyethoxy] ethyl ester and 2- (2-hydroxyethoxy) ethyl ester, phenyl glycolate, Benzophenone, and the like are preferable. Examples of commercially available photopolymerization initiators include “OXE01”, “OXE02”, “369”, “907”, “651”, “2959”, “184”, “184” of “IRGACURE” series manufactured by BASF Japan Ltd. 250 ”,“ 754 ”;“ MBF ”,“ BP ”,“ 1173 ”in the“ DAROCUR ”series, or mixtures thereof. Preferably, the photopolymerization initiator is used alone.
In the present composition, a photoinitiator may be further combined with a photopolymerization initiator. Examples of the photoinitiator aid include triethanolamine and methyldiethanolamine.

  The blending amount of the photopolymerization initiator in the present invention is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and more preferably 5 to 10% by mass compared to the mass of the vinyl derivative of the formula (1) of the present composition. More preferred is mass%.

  Since the vinyl derivative of the formula (1) can be self-crosslinked, the amount of the photopolymerization initiator added to the composition can be reduced. Although it can be selected depending on the apparatus and process conditions, when the amount of the photopolymerization initiator is reduced, the concentration of the photopolymerization initiator is preferably 0 to 1,000 ppm compared to the present composition. More preferably, it is 0-500 ppm. From the viewpoint of process control, the film is formed only by self-crosslinking of the vinyl derivative of formula (1), and no photopolymerization initiator is added (the amount of the photopolymerization initiator is 0 ppm as compared with the present composition). This is also an embodiment of the present invention.

Acid generator The composition of the present invention may further contain an acid generator. The amount of the acid generator contained in the composition is preferably 0.1 to 10% by mass and more preferably 1 to 7% by mass compared to the mass of the vinyl derivative of the formula (1). preferable.
The acid generator can be a thermal acid generator capable of generating a strong acid by heating. The thermal acid generator (TAG) used in the present invention is any one that generates an acid that reacts with the vinyl derivative of the formula (1) present in the present invention and can propagate the crosslinking of the monomer by heating. One or more can be used, and a strong acid such as sulfonic acid is more preferable. Preferably, the thermal acid generator is activated at a temperature greater than 80 degrees. Examples of thermal acid generators include metal-free sulfonium and iodonium salts, such as strongly non-nucleophilic triarylsulfonium, dialkylarylsulfonium, and diarylalkylsulfonium salts, strongly non-nucleophilic alkylaryliodonium, diaryliodonium. Salts; and ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium salts of strongly non-nucleophilic nucleic acids. Covalent thermal acid generators are also considered as useful additives, such as 2-nitrobenzyl esters of alkyl or aryl sulfonic acids, and other sulfonic acids that thermally decompose to give free sulfonic acids. There is an ester. Examples are diaryl iodonium perfluoroalkyl sulfonate, diaryl iodonium tris (fluoroalkylsulfonyl) methide, diaryl iodonium bis (fluoroalkylsulfonyl) methide, diaryl iodonium bis (fluoroalkylsulfonyl) imide, diaryl iodonium quaternary ammonium perfluoroalkyl Sulfonate. Examples of labile esters are 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate; 2-trifluoromethyl-6-nitrobenzyl Benzene sulfonates such as 4-chlorobenzene sulfonate and 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzene sulfonate; phenolic sulfonate esters such as phenyl and 4-methoxybenzene sulfonate; quaternary ammonium tris (fluoroalkylsulfonyl) methides; And quaternary alkylammonium bis (fluoroalkylsulfonyl) imides, alkylammonium salts of organic acids, such as the triethylammonium salt of 10-camphorsulfonic acid. Various aromatic (anthracene, naphthalene, or benzene derivatives) sulfonic acid amine salts are described in U.S. Pat. Nos. 3,474,054, 4,200,729, 4,251,665, and 5,187. , 019, and the like can be used as a TAG.
Specific examples of the acid generator that can be contained in the composition are as follows, but the scope of the present invention is not limited thereto.

  Since the vinyl derivative of the formula (1) can self-crosslink, the amount of the acid generator added to the present composition can be reduced. Although it can be selected depending on the apparatus and process conditions, when the amount of the acid generator is reduced, the concentration of the acid generator is preferably 0 to 500 ppm as compared with the present composition. From the viewpoint of process management, it is also an embodiment of the present invention that no acid generator is added (the amount of the acid generator is 0 ppm compared to the present composition).

Radical generator In the present composition, a radical generator can be added to initiate polymerization. The radical generator generates radicals by heating, and examples thereof include azo compounds and peroxides. Specifically, hydroperoxides such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, α, α-bis (t-butylperoxy-m-isopropyl) benzene, dicumyl peroxide 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t- Such as dialkyl peroxides such as (bitylperoxy) hexyne-3, t-butylperoxy-2-ethylhexanoate, ketone peroxides, n-butyl 4,4-di- (t-butylperoxy) valerate, etc. Peroxyketals, diacyl peroxides, peroxydicarbonates , Organic peroxides such as peroxyesters, and 2,2′-azobisisobutylnitrile, 1,1 ′-(cyclohexane-1-carbonitrile), 2,2′-azobis (2-cyclopropylpropyl) And azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile). These thermal radical generators may be used alone or in combination of two or more, but are preferably used alone. These known radical generators can be used in the present composition, and these radical generators are available from NOF Corporation.

  Since the vinyl derivative of the formula (1) can be self-crosslinked, it is possible to reduce the amount of the radical generator added to the present composition. Although it can be selected depending on the apparatus and process conditions, when the amount of the radical generator is decreased, the concentration of the radical generator is preferably 0 to 500 ppm as compared with the present composition. From the viewpoint of process management, it is also an embodiment of the present invention that no radical generator is added (the amount of radical generator is 0 ppm compared to the present composition).

Other crosslinking agent This composition can contain crosslinking agents other than the crosslinking agent represented by Formula (8) (referred to as another crosslinking agent). The crosslinking agent is added for the purpose of improving the film formability of the formed carbon-containing lower layer film, eliminating intermixing with the upper layer film (for example, silicon-containing intermediate layer and resist), and eliminating the diffusion of low molecular components into the upper layer film. It is possible.
Specific examples of other crosslinking agents that can be used in the present invention include a melamine compound, a guanamine compound, a glycoluril compound, or a urea substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Examples include compounds containing double bonds such as compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and alkenyl ether groups. These may be used as additives, but may be introduced as pendant groups in the polymer side chain. A compound containing a hydroxy group is also used as a crosslinking agent.
Examples of the epoxy compound among the various compounds include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether and the like. Specific examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, and a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, Examples thereof include compounds in which 1 to 6 methylol groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof. Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, and a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, and tetramethylolguanamine. Examples include compounds in which 4 methylol groups are acyloxymethylated and mixtures thereof. Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 of the methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, tetramethylolglycoluril Or a mixture thereof in which 1 to 4 of the methylol groups are acyloxymethylated. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, tetramethoxyethyl urea, and the like.
Examples of the compound containing an alkenyl ether group 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, Examples include 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.

Specific examples of other cross-linking agents that may be included in the present composition may include the following. The following description is not intended to limit the invention.
3-50 mass% is preferable compared with the mass of the vinyl derivative of Formula (1) of this composition, and, as for the compounding quantity of the other crosslinking agent in this invention, 5-40 mass% is more preferable.

  Since the vinyl derivative of the formula (1) can be self-crosslinked, it is possible to reduce the amount of other crosslinking agent added to the present composition. Although it can be selected depending on the apparatus and process conditions, when the amount of the other cross-linking agent is reduced, the amount of the other cross-linking agent is preferably a concentration of 0 to 1,000 ppm as compared with the present composition. More preferably, it is 0-500 ppm. From the viewpoint of process control, crosslinking is carried out only by self-crosslinking of the vinyl derivative of formula (1), and no other crosslinking agent is added (the amount of the other crosslinking agent is 0 ppm compared to the present composition). This is also an embodiment of the present invention.

Other Components The carbon-containing underlayer film-forming composition of the present invention further includes other components such as a smoothing agent, a monomeric dye, a lower alcohol (C _1-6 alcohol), a surface leveling agent, an antifoaming agent, and an antiseptic. May be added. The amount of these components in the present composition is preferably 0.005 to 10% by mass, and 0.05 to 5% by mass, compared to the vinyl derivative of the formula (1) in the present composition. More preferably, the content is 0.05 to 1% by mass. It is also an embodiment of the present invention that the composition does not contain these components (0% by mass).

Carbon-containing film-forming composition The composition according to the present invention can be used for forming a carbon-containing film because of good embedding and flatness during film formation. The carbon-containing film-forming composition is advantageously used in the production of a pattern using a lithography technique. Examples of the carbon-containing film-forming composition include a photoresist film-forming composition, a carbon-containing lower layer film-forming composition, and a carbon-containing upper layer film-forming composition. Preferably, the carbon-containing film-forming composition according to the present invention is a carbon-containing underlayer film-forming composition.

The carbon-containing lower layer film is a carbon-containing film formed between the substrate and the photoresist layer, and examples thereof include a planarization film, an adhesion layer, and a lower layer anti-reflective coating (BARC layer). The present carbon-containing lower layer film may serve as these functions, for example, may function as both a planarizing film and a BARC layer. The present carbon-containing lower layer film-forming composition is a composition that forms a carbon-containing lower layer film. A preferred embodiment of the present carbon-containing underlayer film is a planarizing film, and a preferred embodiment of the present carbon-containing underlayer film forming composition is a planarizing film-forming composition.
The planarization film forming composition in the present invention refers to a composition in which the flatness of the upper surface (photoresist side) of the film is high between the substrate and the photoresist film. Preferably, an intermediate layer (Si-containing resist intermediate layer, adhesion layer, lower antireflection film, or a combination thereof) is formed above the planarizing film (on the photoresist side), and a photoresist layer is formed thereon. May be. The substrate in the present invention may be a flat substrate because of the high etching resistance of the composition or ease of handling, but the substrate is not flat because of the excellent flatness of the composition. Demonstrate the effect sufficiently.
Similarly, the carbon-containing upper layer film-forming composition is a composition that forms a carbon-containing upper layer film. A preferred embodiment of the present carbon-containing upper layer film is a TARC layer (Top anti-reflective coating).

Method for Producing Carbon-Containing Film One aspect of the method for forming a carbon-containing film according to the present invention will be described.
As described above, the carbon-containing lower layer film in the present invention is a carbon-containing film formed between the substrate and the photoresist layer, and a preferred embodiment of the present invention is a planarizing film. The planarization film forming composition in the present invention refers to a composition in which the flatness of the upper surface (photoresist side) of the film is high between the substrate and the photoresist film. High flatness means that the upper surface of the flattening film is formed horizontally. Further, if the flatness is high, the variation in the distance between the bottom surface of the substrate set horizontally (the lowest substrate when a plurality of substrates are stacked) and the top surface of the planarization film is reduced. A flat substrate means that the distance between the bottom surface of the substrate and the top surface of the substrate is substantially equal (the difference between the distances in the substrate is 0 to 3%).

  A non-flat substrate means a substrate that is not a flat substrate in a broad sense. In the present invention, examples of the substrate that is not flat include a stepped substrate and an uneven substrate. Examples of the substrate that is not flat include a metal-containing substrate having a height difference between the top of the substrate surface and the substrate of 10 to 10,000 nm, preferably 50 to 1,000 nm, and more preferably 100 to 100 nm. 1,000 nm. Further, examples of the substrate that is not flat include a substrate in which walls and contact holes are present by pretreatment. The wall and contact hole can be formed by a known method such as lithography, etching, DSA, etc., and those having an aspect ratio of 10 to 100 (preferably 25 to 75) are suitable. Furthermore, the flat film forming composition of the present invention can be applied to a substrate having a step. The step is preferably 10 to 10,000 nm, more preferably 25 to 1,000 nm, and even more preferably 50 to 300 nm.

As the substrate, a flat substrate and a non-flat substrate can be used as described above.
As the substrate, a metal-containing substrate or a silicon-containing substrate can be used. The substrate in the present invention includes both the case of a single substrate layer and the lamination of a plurality of substrate layers. Substrates include silicon-coated substrates, silicon dioxide-coated substrates, silicon nitride substrates, silicon wafer substrates (SiO ₂ wafers, etc.), glass substrates, indium-containing substrates (ITO substrates, etc.), titanium-containing substrates (titanium nitride, titanium oxide). Etc.) can be used.
In the semiconductor manufacturing process of the present invention, the layer structure of the substrate may be a known method according to the process conditions. For example, the following stacked structure may be mentioned. In the following laminated structure, the left means the lower direction and the right means the upper direction.
Silicon wafer substrate Silicon wafer substrate / titanium containing substrate Silicon wafer substrate / titanium containing substrate / silicon coated substrate Silicon wafer substrate / titanium containing substrate / silicon dioxide coated substrate Silicon wafer substrate / silicon dioxide coated substrate / titanium containing substrate Silicon nitride substrate Silicon Nitride substrate / titanium-containing substrate Silicon nitride substrate / titanium-containing substrate / silicon-coated substrate Silicon nitride substrate / titanium-containing substrate / silicon dioxide-coated substrate Silicon nitride substrate / silicon dioxide-coated substrate / titanium-containing substrate Other substrates stacked on top can be stacked using a known method such as a CVD method. The other substrate can be patterned using a known lithography technique or etching technique. It is also possible to laminate another substrate on the patterned substrate using a known method such as a CVD method.

In the present invention, the carbon-containing film-forming composition of the present invention is applied by an appropriate application method such as a spinner or a coater. The solid component of the present carbon-containing film-forming composition is excellent in embedding in a substrate because the solid component is a vinyl derivative of the formula (1) at the time of application. In the application of the carbon-containing film-forming composition to the substrate, it is preferable that the substrate and the carbon-containing film-forming composition are in direct contact with the substrate, but through another thin film (for example, a substrate modification layer) It may be applied. After application of the composition, the composition is cured by irradiation with ultraviolet light and / or heating to form a carbon-containing film. Preferably, the present carbon-containing film-forming composition is cured by ultraviolet irradiation or ultraviolet irradiation after heating.
The conditions for ultraviolet irradiation of the carbon-containing film-forming composition after coating are preferably such that ultraviolet rays having a wavelength of 10 to 380 nm are irradiated with light at an integrated dose of 100 to 10,000 mJ / cm ² . Thereby, the vinyl derivative of the formula (1) is cured to obtain a carbon-containing film. When the wavelength is short (for example, 10 to 200 nm), since the self-crosslinking of the vinyl derivative of the formula (1) proceeds efficiently, the amount of the photopolymerization initiator can be reduced, and the formed carbon-containing High film thickness uniformity is preferable. In the present specification, the film thickness uniformity means a variation in film thickness when applied to a flat substrate and formed into a film, and a high film thickness uniformity means that the variation is small. When the wavelength is long (for example, greater than 200 nm and 380 nm or less), the curing can be efficiently performed by adding a photopolymerization initiator that accepts these ultraviolet rays to the carbon-containing film-forming composition.
10-200 nm is suitable for the said wavelength, 100-200 nm is more suitable, 125-195 nm is still more suitable, and 170-175 nm is still more suitable. The integrated irradiation dose is suitably a 100~5,000mJ / cm ^2, it is more preferably from 200~1,000mJ / cm ^2, further preferably be a 300~800mJ / cm ² It is. The above conditions can be modified as appropriate depending on the thickness of the carbon-containing film to be formed.
When the present carbon-containing film forming composition is cured by heating, the heating temperature is generally 100 to 400 ° C. (preferably 150 to 350 ° C., more preferably 175 to 300), and the heating time is generally 30 to 180 seconds. It is appropriately selected from the range (preferably 30 to 120 seconds). Heating can be performed in multiple steps (step baking). For example, heating is performed in two steps, the solvent is removed by the first heating, embedding in the substrate, and light reflow is performed by the second heating. Thus, a film can be formed while ensuring flatness. For example, it is also preferable to perform the first heating at 100 to 300 ° C. for 30 to 120 seconds and the second heating at 150 to 400 ° C. for 30 to 120 seconds. Although the present carbon-containing film-forming composition may be cured only by heating, a combination with ultraviolet irradiation is also suitable. When performing the same curing only by heating, it is desirable to add a crosslinking agent, an acid generator and / or a radical generator.
The atmosphere for ultraviolet irradiation or heating may be air, but the oxygen concentration can be reduced to prevent oxidation of the present carbon-containing film-forming composition and the present carbon-containing underlayer film. For example, the oxygen concentration may be 1,000 ppm or less (preferably 100 ppm or less) by injecting an inert gas (N ₂ , Ar, He, or a mixture thereof) into the atmosphere.

  Etching resistance can be increased by adding a high carbon material to the present carbon-containing film-forming composition, which is suitable as a carbon-containing underlayer film formed by a spin-on coating method. For the evaluation of the etching rate, a known method can be used. For example, a film having an etching rate of 1.0 or less compared to a resist (UV1610, manufactured by Dow) is preferable, and a film having a value of 0.9 or less is more preferable. More preferred is a film of 0.8 or less.

Formation of photoresist film and other films A photoresist composition (for example, a positive photoresist composition) is applied on the carbon-containing lower layer film thus formed. In the case of a carbon-containing upper layer film, the carbon-containing upper layer film is applied after forming a photoresist film. Preferably, the composition of the present invention is a carbon-containing underlayer film forming composition, and a photoresist film is formed above the carbon-containing underlayer film.
Here, the positive photoresist composition refers to one that reacts when irradiated with light and increases the solubility of the irradiated portion in the developer. The photoresist composition used is not particularly limited, but any positive photoresist composition, negative photoresist composition, or negative tone development (NTD) photo may be used as long as the exposure light for pattern formation is sensitive. Resist compositions can be used.
In the resist pattern manufacturing method of the present invention, the presence of a film or layer other than the carbon-containing film or the photoresist film formed from the present carbon-containing film-forming composition is allowed. An intermediate film may be interposed without the carbon-containing film and the photoresist film being in direct contact with each other. The intermediate layer is a film formed between the photoresist film and the carbon-containing film, and examples thereof include a BARC layer, an inorganic hard mask intermediate layer (silicon oxide film, silicon nitride film, and silicon nitrogen oxide film) and an adhesion film. . Regarding the formation of the inorganic hard mask intermediate layer, Japanese Patent No. 5336306 can be referred to. The intermediate film may be composed of one layer or a plurality of layers. A TARC layer may be formed on the photoresist film.
In the manufacturing process of the semiconductor of the present invention, the layer configuration other than the present carbon-containing film can use a known method in accordance with the process conditions. In the case where the present carbon-containing film is a planarizing film, for example, the following laminated structure can be given.
Substrate / flattened film / photoresist film Substrate / flattened film / BARC layer / photoresist film Substrate / flattened film / BARC layer / photoresist film / TARC layer Substrate / flattened film / inorganic hard mask intermediate layer / photoresist Film / TARC layer substrate / planarizing film / inorganic hard mask intermediate layer / BARC layer / photoresist film / TARC layer substrate / planarizing film / adhesion film / BARC layer / photoresist film / TARC layer substrate / substrate modification layer / Planarization film / BARC layer / photoresist film / TARC layer Substrate / substrate modification layer / planarization film / adhesion film / BARC layer / photoresist film / TARC layer These layers are heated and / or exposed after coating. The film can be cured by using a known method such as a CVD method. These layers can be removed by a known method (etching or the like), and each layer can be patterned using the upper layer as a mask.

  As one embodiment of the present invention, the carbon-containing film can be formed over a non-planar substrate, and another substrate can be formed thereover. For example, another substrate can be formed by a method such as CVD. The lower substrate and the upper substrate may have the same composition or different compositions. Furthermore, another layer can be formed on the upper substrate. By forming this carbon-containing film and / or a photoresist film with this other layer, the upper substrate can be processed. Usable photoresist films and other films are the same as described above.

Patterning, device fabrication The photoresist film is exposed through a predetermined mask. Although the wavelength of the light used for exposure is not specifically limited, It is preferable to expose with the light whose wavelength is 13.5-248 nm. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet light (wavelength 13.5 nm), and the like can be used, and KrF excimer laser is more preferable. These wavelengths allow a range of ± 1%. After the exposure, post-exposure bake can be performed as necessary. The post-exposure heating temperature is appropriately selected from 80 to 150 ° C, preferably 100 to 140 ° C, and the heating time is 0.3 to 5 minutes, preferably 0.5 to 2 minutes.
Next, development is performed with a developer. When the positive photoresist composition is used, the exposed portion of the positive photoresist layer is removed by development to form a photoresist pattern. This photoresist pattern can be further miniaturized by using a shrink material or the like.

As the developer used for development in the above-described photoresist pattern forming method, a 2.38% by mass TMAH aqueous solution is preferable. By using such a developer, the carbon-containing lower layer film can be easily dissolved and removed at room temperature. Further, a surfactant or the like can be added to these developers. The temperature of the developer is generally 5 to 50 ° C., preferably 25 to 40 ° C., and the development time is generally appropriately selected from 10 to 300 seconds, preferably 30 to 60 seconds.
The intermediate layer can be patterned using the obtained photoresist pattern as a mask. A known method such as etching (dry etching or wet etching) can be used for pattern formation. For example, the intermediate layer can be etched using the photoresist pattern as an etching mask, and the planarization film and the substrate can be etched using the obtained intermediate layer pattern as an etching mask to form a pattern on the substrate. As another form, the inorganic hard mask intermediate layer is etched using the photoresist pattern as an etching mask, the planarizing film is etched using the obtained inorganic hard mask intermediate layer pattern as an etching mask, and the obtained planarizing film pattern A pattern can be formed on the substrate by etching the substrate using the etching mask. Further, the substrate can be etched as it is while etching a layer below the photoresist layer (for example, an intermediate layer and / or a lower layer film) using the photoresist pattern as an etching mask. Wiring can be formed on the substrate using the formed pattern.
For example, the carbon-containing film can be removed preferably by dry etching with O ₂ , CF ₄ , CHF ₃ , Cl ₂ or BCl ₃ , and preferably O ₂ or CF ₄ can be used.

  Thereafter, if necessary, the substrate is further processed to form a device. For these further processing, known methods can be applied. After forming the device, the substrate is cut into chips as necessary, connected to a lead frame, and packaged with a resin. In the present invention, this packaged product is called a device. The device is preferably a semiconductor.

The present invention will be described in the specific examples in the following examples. These examples are illustrative only and are not intended to limit the scope of the present invention.
Hereinafter, “parts” means parts by mass.

Synthesis Example 1, Synthesis of Example Compound 1
Intermediate 1 was obtained by the following steps. In a reaction vessel equipped with a Liebig condenser, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (25 parts, Tokyo Chemical Industry Co., Ltd.), potassium carbonate (80 parts, Wako Pure Chemical Industries, Ltd.), 18 -Crown 6-ether (3 parts, Tokyo Chemical Industry Co., Ltd.) and N, N-dimethylformamide (610 parts, Kanto Chemical Co., Inc.) were added. 2-iodoethanol (80 parts, Tokyo Chemical Industry Co., Ltd.) was gradually added while heating and stirring this at 140 ° C. This was stirred at 140 ° C. for 8 hours to be reacted. After completion of the reaction, this was returned to room temperature, and the insoluble inorganic salt was filtered through filter paper (Pore size 1 μm, hereinafter the same) to obtain a filtrate. N, N-dimethylformamide in the filtrate was distilled off under reduced pressure using an evaporator. This liquid was poured into pure water (1500 parts) under stirring to produce a precipitate. This was filtered with a filter paper, and the precipitate was collected. The obtained precipitate was dissolved in dichloromethane (1000 parts, Wako Pure Chemical Industries, Ltd.), magnesium sulfate (50 parts, Wako Pure Chemical Industries, Ltd.) was further added, and the mixture was stirred. After stirring, insoluble magnesium sulfate was filtered through a filter paper to obtain a filtrate. Dichloromethane in the filtrate was distilled off under reduced pressure using an evaporator to obtain a reaction product containing Intermediate 1.

Subsequently, Example Compound 1 was obtained by the following steps. Dichloromethane (765 parts, Wako Pure Chemical Industries, Ltd.) was prepared in a reaction vessel, and the whole reaction product including intermediate 1 and triethylamine (24 parts, Kanto Chemical Co., Inc.) were added thereto. While stirring this at room temperature, acrylic acid chloride (16 parts, Tokyo Chemical Industry Co., Ltd.) was slowly added. This was stirred at room temperature for 4 hours to be reacted. After completion of the reaction, pure water (580 parts) was added thereto and stirred to stop the reaction, and the liquid layer was separated. Since the target Example Compound 1 was contained in the organic liquid layer (dichloromethane), the steps described below were performed three times and extracted. That is, the organic liquid layer of the liquid after the reaction was stopped was separated, pure water (580 parts) was added to and mixed with the organic liquid layer, and then allowed to stand until the separation was completed to separate the organic liquid layer.
Magnesium sulfate (50 parts, Wako Pure Chemical Industries, Ltd.) was added to the organic liquid layer obtained by separation and stirred. After stirring, insoluble magnesium sulfate was filtered through a filter paper to obtain a filtrate. Dichloromethane in the filtrate was distilled off under reduced pressure with an evaporator to obtain a reaction mixture. The resulting reaction mixture was purified by silica gel column chromatography. In this purification, heptane: dichloromethane = 80: 20 volume ratio was used as a developing solution, and Wako Gel C-300HG was used as a silica gel filler. The solvent of the obtained purified product was distilled off under reduced pressure using an evaporator to obtain 23 parts of Example Compound 1.
The yield of Example Compound 1 obtained from the starting material 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane was 67%.

Synthesis Example 2, Synthesis of Example Compound 2

  1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (25 parts, Tokyo Chemical Industry Co., Ltd.) of Synthesis Example 1 was replaced with 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane (24 parts). The synthesis was carried out in the same manner as in Synthesis Example 1 except that it was changed to Honshu Chemical Industry Co., Ltd.). The yield of Example Compound 2 was 59%.

Synthesis Example 3, Synthesis of Example Compound 3
1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (25 parts, Tokyo Chemical Industry Co., Ltd.) of Synthesis Example 1 was replaced with 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclododecane (29 Synthesis was performed in the same manner as in Synthesis Example 1 except that the composition was changed to HONJU CHEMICAL CO., LTD. The yield of Example Compound 3 was 52%.

Synthesis Example 4, Synthesis of Example Compound 4
In a reaction vessel equipped with a Liebig condenser, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (25 parts, Tokyo Chemical Industry Co., Ltd.), potassium carbonate (80 parts, Wako Pure Chemical Industries, Ltd.), 18 -Crown 6-ether (3 parts, Tokyo Chemical Industry Co., Ltd.) and N, N-dimethylformamide (610 parts, Kanto Chemical Co., Inc.) were added. While this was heated and stirred at 80 ° C., 4- (chloromethyl) styrene (42 parts, Tokyo Chemical Industry Co., Ltd.) was gradually added. This was stirred at 100 ° C. for 10 hours to be reacted. After completion of the reaction, this was returned to room temperature, and insoluble salts were filtered through filter paper to obtain a filtrate. N, N-dimethylformamide in the filtrate was distilled off under reduced pressure using an evaporator. This liquid was poured into pure water (1500 parts) under stirring to produce a precipitate. This was filtered with a filter paper, and the precipitate was collected. The obtained precipitate was dissolved in dichloromethane (1000 parts, Wako Pure Chemical Industries, Ltd.), magnesium sulfate (50 parts, Wako Pure Chemical Industries, Ltd.) was further added, and the mixture was stirred. After stirring, insoluble magnesium sulfate was filtered through a filter paper to obtain a filtrate. Dichloromethane in the filtrate was distilled off under reduced pressure using an evaporator to obtain a reaction product. Heptane (700 parts, Wako Pure Chemical Industries, Ltd.) was added to the obtained reaction product and stirred at 80 degrees for 30 minutes. This was filtered with a filter paper to remove insoluble precipitates. The heptane in the obtained filtrate was distilled off under reduced pressure with an evaporator to obtain a reaction mixture. The obtained reaction mixture was purified by silica gel column chromatography in the same manner as in Synthesis Example 1. The solvent of the obtained purified product was distilled off under reduced pressure using an evaporator to obtain 16 parts of Example Compound 4.
The yield of Example Compound 4 obtained was 42%.

Synthesis Example 5, Synthesis of Example Compound 5
1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (25 parts, Tokyo Chemical Industry Co., Ltd.) of Synthesis Example 4 was replaced with 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane (24 parts). The synthesis was carried out in the same manner as in Synthesis Example 4 except that it was changed to Honshu Chemical Industry Co., Ltd.). The yield of Example Compound 5 was 46%.

Synthesis Example 6, Synthesis of Example Compound 6 Synthesis Example 6: Formula 9
1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (25 parts, Tokyo Chemical Industry Co., Ltd.) of Synthesis Example 4 was replaced with 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclododecane (29 Synthesis was carried out in the same manner as in Synthesis Example 4 except that the composition was changed to HONJU CHEMICAL CO., LTD. The yield of Example Compound 6 was 41%.

Synthesis Example 7, Synthesis of Example Compound 7
1,1-bis (3-cyclohexyl-4-hydroxycyclohexyl) cyclohexane was synthesized from 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane (50 parts, Tokyo Chemical Industry Co., Ltd.). The synthesis is described in Chem. Eur. J. vol.15, p6953, according to “Efficient and Practical Area Hydrogenation by Heterogeneous Catalysts under Mild Conditions” Tomohiro Maegawa et al, (2009).

2-Iodoethyl acrylate was synthesized from 2-iodoethanol (50 parts, Tokyo Chemical Industry Co., Ltd.). The synthesis is described in Polymer vol. 53, p2008- “Extraordinary aspects of bromo-functionalized multi-walled carbon nanotubes as initiator for homogeneity of ionic liquids”.

Tetrahydrofuran (516 parts, Wako Pure Chemical Industries) was placed in a reaction vessel equipped with a Liebig condenser, and 1,1-bis (3-cyclohexyl-4-hydroxycyclohexyl) cyclohexane (25 parts) was added. While this was stirred at 0 ° C., sodium hydride (7 parts, Wako Pure Chemical Industries) was gradually added. The solution was heated to 65 ° C., and 2-iodoethyl acrylate (30 parts) was slowly added. This solution was stirred at 65 ° C. for 10 hours to be reacted. After completion of the reaction, this was returned to room temperature, and insoluble inorganic salts were filtered with a filter paper to obtain a filtrate. The tetrahydrofuran in the filtrate was distilled off under reduced pressure using an evaporator. This was poured into pure water (1500 parts) under stirring to produce a precipitate, and the precipitate was collected by filtering with a filter paper. The obtained precipitate was dissolved in dichloromethane (1000 parts, Wako Pure Chemical Industries, Ltd.), magnesium sulfate (50 parts, Wako Pure Chemical Industries, Ltd.) was further added, and the mixture was stirred. After stirring, insoluble magnesium sulfate was filtered through a filter paper to obtain a filtrate. Dichloromethane in the filtrate was distilled off under reduced pressure with an evaporator to obtain a reaction mixture. The resulting reaction mixture was purified by silica gel column chromatography. In this purification, heptane: dichloromethane = 80: 20 volume ratio was used as a developing solution, and Wako Gel C-300HG was used as a silica gel filler. The solvent of the obtained purified product was distilled off under reduced pressure using an evaporator to obtain 14 parts of Example Compound 7.
The yield of 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane and the obtained Example compound 7 was 38%.

Synthesis Example 8, Synthesis of Example Compound 8
The synthesis was performed in the same manner as in Synthesis Example 1 except that acrylic acid chloride (16 parts, Tokyo Chemical Industry Co., Ltd.) in Synthesis Example 1 was changed to methacrylic acid chloride (18 parts, Tokyo Chemical Industry Co., Ltd.). The yield of Example Compound 8 was 58%.

NMR Structural Analysis The compounds prepared in the above synthesis examples and comparative synthesis examples were each subjected to NMR measurement and subjected to structural analysis. The results are as follows. It confirmed that it was the said structure, respectively.
Example Compound 1
¹ H-NMR (400 MHz in d-DMSO): 1.18-1.37 (m-br, 10H), 1.41 (s-br, 6H), 1.60-1.72 (m-br, 10H), 2.16 (s-br, 4H), 2.76 (t-br, 2H), 4.12 (t, 4H), 4.42 (t, 4H), 5.96 (d, 2H) ), 6.17 (q, 2H), 6.31 (d, 2H), 6.80 (d, 2H), 6.97 (d, 2H), 7.06 (s, 2H),
¹³ C-NMR (100 MHz in d-DMSO): 166.5, 150.4, 137.4, 133.3, 131.1, 128.2, 124.9, 112.1, 66.8, 64. 4, 40.3, 39.7, 37.8, 34.9, 26.3, 26.0, 25.4, 22.8
Example Compound 2
¹ H-NMR (400 MHz in d-DMSO): 1.44 (s-br, 6H), 2.02 (s-br, 4H), 4.42 (t, 4H), 4.52 (t, 4H) ), 5.59 (d, 2H), 6.05 (q, 2H), 6.27 (d, 2H), 6.97-7.15 (m, 4H), 7.41-7.52 ( m, 6H), 7.75 (d, 2H),
¹³ C-NMR (100 MHz in d-DMSO): 166.5, 155.7, 138.2, 137.9, 131.3, 130.6, 129.9, 129.2, 128.2, 127. 9,127.6,126.6,126.2,113.9,66.8,64.4,40.3,39.7,22.8,26.3
Example Compound 3
¹ H-NMR (400 MHz in d-DMSO): 0.90 (s-br, 4H), 1.29 (s-br, 14H), 2.05 (s-br, 4H), 4.16 (t , 4H), 4.33 (t, 4H), 5.91 (d, 2H), 6.14 (q, 2H), 6.28 (d, 2H), 6.96-7.10 (m, 6H), 7.19-7.30 (m, 6H), 7.40 (d, 4H),
¹³ C-NMR (100 MHz in d-DMSO): 166.5, 155.7, 138.2, 137.9, 131.3, 130.6, 129.2, 128.2, 127.9, 127. 6,126.6,126.2,113.9,66.8,43.5,42.9,25.0,24.4,19.2
Example Compound 4
¹ H-NMR (400 MHz in d-DMSO): 1.20-1.43 (m-br, 16H), 1.67-1.76 (m-br, 10H), 2.19 (s-br, 4H), 2.90 (t-br, 2H), 5.04 (s, 4H), 5.25 (d, 2H), 5.83 (d, 2H), 6.72 (q, 2H), 6.85 (d, 2H), 6.97 (d, 2H), 7.10 (s, 2H), 7.38 (d, 2H), 7.48 (d, 2H),
¹³ C-NMR (100 MHz in d-DMSO): 153.6, 138.1, 136.8, 136.1, 135.9, 133.0, 129.3, 128.8, 128.6, 125. 3, 114.3, 112.0, 71.1, 40.3, 39.7, 37.8, 34.9, 26.3, 26.0, 25.4, 22.8,
Example Compound 5
¹ H-NMR (400 MHz in d-DMSO): 1.50 (s-br, 6H), 2.29 (s-br, 4H), 5.06 (s, 4H), 5.24 (d, 2H) ), 5.81 (d, 2H), 6.70 (q, 2H), 7.06 (d, 2H), 7.25-7.49 (m, 22H)
¹³ C-NMR (100 MHz in d-DMSO): 145.8, 138.9, 137.9, 136.8, 136.1, 135.9, 131.0, 129.3, 129.2, 128. 8, 127.9, 127.6, 127.0, 126.1, 114.3, 113.8, 71.1, 40.3, 39.7, 22.8, 26.3
Example Compound 6
¹ H-NMR (400 MHz in d-DMSO): 0.98 (s-br, 4H), 1.28 (s-br, 14H), 2.02 (s-br, 4H), 5.08 (s , 4H), 5.12 (d, 2H), 5.79 (d, 2H), 6.75 (q, 2H), 7.12 (d, 2H), 7.20-7.60 (m, 22H)
¹³ C-NMR (100 MHz in d-DMSO): 145.8, 138.9, 137.9, 136.8, 136.1, 135.9, 131.0, 129.3, 129.2, 128. 8, 127.9, 127.6, 127.0, 126.1, 114.3, 113.8, 71.1, 43.5, 42.9, 25.0, 24.4, 19.2.
Example Compound 7
¹ H-NMR (400 MHz in d-DMSO): 1.27—1.74 (m, 48H), 2.78 (q, 2H), 4.01 (t, 4H), 4.32 (t, 4H) ), 5.76 (d, 2H), 6.07 (q, 2H), 6.30 (d, 2H)
¹³ C-NMR (100 MHz in d-DMSO): 166.5, 131.3, 128.2, 95.4, 67.5, 65.1, 41.6, 38.1, 37.5, 34. 3, 34.2, 33.0, 29.3, 27.4, 26.3, 26.1, 26.0, 25.5, 22.3
Example Compound 8
¹ H-NMR (400 MHz in d-DMSO): 1.16 to 1.42 (m-br, 10H), 1.45 (s-br, 6H), 1.65 to 1.78 (m-br, 10H), 2.01 (s, 6H), 2.26 (s-br, 4H), 2.86 (t-br, 2H), 4.24 (t, 4H), 4.39 (t, 4H) ), 5.96 (d, 2H), 6.31 (d, 2H), 6.83 (d, 2H), 7.01 (d, 2H), 7.13 (s, 2H)
¹³ C-NMR (100 MHz in d-DMSO): 167.2, 150.4, 137.4, 136.0, 133.1, 128.2, 125.2, 124.9, 112.1, 66. 8, 64.7, 40.3, 39.7, 37.8, 34.9, 26.3, 26.0, 25.4, 22.8, 17.9

Preparation Example 1 of Example Composition 1
1: 1 mixture of PGME and cyclopentanone (mass ratio) so that the above-mentioned Example Compound 1 is 3.0% by mass and the surfactant (F-563, DIC Corporation) is 0.003% by mass. In Example composition 1. Each of these amounts is relative to the total composition.

Example 1-1, Evaluation of Solubility of Example Composition 1 The state of dissolution of the solute of Example Composition 1 was visually confirmed and evaluated as follows.
A: The solute is completely dissolved.
B: The solute is not completely dissolved but remains.
The evaluation results are shown in Table 1.

Example 1-2, Evaluation of Film Formability and Film Thickness Uniformity of Example Composition 1 Using an ACT12 apparatus (made by TEL Corporation), Example Composition 1 was applied to a 12 inch bare silicon wafer at 1,500 rpm. It was applied, baked at 200 ° C. for 1 minute, and irradiated with 172 nm vacuum ultraviolet (VUV) at 500 mJ / cm ² in the same apparatus to obtain a carbon-containing film. It was confirmed with a Lambda Ace VM-3110 optical interference type film thickness measuring device (manufactured by Dainippon Screen Mfg. Co., Ltd.) that the carbon-containing film had an average film thickness of 100 nm.
The surface of the carbon-containing film was confirmed with an optical microscope, and the film forming property was evaluated as follows.
A: A uniform film was formed.
B: A uniform film was not formed.
The evaluation results are shown in Table 2.
Furthermore, the film thickness uniformity (FTU) was obtained by dividing the difference between the maximum and minimum lamda ace VM-3110 under the condition of n = 55 by 100 nm. The FTU of the film was 2.5%, which was a practical level.
The evaluation results are shown in Table 2.

Example 1-3 Evaluation of Solvent Resistance of Example Composition 1 In order to evaluate the resistance of the carbon-containing film to the solvent, the following experiment was conducted.
In a state where the substrate on which the carbon-containing film obtained in Example 1-2 was formed was rotated at 1,000 rpm, a 70:30 mixed solution (mass ratio) of PGME and PGMEA was 1 on the carbon-containing film. The flow continued for a minute.
These substrates were spin-dried (1,500 rpm, 1 minute) to dry the carbon-containing film. Moreover, the experiment which dried the carbon containing film | membrane by baking (150 degreeC, 120 second) of these board | substrates was conducted separately.
The film thickness of the carbon-containing film after drying was confirmed with Lambda Ace VM-3110. The amount of film reduction was 0.7%.
The evaluation results are shown in Table 2.

Example 1-4, Evaluation of Flatness of Composition 1 Using an ACT12 apparatus (manufactured by TEL Co., Ltd.), Example Composition 1 was converted into a SiO ₂ stepped wafer (width 50 μm, height 100 nm wall, width 50 μm trench). ) At 1,500 rpm. FIG. 1 shows the same SiO ₂ step wafer. The SiO ₂ step wafer is a substrate that is not flat, and the walls and the trenches continue at equal intervals. Note that the scale is not accurate for the sake of understanding. This was baked at 200 ° C. for 1 minute, and irradiated with 172 nm vacuum ultraviolet (VUV) at 500 mJ / cm ² in the same apparatus to obtain a carbon-containing film.
A section of the carbon-containing film was prepared to obtain a SEM (S-5500, manufactured by Hitachi High-Tech Fielding). The flatness of Example Composition 1 was evaluated as follows. The difference between the thickest part of the carbon-containing film formed on the wall and the thinnest part of the carbon-containing film formed on the trench was defined as flatness. The difference can be obtained by the difference between 7 and 8 in FIG. The flatness of Example Composition 1 was 64 nm.
The evaluation results are shown in Table 2.

Example Preparation Examples 2-7 of Example Compositions 2-7 and Comparative Example Adjustment Examples 1-3 of Comparative Compositions 1-3
Except having changed the solid component into the kind and quantity of Table 1, Example composition 2-7 and Comparative composition 1-3 were adjusted similarly to Example adjustment example 1. As in Example Preparation Example 1, 0.003% by mass of surfactant (F-563) was added to Example Compositions 2 to 7 and Comparative Example Compositions 1 to 3. Each of these amounts is relative to the total composition. Sub. Component means the second component of the solid component that forms the film.

Evaluation of Example Compositions 2 to 7 and Comparative Example Compositions 1 to 3 The same evaluation as Example 1 (Examples 1-1 to 1-4) was performed for Compositions 2 to 7. The evaluation results are shown in Tables 1 and 2. In the table, “%” means mass% of the component in the entire composition.
When Comparative Composition 3 tried to obtain a carbon-containing film in Example 1-2, it could not be formed because it sublimated in the firing step. Therefore, the comparative composition 3 was not used for the evaluation after the film forming property.
Even if the structure has vinyl, the composition not containing this vinyl derivative has poor heat resistance (Comparative composition 3), low resistance to a solvent after film formation (Comparative composition 1), and flatness. Was found to be low (Comparative Composition 2). The composition of this example contained the vinyl derivative, and was excellent in solubility, film formability, heat resistance, film thickness uniformity, solvent resistance and flatness.

1. Wall width 2. Wall height 3. Trench width 4. Bottom of substrate 5. Bottom of substrate 6. Top of substrate 7. Difference between the thickest portion of the carbon-containing film formed on the wall and the bottom surface of the substrate The difference between the thinnest part of the carbon-containing film created on the trench and the bottom of the substrate

Claims (23)

A vinyl derivative represented by the following formula (1).
{Where,
Each ring A is independently a C _6-14 aromatic hydrocarbon ring or a C _6-14 saturated hydrocarbon ring;
Each X is independently a C _6-14 aromatic hydrocarbon ring, a C _6-14 saturated hydrocarbon ring or C _1-4 alkyl;
Each R ₁ is independently hydrogen or C _1-4 alkyl;
n is any integer from 0 to 13,
L is each independently a C _1-4 alkylene, a linker unit represented by the following formulas (2), (3), (4), or a combination thereof, and the number of linker units in one L is Each independently 1 to 4,
Each R ₂ is independently hydrogen or C _1-4 alkyl;
Each R ₃ is independently hydrogen or C _1-4 alkyl. } The vinyl derivative according to claim 1, wherein the formula (1) is represented by the following formula (5) or (6).
{In the formulas (5) and (6),
The definitions of X, n, L, and R ₁ are the same as those in claim 1 independently. } X is a _C6-10 aromatic hydrocarbon or _C6-10 saturated hydrocarbon ring,
R ₁ is hydrogen or methyl;
n is an integer from 1 to 7,
The number of linker units that one L has is 1 or 2,
R ₂ is hydrogen or methyl;
R ₃ is hydrogen;
The vinyl derivative according to claim 1 or 2, which is symmetrical.   The electronic material which consists of a vinyl derivative as described in any one of Claims 1-3.   A lithography material comprising the electronic material according to claim 4. A composition comprising the vinyl derivative according to any one of claims 1 to 3 and an organic solvent.   The organic solvent is cyclohexanone, cyclopentanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol 1-monomethyl ether 2- Claims selected from acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, γ-butyrolactone, ethyl lactate, butyl lactate, benzyl alcohol, butyl carbitol acetate, ethyl 3-ethoxypropionate, or mixtures thereof Item 7. The composition according to Item 6.   The composition according to claim 6 or 7, wherein a proportion of the vinyl derivative and the organic solvent in the total mass of the composition is 1 to 15% by mass and 75 to 99% by mass, respectively. The composition according to any one of claims 6 to 8, wherein the number of atoms contained in one or more solid components in the composition satisfies the following formula (7).
1.5 ≦ {total number of atoms / (C number−O number)} ≦ 3.5 (7)
{C number is the number of carbon atoms in the total number of atoms,
The O number is the number of oxygen atoms in the total number of atoms. }   The composition according to any one of claims 6 to 9, further comprising a crosslinking agent, wherein a ratio of the crosslinking agent to the total mass of the composition is 0.05 to 5% by mass. The composition according to claim 10, wherein the crosslinking agent is represented by the following formula (8).
{Where,
The P ring is a hydroxyl-bearing phenyl;
Y is C _1-6 alkyl, C _6-14 aryl, C _6-12 cycloalkyl, C _7-20 aralkyl, C _7-20 alkyl substituted aralkyl, C _7-20 cycloalkyl substituted alkyl cycloalkyl, or two P A direct bond connecting the rings,
Each R ₄ is independently hydrogen, methyl, ethyl, phenyl, methylol, C _1-3 alkoxymethyl or C _6-12 cycloalkyl;
Each R ₅ is independently hydrogen or C _1-3 alkyl;
m is 1, 2, 3 or 4, and m ′ is 0 or 1. }   The composition according to any one of claims 6 to 11, further comprising a high carbon material, wherein a ratio of the high carbon material to a total mass of the composition is 0.02 to 5 mass%. The composition according to claim 12, wherein the high-carbon material is represented by the following formula (9), (10), or (11).
{Where,
Ar ₁ is a direct bond, C _1-6 alkylene, C _6-12 cycloalkylene or C _6-14 arylene;
Ar ₂ is C _1-6 alkyl, C _6-12 cycloalkyl or C _6-14 aryl;
R ₆ and R ₇ are each independently C _1-6 alkyl, hydroxy, halogen or cyano,
R ₈ is hydrogen, C _1-6 alkyl or C _6-14 aryl,
When Ar ₂ is C _1-6 alkyl or C _6-14 aryl and R ₈ is C _1-6 alkyl or C _6-14 aryl, Ar ₂ and R ₈ are combined to form a hydrocarbon ring. Or do not form,
r and s are each independently 0, 1, 2, 3, 4 or 5;
At least one of the C _1, C _2, and C ₃ rings surrounded by a broken line is an aromatic hydrocarbon ring that condenses with an adjacent aromatic hydrocarbon ring P ₁ ;
At least one of C _4, C ₅ and C ₆ ring surrounded by a broken line is an aromatic hydrocarbon ring condensed with an aromatic hydrocarbon ring P ₂ adjacent. }
{Where,
Each R ₉ is independently hydrogen, C _1-6 alkyl, halogen or cyano;
Each R ₁₀ is independently C _1-6 alkyl, halogen or cyano;
p is independently 0, 1, 2, 3, 4 or 5. }
{Where,
Z is C _1-6 alkyl, C _6-60 aryl, C _6-12 cycloalkyl, C _7-20 aralkyl, C _7-20 alkyl substituted aralkyl, or C _7-20 cycloalkyl substituted alkyl cycloalkyl,
Each L ′ is independently a direct bond or —O—CH ₂ —CH ₂ —,
Each R ₁₁ is independently hydrogen, methyl, ethyl, phenyl or C _6-12 cycloalkyl;
Each R ₁₂ is independently hydrogen, methyl, ethyl, phenyl or C _6-12 cycloalkyl;
q is 1, 2, 3 or 4. }   The composition further comprises a surfactant, a photopolymerization initiator, a crosslinking agent other than the crosslinking agent represented by formula (8), an acid generator, a radical generator, a substrate adhesion enhancer, or a mixture thereof. The composition according to any one of claims 6 to 13.   The composition according to any one of claims 6 to 14, wherein the photopolymerization initiator contained in the composition has a concentration of 0 to 1,000 ppm.   The composition according to any one of claims 6 to 15, wherein the acid generator contained in the composition has a concentration of 0 to 500 ppm and / or the radical generator has a concentration of 0 to 500 ppm. A carbon-containing film-forming composition comprising the composition according to claim 6. A carbon-containing underlayer film-forming composition comprising the carbon-containing film-forming composition according to claim 17. The composition according to any one of claims 6 to 16 is applied to the upper direction of the substrate,
A method for producing a carbon-containing film by curing the composition.   The method for producing a carbon-containing film according to claim 19, wherein the condition for curing the composition comprises irradiating ultraviolet rays having a wavelength of 10 to 380 nm.   The method for producing a carbon-containing film according to claim 20, wherein the wavelength of the ultraviolet light is 10 to 200 nm. A carbon-containing film is produced by the method according to any one of claims 19 to 21,
Laminating a photoresist composition in an upward or downward direction of the carbon-containing film,
Curing the photoresist composition to form a photoresist layer;
Exposing the substrate coated with the photoresist layer;
Developing the exposed substrate to form a resist pattern;
Etching using the resist pattern as a mask,
A method for manufacturing a semiconductor, comprising processing a substrate.   The semiconductor manufacturing method according to claim 22, further comprising forming a wiring on the processed substrate.