JP2011122081A - Thermosetting film-forming composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film-forming composition to be used in liquid crystal displays, recording materials for hard discs, solid imaging elements, solar cell panels light-emitting diodes, organic luminescent devices, luminescent films, fluorescent films, MEMS, actuators, antireflective materials, resists, resist lower layer films, resist upper layer films or templates (molds) for nanoimprinting use. <P>SOLUTION: The film-forming composition comprises a block copolymer comprising: a polymer chain (A) including a monomer (a) as a structural unit, and adjacent at least one polymer chain (B) including a monomer (b) different from the monomer (a) as a structural unit; a crosslinking agent; and an organic solvent. In the composition, the kinds of blocks present in the block copolymer are 2 or 3; and the number of the blocks present in the block copolymer is 2 or 3. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention has at least one of refractive index, absorption coefficient, alkali dissolution rate, solvent dissolution rate, plasma etching rate, elastic modulus, dielectric constant, conductivity, surface resistance value, thermal expansion coefficient, gas permeability, and magnetic susceptibility. The present invention relates to a thermosetting self-assembled film composition for electronic materials comprising a block copolymer having two local property distributions.
Specifically, liquid crystal displays, recording materials for hard disks, solid-state imaging devices, solar cell panels, light-emitting diodes, organic light-emitting devices, luminescent films, fluorescent films, MEMS, actuators, antireflection materials, resists, resist underlayer films, resist upper layer films The present invention also relates to a thermosetting self-assembled film forming composition for forming an electronic material used for a template (mold) for nanoimprinting by thermal firing. Moreover, it is related with the formation method of the self-organization film | membrane using the said thermosetting self-organization film formation composition, and the formation method of a process pattern.

Thermosetting self-assembled films with nanoscale repeat structures are known to have different properties from normal homogeneous films, and self-assembled films with nanoscale repeat structures using block copolymers Has been proposed.

  The properties of mixing organic photochromic materials in non-curable polystyrene / poly (methyl methacrylate) copolymers have been reported (see Non-Patent Document 1).

Nano patterning characteristics using plasma etching using non-curable polystyrene / poly (methyl methacrylate) copolymer have been reported (see Non-Patent Document 2).
Non-Patent Document 3 reports nano-patterning characteristics using non-curable polystyrene / poly (methyl methacrylate) copolymers.
However, development of a thermosetting (crosslinkable) self-assembled film containing a block copolymer has not been made (see Non-Patent Document 3).

  A thin film coating composition using a block polymer comprising a polymer chain having a fluorine-containing vinyl monomer unit and a polymer chain having at least a vinyl monomer unit having a silyl group is disclosed (see Patent Document 1). ).

  A pattern forming method for forming a pattern in a block polymer layer by regularly arranging a plurality of segments constituting the block polymer is disclosed (see Patent Document 2).

JP2007-284623 JP2009-234114A

Toshiko Mizokuro et. al., Japan Journal of Applied Physics 42, L983 (2003) Koji Asakawa et. al., Japan Journal of Applied Physics 41, 6112 (2002). Rachel A. Segalaman, Materials Science and Engineering R48, 191 (2005)

In the method using a non-cured (non-crosslinkable) self-assembled film containing a block copolymer, it is difficult to coat the upper layer by spin coating. Even when a dissolution preventing film is deposited and laminated one layer at a time to form a multilayer structure, the procedure is particularly troublesome, particularly when different types of materials are used. In addition, since there are materials with a crystal structure that cannot be easily peeled off and materials that cannot be formed into a film, materials to which these methods can be applied are limited.
Furthermore, when used as a resist lower layer film, it is mixed with the resist solution applied to the upper layer, and the target patterning cannot be performed.
In view of the above problems, the present invention has an object to provide a thermosetting self-assembled film composition for use in electronic materials and a method for forming a resist pattern using the same.
Furthermore, the thermosetting self-assembled film forming composition of the present invention includes a semiconductor, a liquid crystal display, a recording material for a hard disk, a solid-state imaging device, a solar cell panel, a light emitting diode, an organic light emitting device, a luminescent film, a fluorescent film, and a MEMS. An object of the present invention is to provide a thermosetting self-assembled film forming composition for curing and forming a resist underlayer film used as a lower layer of a resist in lithography of a pattern forming process used for an actuator by thermal baking.
Moreover, it is providing the formation method of the lower layer film | membrane used for the lower layer of a resist in the lithography of the pattern formation process using the said composition, and the formation method of the thermosetting self-organization film | membrane in an electronic material use.

As a first aspect of the present invention, a polymer chain (A) containing the monomer (a) as a unit structure and at least one polymer chain (B) adjacent to the monomer (a) containing a monomer (b) different from the monomer (a) as a unit structure A film-forming composition comprising a block copolymer comprising: a cross-linking agent; and an organic solvent,
As a second aspect, the film-forming composition according to the first aspect, wherein the type of block present in the block copolymer is 2 or 3,
As a third aspect, the film forming composition according to the first aspect or the second aspect, wherein the number of blocks present in the block copolymer is 2 or 3,
As a fourth aspect, the monomer (a) and the monomer (b) are acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, N, N-dimethylacrylamide, and quaternized dimethylaminoethyl methacrylate, respectively. , Methacrylamide, Nt-butylacrylamide, maleic acid and its hemiester, maleic anhydride, crotonic acid, itaconic acid, acrylamide, hydroxylated (meth) acrylate, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ether, maleimide, vinylpyridine , Vinylimidazole, heterocyclic vinyl compound, styrene sulfonate, allylic alcohol, vinyl alcohol, ester of acrylic acid or methacrylic acid having 1 to 13 carbon atoms, It is a compound selected from fluoroacrylate, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl propionate, α-methylstyrene, t-butylstyrene, isoprene, butadiene, cyclohexadiene, ethylene, propylene, and vinyltoluene. The film forming composition according to any one of the first aspect to the third aspect,
The film forming composition according to any one of the first to third aspects, wherein the monomer (a) and the monomer (b) are styrene and methyl methacrylate, styrene and isoprene, or styrene and butadiene. object,
As a sixth aspect, the film-forming composition according to any one of the first aspect to the fifth aspect, wherein the weight average molecular weight of the block copolymer is 1000 to 100,000.
As a seventh aspect, the film forming composition according to any one of the first aspect to the sixth aspect, further including a cross-linking polymer,
As an eighth aspect, the film formation according to any one of the first to seventh aspects, in which the crosslinking agent is an amino resin compound having at least two amino groups, a polyfunctional epoxy resin, or a dianhydride. Composition,
As a ninth aspect, liquid crystal displays, recording materials for hard disks, solid-state imaging devices, solar battery panels, light emitting diodes, organic light emitting devices, luminescent films, fluorescent films, MEMS, actuators, antireflection materials, resists, resist underlayer films, resists The film forming composition according to any one of the first to eighth aspects used for an upper layer film or a template (mold) for nanoimprinting,
As a tenth aspect, a method for forming a film by applying and baking the film-forming composition according to any one of the first to eighth aspects on a substrate,
As an eleventh aspect, the step of forming a lower layer film on the substrate, the step of processing the lower layer film by electron beam drawing or laser irradiation, and the film forming composition according to any one of the first to ninth aspects as a substrate A pattern forming method including a step of forming a film by applying and baking on the film, and a step of removing the film with a developer;
As a twelfth aspect, a step of forming a film by applying and baking the film forming composition according to any one of the first aspect to the eighth aspect on a substrate, coating the resist, and irradiating with ultraviolet rays or radiation A pattern forming method including a developing step;
As a thirteenth aspect, the step of forming a lower layer film on a substrate, the step of processing the lower layer film by electron beam drawing or laser irradiation, and the film forming composition according to any one of the first to ninth aspects as a substrate It is a pattern forming method including a step of coating on a film to form a film, and a step of coating a resist, irradiating with ultraviolet rays or radiation and developing.

The thermosetting self-assembled film obtained by heat-firing the film-forming composition of the present invention has a polymer chain (A) containing the monomer (a) as a unit structure and a monomer (b) different from the monomer (a). Is a block copolymer containing at least one polymer chain (B) containing as a unit structure. The polymer chain (A) has a refractive index, an absorption coefficient, an alkali dissolution rate, a solvent dissolution rate, a plasma etching rate, an elastic modulus, a dielectric constant, an electrical conductivity, a surface resistance value, and a thermal expansion coefficient with respect to the adjacent polymer chain (B). The gas permeability and magnetic susceptibility have different physical property values.
This block polymer (self-assembled) film is a patterning material, a liquid crystal display, an organic light emitting device, a luminescent film, a light scattering film used in a solar cell panel, a flexible cover film for an actuator, and a recording material for a hard disk. It can be used in mold materials used in manufacturing.

In particular, as a resist underlayer film used as a resist underlayer in lithography for pattern formation processes used for semiconductors, a self-assembled film is arranged on a processing substrate by an electron beam drawing apparatus or a laser irradiation apparatus in order to arrange it at a target position. Resist underlayer film in which alkali dissolution rate and solvent dissolution rate change (self-organization) by applying the (self-organization) film-forming composition of the present invention on a processed substrate after the step of making irregularities and hydrophobicity changes By aligning at the desired position and changing the alkali dissolution rate and solvent dissolution rate (self-organization), the resist is dissolved at the same time as the resist underlayer film, thereby increasing the dissolution contrast compared to the conventional resist underlayer film. Excellent in fine resist patterning properties and large dry etching compared to conventional resist under CF ₄ gas conditions. It is possible to form an excellent resist underlayer film that has a high speed and does not cause intermixing with the resist.
Since the block copolymer has different physical properties in the copolymer components (for example, A and B), if characteristic information is input in advance on the substrate, the block copolymer can also be arranged according to the information and exhibit patterning properties. If this property is used, a new patterning technique that can replace conventional lithography can be obtained.
If the copolymer components (for example, A and B) are incompatible with each other, an aggregate (higher order structure) is formed in the polymer chain portion of A and the polymer chain portion of B, and phase separation occurs. If there is information such as hydrophilicity and hydrophobicity on the substrate in advance, a pattern according to the information is formed.

Block copolymer and cross-linking agent comprising polymer chain (A) containing monomer (a) as a unit structure and at least one polymer chain (B) adjacent to monomer (b) different from monomer (a) as a unit structure And a film-forming composition containing an organic solvent.
The film-forming composition can have a solid content of 1 to 70 mass%, or 1 to 50 mass%, or 1 to 30 mass%. Solid content is the remaining ratio which remove | excluded the solvent from the film formation composition.
The proportion of the block copolymer in the solid content can be 30 to 100% by mass, or 50 to 100% by mass, or 50 to 90% by mass, or 50 to 80% by mass.
The film-forming composition tends to self-assemble due to the properties of the block copolymer, and can be a self-assembled film-forming composition.
The type of block present in the block copolymer can be 2 or 3. The number of blocks present in the block copolymer can be 2 or 3.
By changing the polymer chain (B), for example, the adjacent polymer chain (C) containing the monomer (c) as a unit structure can be used.

As the block polymer, patterns of AB, ABAB, ABA, ABC and the like are obtained.
As one of the methods for synthesizing a block copolymer, the polymerization process consists only of an initiation reaction and a growth reaction, and can be obtained by living radical polymerization or living cation polymerization without a side reaction that deactivates the growth terminal. The growth terminal can continue to maintain a growth active reaction during the polymerization reaction. By eliminating chain transfer, a polymer (A) having a uniform length can be obtained. By adding a different monomer (b) using the growing terminal of the polymer (A), polymerization proceeds under the monomer (b) to form a block copolymer (AB).
For example, when there are two types of blocks A and B, the polymer chain (A) and the polymer chain (B) have a molar ratio of 1: 9 to 9: 1, preferably 3: 7 to 5: 5. be able to.
Homopolymer A or B is a polymerizable compound having at least one reactive group capable of radical polymerization (vinyl group or vinyl group-containing organic group).
The weight average molecular weight Mn of the block copolymer used in the present invention is 1000 to 100,000, preferably 2000 to 10,000. If it is less than 1000, the applicability to the base substrate may be poor, and if it is 100,000 or more, the solubility in a solvent may be poor.

The monomer (a) and monomer (b) forming the block copolymer are, for example, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, N, N-dimethylacrylamide, and quaternized dimethylaminoethyl. Methacrylate, methacrylamide, Nt-butylacrylamide, maleic acid and its hemiester, maleic anhydride, crotonic acid, itaconic acid, acrylamide, hydroxylated (meth) acrylate, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ether, maleimide, vinyl Pyridine, vinylimidazole, heterocyclic vinyl compound, styrene sulfonate, allyl alcohol, vinyl alcohol, acrylic acid or methacrylate having 1 to 13 carbon atoms Selected from esters of phosphoric acid, fluoroacrylate, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl propionate, α-methylstyrene, t-butylstyrene, isoprene, butadiene, cyclohexadiene, ethylene, propylene, and vinyltoluene Compounds.
In the thermosetting (self-assembled) film-forming composition of the present invention, when a block polymer having no crosslinking reactive group is used, a polystyrene / poly (methyl methacrylate) copolymer, a polystyrene / polyisoprene copolymer, or polystyrene / Polybutadiene copolymer is preferred.

  The thermosetting (self-assembled) film-forming composition of the present invention includes, in addition to the block copolymer, solvent, crosslinkable compound, and crosslinking catalyst, if necessary, a light absorbing compound, a surfactant, and a hardness adjusting polymer. A compound, an antioxidant, a thermal polymerization inhibitor, a surface modifier, a defoaming agent, and the like can be added.

The thermosetting (self-assembled) film-forming composition of the present invention is usually obtained by dissolving or dispersing a block copolymer containing two homopolymer chains (A) and (B) in an organic solvent. Examples of the organic solvent include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents.
The thermosetting (self-assembled) film forming composition of the present invention further includes β-diketone, colloidal silica, colloidal alumina, organic polymer, surfactant, silane coupling agent, radical generator, triazene compound, Components such as alkali compounds may be added.

  Examples of the organic solvent used in the thermosetting (self-assembled) film-forming composition of the present invention include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2, Aliphatic hydrocarbon solvents such as 2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl Aromatic hydrocarbon solvents such as benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol , I-butanol, sec Butanol, t-butanol, n-pentanol, i-pentanol, 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-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenyl Monoalcohol solvents such as lucarbinol, diacetone alcohol, cresol; ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5 , Heptanediol-2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin and other polyhydric alcohol solvents; 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, trimethyl Ketone solvents such as nonanone, cyclohexanone, methylcyclohexanone, 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-ethyl butyl ether Ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di -N-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether Ether solvents such as dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-acetate Propyl, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, Cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl acetate Glycol monomethyl ether, 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 , Dipropylene glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, lactic acid S, such as ethyl, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate Tellurium solvents; including N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, etc. Nitrogen-based solvents: Sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone and the like can be mentioned.

  In particular, 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate is preferred from the viewpoint of storage stability of the solution of the composition.

  A catalyst may be used when the thermosetting (self-organized) film forming composition is thermoset. Examples of the catalyst used at this time include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonate) ) Titanium, di-t-butoxy bis Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy Tris (acetylacetonato) titanium, mono-sec-butoxytris (acetylacetonato) titanium, mono-t-butoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethyl) Acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di- i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) Acetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tris (Ethyl acetoacetate Tate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium, and other titanium chelate compounds; triethoxy mono (acetylacetonato) zirconium, tri- n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri-s c-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, Di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis ( Acetylacetonato) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconi Mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) Zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl aceto) Acetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethylacetoa Cetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec- Butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono -I-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirco , Mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonato) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonato) aluminum and tris (ethylacetoacetate) aluminum; Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid , Butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid Monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

  Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, Examples thereof include diazabicycloundecene and tetramethylammonium hydroxide. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and titanium chelate compounds and organic acids are more preferable. These may be used alone or in combination of two or more.

Furthermore, in order to improve adhesion, wettability to the base substrate, flexibility, flatness, etc., the above-mentioned block copolymer is used by using a polymer obtained by radical polymerization of the following polymerizable compound which does not contain a block copolymer if necessary. It can be mixed with a thermosetting (self-assembled) film-forming composition. The mixing ratio may be 10 to 1000 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the block copolymer.
As the polymer not containing the block polymer, a cross-linking polymer can be used. Examples thereof include polymers such as hydroxystyrene, tris- (2-hydroxylethyl) -isocyanuric acid, and tris- (2-hydroxylethyl) -isocyanuric acid ester (meth) acrylate.

  Polymers that do not contain block polymers include, as specific examples of polymerizable compounds other than those described above, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) pheny ] Propane, 3-phenoxy-2-propanoyl acrylate, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate Glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Here, for example, ethylene glycol di (meth) acrylate means ethylene glycol diacrylate and ethylene glycol dimethacrylate.

Examples of the polymerizable compound having an ethylenically unsaturated bond include a urethane compound, a polyvalent epoxy compound and a hydroxyalkyl unsaturated carboxylic acid which can be obtained by reacting a polyvalent isocyanate compound with a hydroxyalkyl unsaturated carboxylic acid ester compound. There can also be mentioned compounds obtainable by reaction with ester compounds, diallyl ester compounds such as diallyl phthalate, and divinyl compounds such as divinyl phthalate.
Examples of the polymerizable compound not containing a block polymer and having a vinyl ether structure include vinyl-2-chloroethyl ether, vinyl-normal butyl ether, 1,4-cyclohexanedimethanol divinyl ether, vinyl glycidyl ether, bis (4- (vinyl Roxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, diethylene glycol divinyl ether, tris (4-vinyloxy) butyl trimellrate, bis (4- (vinyloxy) butyl) terephthalate, bis (4 -(Vinyloxy) butyl isophthalate, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, tetraether Lenglycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylol ethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol Examples thereof include trivinyl ether and cyclohexane dimethanol divinyl ether.

In the present invention, a crosslinking agent can be used. Examples of the crosslinking agent include nitrogen-containing compounds having a nitrogen atom substituted with a hydroxymethyl group or an alkoxymethyl group. It is a nitrogen-containing compound having a nitrogen atom substituted with a group such as a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a butoxymethyl group, and a hexyloxymethyl group. The cross-linking agent can form a cross-link with a block copolymer or a cross-linking polymer, but when the cross-linking group does not exist in the block copolymer, it can form a matrix by self-crosslinking and can immobilize the block copolymer.
Specifically, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3 -Bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4, And nitrogen-containing compounds such as 5-dihydroxy-2-imidazolinone and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.

  As cross-linking agents, methoxymethyl type melamine compounds (trade names: Cymel 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade names: Mycoat 506, Mycoat 508) , Compounds such as glycoluril compounds (trade names Cymel 1170, Powder Link 1174), methylated urea resins (trade names UFR65), butylated urea resins (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), Examples include commercially available compounds such as urea / formaldehyde resins (high condensation type, trade names Beccamin J-300S, Beccamin P-955, and Beckamine N) manufactured by Dainippon Ink & Chemicals, Inc. Further, it may be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. The high molecular weight compound manufactured from the melamine compound (brand name Cymel 303) and the benzoguanamine compound (trade name Cymel 1123) described in the patent 6323310 can also be mentioned.

As the crosslinking agent, acrylamide compounds or methacrylamides substituted with hydroxymethyl groups or alkoxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. Polymers produced using the compounds can be used. Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethylmethacrylamide. And a copolymer of benzyl methacrylate and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
As the crosslinking agent, only one kind of compound can be used, or two or more kinds of compounds can be used in combination.
The crosslinking agent can be used at 1 to 50 parts by weight, or 3 to 50 parts by weight, or 5 to 50 parts by weight, or 10 to 40 parts by weight, or 20 to 30 parts by weight with respect to 100 parts by weight of the block copolymer. . By changing the type and content of the crosslinking agent, the elastic modulus and the step coverage can be adjusted.

Furthermore, a crosslinking catalyst capable of generating cations and radicals by thermal baking (heating) and causing a thermal polymerization reaction of the thermosetting (self-organized) film of the present invention can be included. By using a crosslinking catalyst, the reaction of the crosslinking agent is promoted.
As the crosslinking catalyst, acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid can be used. .
An aromatic sulfonic acid compound can be used as the crosslinking catalyst. Specific examples of the aromatic sulfonic acid compound include p-toluenesulfonic acid, pyridinium-p-toluenesulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, and 1-naphthalenesulfonic acid. And pyridinium-1-naphthalenesulfonic acid. A crosslinking catalyst can use only 1 type and can also be used in combination of 2 or more type.

The crosslinking catalyst is 0.01 to 10 parts by mass, or 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.3 to 2 parts by mass, or 0.5 to 100 parts by mass of the block copolymer. It can be used at ˜1 part by mass. If the amount of the crosslinking catalyst is less than this, the crosslinking reaction does not proceed sufficiently, and the hardness and wear resistance of the resulting lower layer film may be insufficient. If the amount of the crosslinking catalyst is larger than this, curing may occur only in the vicinity of the surface of the lower layer film, and it may be difficult to completely cure the lower layer film. Furthermore, if the amount of the crosslinking catalyst is larger than this, the amount of sublimation of the crosslinking catalyst increases, which causes the inside of the firing furnace to be contaminated.
When the thermosetting (self-assembled) film-forming composition of the present invention is used as a resist underlayer film (antireflection film) for semiconductor lithography, as a light absorbing compound, a photoresist layer provided on the underlayer film It can be used without particular limitation as long as it has high absorptivity for light in the photosensitive characteristic wavelength region of the photosensitive component, and can prevent standing wave generated by reflection from the substrate or irregular reflection due to a step on the substrate surface. it can.

  Examples of such light-absorbing compounds include benzophenone compounds, benzotriazole compounds, azo compounds, naphthalene compounds, anthracene compounds, anthraquinone compounds, triazine compounds, triazine trione compounds, quinoline compounds, and the like. Naphthalene compounds, anthracene compounds, triazine compounds, and triazine trione compounds are used. And it is preferable that a light absorbing compound can react with the component which has the said hydroxyl group or epoxy group, Therefore, the compound which has a carboxyl group or a phenolic hydroxyl group is used preferably. Specific examples include, for example, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1-naphthol, 2-naphthol, naphthylacetic acid, 1-hydroxy-2-naphthalenecarboxylic acid, 3-hydroxy-2-naphthalenecarboxylic acid, 3,7-dihydroxy-2-naphthalenecarboxylic acid, 6-bromo-2-hydroxynaphthalene, 2,6-naphthalenedicarboxylic acid, 9-anthracenecarboxylic acid, 10-bromo-9-anthracenecarboxylic acid, anthracene-9,10 -Dicarboxylic acid, 1-anthracenecarboxylic acid, 1-hydroxyanthracene, 1,2,3-anthracentriol, 2,7,9-anthracentriol, benzoic acid, 4-hydroxybenzoic acid, 4-bromobenzoic acid, 3- Iodobenzoic acid, 2,4,6-tribromophenol 2,4,6-tribromoresorcinol, 3,4,5-triiodobenzoic acid, 2,4,6-triiodo-3-aminobenzoic acid, 2,4,6-triiodo-3-hydroxybenzoic acid, 2, Examples include 4,6-tribromo-3-hydroxybenzoic acid.

  Further, by adding a surfactant, it is possible to suppress the occurrence of pinholes and installations and to improve the applicability of the thermosetting (self-organized) film forming composition. Examples of the surfactant include polyoxyethylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether and the like. Oxyethylene alkyl allyl ether compounds, polyoxyethylene / polyoxypropylene block copolymer compounds, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, sorbitan trisoleate and other sorbitan fatty acid ester compounds, polyoxy Ethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxye Polyoxyethylene sorbitan fatty acid ester compounds such as alkylene sorbitan monostearate and polyoxyethylene sorbitan tristearate and the like. In addition, trade names F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names MegaFuck F171, F173, R-08, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), trade names Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and other fluorosurfactants and organosiloxane polymers KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be raised. When a surfactant is used, the addition amount is, for example, 0.1 to 5 parts by mass or 0.5 to 2 parts by mass with respect to 100 parts by mass of the block copolymer.

Further, a hardness adjusting polymer compound can be added. There is no restriction | limiting in particular as a hardness adjustment high molecular compound, The various polymer compound whose weight average molecular weight is about 1000-1 million can be used. Examples thereof include acrylate polymers, methacrylate polymers, novolak polymers, styrene polymers, polyamides, polyamic acids, polyesters and polyimides having a benzene ring, naphthalene ring or anthracene ring. When the hardness adjusting polymer compound is used, the addition amount is, for example, 0.1 to 50 parts by mass with respect to 100 parts by mass of the block copolymer.
In the present invention, a thermosetting (self-organizing) film forming composition is applied on a processed substrate to form a coating film, and the coating film is irradiated with light or thermally baked (self-organizing) film. Including the process of forming, liquid crystal display, recording material for hard disk, solid-state imaging device, solar cell panel, light emitting diode, organic light emitting device, luminescent film, fluorescent film, MEMS, actuator, antireflection material, resist, resist underlayer film, A resist upper layer film or a template (mold) for nanoimprinting is manufactured.

In the present invention, before the thermosetting (self-organizing) film is formed, a case where a lower layer film for storing pattern information is applied by electron beam drawing or laser irradiation (case 2) and a case where they are not applied (case 1). In cases 1 and 2, the resist is coated on the thermosetting (self-assembled) film and lithography is performed (case 4), and the resist is not coated and lithography is performed (case 4). Case 3). Since the block copolymer itself used in the present invention has the ability to form a pattern by self-organization, a resist may not necessarily be required in order to utilize the effect.
Hereinafter, the use of the thermosetting (self-organizing) film forming composition of the present invention will be described.
Semiconductors, liquid crystal displays, recording materials for hard disks, solid-state imaging devices, solar cell panels, light emitting diodes, organic light emitting devices, luminescent films, fluorescent films, MEMS, actuators, antireflection materials, resists, resist underlayer films, resist upper layer films, Or a processed substrate (for example, a silicon / silicon dioxide coated substrate, a silicon wafer substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, a low dielectric constant material (low−)) used in the manufacture of a template (mold) for nanoimprinting k material) is coated on the coated substrate, etc.) by a suitable coating method such as spinner, coater, spray, ink jet or the like to form a coating film by applying the thermosetting (self-organizing) film forming composition of the present invention. Then, before applying the (self-assembled) film, a lower layer film (BrushLayer, Migaku Layer) for inputting pattern information due to unevenness or surface energy change caused by electron beam or laser irradiation can be applied as necessary. .

When a thermosetting (self-assembled) film-forming composition containing a solvent is used, it is preferable to provide a drying step. The drying process is not particularly limited unless it is a method of heating at a high temperature. This is because when heated at a high temperature (for example, a temperature of 300 ° C. or higher), sublimation or the like of the solid content contained in the thermosetting (self-assembled) film occurs, and the device may be contaminated. The drying step can be performed, for example, by heating the substrate at 50 to 100 ° C. for 0.1 to 10 minutes on a hot plate. For example, it can carry out by air-drying at room temperature (about 20 degreeC).
In addition, when the thermosetting (self-organizing) film forming composition of the present invention is used as a resist underlayer film (antireflection film), it is applied and formed on the thermosetting (self-organizing) film of the present invention. The photoresist is not particularly limited as long as it is sensitive to light used for exposure, and either a negative type or a positive type photoresist can be used. A positive photoresist comprising a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist comprising a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, and an acid. Chemically amplified photoresist comprising a low molecular weight compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, a binder and an acid having a group that decomposes with acid to increase the alkali dissolution rate There are chemically amplified photoresists composed of a low-molecular compound and a photoacid generator that decompose and increase the alkali dissolution rate of the photoresist.

For example, trade names PFi-58 and PFi-88 manufactured by Sumitomo Chemical Co., Ltd., trade names iP5200, iP5700, TDMR-AR80 manufactured by Tokyo Ohka Kogyo Co., Ltd., and trade name S-1808 manufactured by SHIPLEY are listed.
Next, exposure is performed through a predetermined mask. For exposure, ArF (wavelength 193 nm), KrF (wavelength 248 nm), i-line (wavelength 365 nm), g-line (wavelength 432 nm), or the like can be used. After exposure, post-exposure heating (PEB: Post Exposure Bake) can be performed as necessary.
Next, development is performed with an alkaline developer. Thereby, for example, when a positive photoresist is used, the exposed portion of the photoresist and the lower layer antireflection film in the lower layer portion are removed by development.
The developer used in the present invention is, for example, an alkaline developer, such as an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, or a hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline. Examples include aqueous solutions of quaternary ammonium and alkaline aqueous solutions such as aqueous amine solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 ° C. to 50 ° C. and a time of 10 to 300 seconds.

When the film formed from the thermosetting (self-assembled) film-forming composition of the present invention is used as a photosensitive antireflection film for the resist lower layer, 2.38% by mass of water which is widely used as an alkaline developer. Development can be easily performed at room temperature using an aqueous tetramethylammonium oxide solution.
The thermosetting (self-assembled) film forming composition of the present invention comprises a layer for preventing an interaction between a semiconductor substrate and a photoresist, a material used for the photoresist, or a substance generated upon exposure to the photoresist. Reduces the poisoning effect of the photoresist layer by the layer that has the function to prevent adverse effects on the substrate, the layer that prevents the diffusion of the material generated from the substrate during heating and baking to the upper layer photoresist, and the semiconductor substrate dielectric layer It can also be used as a barrier layer.

Before applying the (self-assembled) film-forming composition using the block polymer of the present invention on the processed substrate, the lower layer film (organic film) is formed on the processed substrate in advance to pattern the block polymer into a cylinder shape. Pattern information can be input.
In addition, in order to arrange the pattern in the target position in the lower layer film (organic film) on the processed substrate, ultraviolet rays or radiation is irradiated so as to overlap the arrangement position, thereby causing irregularities and non-surface energy (hydrophilic / hydrophobic) changes. Thus, the polymer chain (A) component and the polymer chain (B) component of the (self-assembled) film-forming composition using the block polymer of the present invention can be arranged at desired positions, respectively.
Then, arrange the film (under the resist underlayer that self-assembles) whose alkali dissolution rate or solvent dissolution rate changes at the target position, form the resist, and irradiate the resist with ultraviolet rays or radiation so that it overlaps the array position. By developing, the resist is dissolved at the same time as the self-assembled resist underlayer film in which the alkali dissolution rate and the solvent dissolution rate change, so that high-contrast development can be performed and an excellent resist pattern can be formed.
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by this.

Example 1
24.03 g of propylene glycol monomethyl ether, 24.03 g of cyclohexanone, polystyrene / poly (methyl methacrylate) copolymer (made by Otsuka Chemical Co., Ltd., trade name PMMA-b-PS (Lot8E99) Mw 70000, polystyrene / poly (methyl methacrylate)) Polymer ratio: polystyrene 50 mol%, poly (methyl methacrylate 50 mol%) 0.9 g, polyhydroxystyrene (manufactured by Maruzen Petrochemical, trade name Marcalinker MS-4, weight average molecular weight Mw 9700, number average molecular weight Mn 4600) 0.30 g , 0.27 g of tetramethoxymethyl glycoluril (trade name Powder Link 1174, manufactured by Mitsui Cytec Co., Ltd.), 0.014 g of pyridinium-p-toluenesulfonic acid and surfactant R- 0 (Dainippon Ink Chemical Co., Ltd.) 0.0030 g was added to make a 10% by mass solution, followed by filtration using a polyethylene microfilter having a pore size of 0.05 μm, and a thermosetting self-assembled film forming composition. A solution of was prepared.

Example 2
24.03 g of propylene glycol monomethyl ether, 24.03 g of cyclohexanone, polystyrene / poly (methyl methacrylate) copolymer (made by Otsuka Chemical Co., Ltd., trade name PMMA-b-PS (Lot7J74) Mw 70000, polystyrene / poly (methyl methacrylate)) Polymer ratio: polystyrene 30 mol%, poly (methyl methacrylate 70 mol%) 0.9 g, polyhydroxystyrene (manufactured by Maruzen Petrochemical, trade name Marcalinker MS-4, weight average molecular weight Mw 9700, number average molecular weight Mn 4600) 30 g, tetramethoxymethyl glycoluril (trade name Powder Link 1174 manufactured by Mitsui Cytec Co., Ltd.) 0.27 g, pyridinium-p-toluenesulfonic acid 0.014 g and surfactant R 30 (Dainippon Ink Chemical Co., Ltd.) 0.0030 g was added to make a 10% by mass solution, followed by filtration using a polyethylene microfilter having a pore size of 0.05 μm, and a thermosetting self-assembled film forming composition. A solution of was prepared.

Comparative Example 1
24.03 g of propylene glycol monomethyl ether, 24.03 g of cyclohexanone, 1.20 g of polyhydroxystyrene (manufactured by Maruzen Petrochemical, trade name Marcalinker MS-4, weight average molecular weight Mw 9700, number average molecular weight Mn 4600), tetramethoxymethyl glycoluril ( Mitsui Cytec Co., Ltd., trade name powder link 1174) 0.27 g, pyridinium-p-toluenesulfonic acid 0.014 g and surfactant R-30 (Dainippon Ink Chemical Co., Ltd.) 0.0030 g were added, After preparing a 10% by mass solution, the solution was filtered using a polyethylene microfilter having a pore size of 0.05 μm to prepare a solution of a thermosetting self-assembled film composition.

(Elution test for resist solvent)
The solution of the thermosetting self-assembled film composition obtained in Example 1, Example 2, and Comparative Example 1 was applied onto a semiconductor substrate (silicon wafer substrate) by a spinner to form a coating film. In order to remove the solvent and dry the coating film, the film was heated on a hot plate at 120 ° C. for 0.5 minutes and then at 200 ° C. for 1.5 minutes to obtain a thermosetting self-assembled film composition (film thickness 102 nm). ) Was formed. Next, these thermosetting self-assembled films were immersed in cyclohexanone, ethyl lactate, propylene glycol monomethyl ether, N, N-dimethylformamide, which are solvents used for the material to be applied to the upper layer, and Example 1 and Example 2 and the thermosetting self-assembled film obtained from the thermosetting self-assembled film composition obtained in Comparative Example 1 were confirmed to be insoluble in these solvents.

(Measurement of coating film surface roughness)
In the same manner as described above, a thermosetting self-assembled film was formed to a thickness of 102 nm on the silicon wafer substrate from the solutions of the thermosetting self-assembled film compositions obtained in Example 1, Example 2, and Comparative Example 1, respectively. Formed with. The coating film surface roughness (surface roughness) was measured with an atomic force microscope (AFM / Atomic Force Microscope, NanoNav SPI3800N + SPA400, microcantilever SI-DF40, manufactured by SII NanoTechnology Co., Ltd.) in the 2 μm × 2 μm region. The maximum height difference (unit: nm) and the average roughness (unit: nm) of the unevenness were evaluated, and the values are shown in Table 1.
The maximum height difference by AFM measurement and the average roughness have a good correlation with the signal intensity of light scattering, and are detected as haze by inspection with a particle counter or a condenser lamp due to light scattering.
In Table 1, Example 1, Example 2, and Comparative Example 1 are the thermosetting self obtained from the thermosetting self-assembled film forming compositions of Example 1, Example 2, and Comparative Example 1. This is an evaluation of an organized membrane.

[Table 1]
Table 1
――――――――――――――――――――――――――――――――――
Maximum height difference of film surface irregularities Average roughness
(Nm) (nm)
Example 1 2.182 1.620
Example 2 1.876 1.477
Comparative Example 1 1.193 0.834
――――――――――――――――――――――――――――――――――
In the thermosetting self-assembled films obtained from Example 1 and Example 2, irregular irregularities were detected as compared with the film obtained from Comparative Example 1, which is considered to be an effect of containing a block copolymer. It is done.

  Therefore, when the resist is coated on the upper layer of the thermosetting self-assembled film obtained in Example 1 and Example 2, the resist is coated on the upper layer of the thermosetting self-assembled film obtained in Comparative Example 1. Compared to the case, the adhesion between the thermosetting self-assembled film and the resist was improved by the large surface area based on the large surface roughness.

The thermosetting self-assembled film forming composition of the present invention uses an information recognition function of a block copolymer contained therein, thereby enabling liquid crystal display, recording material for hard disk, solid-state imaging device, solar cell panel, light emitting diode, organic light emission. It can be used for a device, a luminescent film, a fluorescent film, a MEMS, an actuator, an antireflection material, a resist, a resist underlayer film, a resist overlayer film, or a nanoimprint template (mold).

Claims (13)

Block copolymer and cross-linking agent comprising polymer chain (A) containing monomer (a) as a unit structure and at least one polymer chain (B) adjacent to monomer (b) different from monomer (a) as a unit structure And a film-forming composition comprising an organic solvent. The film-forming composition according to claim 1, wherein the type of block present in the block copolymer is 2 or 3. The film-forming composition according to claim 1 or 2, wherein the number of blocks present in the block copolymer is 2 or 3. Monomer (a) and monomer (b) are acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, N, N-dimethylacrylamide, quaternized dimethylaminoethyl methacrylate, methacrylamide, N T-butylacrylamide, maleic acid and its hemiester, maleic anhydride, crotonic acid, itaconic acid, acrylamide, hydroxylated (meth) acrylate, diallyldimethylammonium chloride, vinylpyrrolidone, vinyl ether, maleimide, vinylpyridine, vinylimidazole, hetero Cyclic vinyl compound, styrene sulfonate, allyl alcohol, vinyl alcohol, acrylic acid or methacrylic acid ester having 1 to 13 carbon atoms, fluoroacrylate And styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl propionate, α-methylstyrene, t-butylstyrene, isoprene, butadiene, cyclohexadiene, ethylene, propylene, and vinyltoluene. The film-forming composition according to any one of claims 1 to 3. The film-forming composition according to any one of claims 1 to 3, wherein the monomer (a) and the monomer (b) are styrene and methyl methacrylate, styrene and isoprene, or styrene and butadiene. The film-forming composition according to any one of claims 1 to 5, wherein the block copolymer has a weight average molecular weight of 1,000 to 100,000. The film-forming composition according to any one of claims 1 to 6, further comprising a cross-linking polymer. The film-forming composition according to any one of claims 1 to 7, wherein the crosslinking agent is an amino resin compound having at least two amino groups, a polyfunctional epoxy resin, or a dianhydride. Liquid crystal display, recording material for hard disk, solid-state imaging device, solar cell panel, light emitting diode, organic light emitting device, luminescent film, fluorescent film, MEMS, actuator, antireflection material, resist, resist underlayer film, resist overlayer film, or nanoimprint The film forming composition according to any one of claims 1 to 8, which is used for a template (mold). A method for forming a film by applying the film-forming composition according to any one of claims 1 to 8 on a substrate and baking the composition. A step of forming a lower layer film on the substrate, a step of processing the lower layer film by electron beam drawing or laser irradiation, and applying and baking the film forming composition according to any one of claims 1 to 9 on the substrate. A pattern forming method including a step of forming a thin film and a step of removing the film with a developer. A step of forming a film by applying and baking the film-forming composition according to any one of claims 1 to 8 on a substrate, and a step of coating the resist and irradiating with ultraviolet rays or radiation to develop the film. Pattern formation method. A step of forming a lower layer film on the substrate, a step of processing the lower layer film by electron beam drawing or laser irradiation, and a film formed by applying the film forming composition according to any one of claims 1 to 9 on the substrate Forming a pattern, and a method of forming a pattern including a step of coating a resist, irradiating with ultraviolet rays or radiation and developing.