Composition for resist pattern metalation process

Abstract

To provide a composition that can improve collapse and roughness of a resist pattern by metalation of a resist in the resist pattern and also realize improvement of etching resistance; and to provide a resist pattern metalation method using the composition.SOLUTION: Provided is a composition for resist pattern metalation process, comprising (A) a component: at least one selected from a group consisting of a hydrolyzable silane compound (a2), a hydrolyzate (a3) of the hydrolyzable silane compound and a hydrolytic condensate (a4) of the hydrolyzable silane compound, (B) a component: an acid compound containing no carboxylic acid group (-COOH), and (C) a component: an aqueous solvent. A resist pattern metalation method provides a resist pattern in which the composition components penetrates into a resist using the composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for application onto a resist pattern in the process of development or onto a resist pattern after development by a lithography process, and more particularly to a composition for use in a metallization process in which the composition is permeated into a resist to obtain a resist pattern permeated with the components of the composition. [Background technology]

[0002] 2. Description of the Related Art In the field of semiconductor device manufacturing, a technique is widely used in which a fine pattern is formed on a substrate, and the substrate is processed by etching according to this pattern. Advances in lithography technology have led to the development of finer patterns, with KrF excimer lasers and ArF excimer lasers being used, and exposure techniques using electron beams (EB) and EUV (Extreme Ultraviolet) being investigated. Technologies such as directed self-assembly (DSA) are also being considered. In recent years, as patterns become finer, a phenomenon in which patterns collapse during the development and developer rinsing steps carried out after exposure of a resist in a lithography process has become a problem. As a means of preventing such pattern collapse, resists are being made thinner. However, the improvement in the etching resistance of the resist itself has not kept up with the trend toward thinner resists, and etching of hard masks and semiconductor substrates is becoming more difficult.

[0003] In light of this, a method has been proposed in which the exposed resist surface is developed with a developer, washed with a rinse solution, the rinse solution is replaced with a coating solution containing a polymer component, the resist pattern is coated with the polymer component, and then the resist is removed by dry etching, and a reverse pattern is formed with the replaced polymer component. For example, a pattern forming method is disclosed that includes a step of forming a resist film on a substrate, a step of selectively irradiating the resist film with energy rays to form a latent image in the resist film, a step of supplying a developer (alkaline developer) onto the resist film to form a resist pattern from the resist film on which the latent image has been formed, a step of supplying the rinsing liquid onto the substrate to replace the developer on the substrate with a rinsing liquid, a step of supplying a coating film material onto the substrate to replace the rinsing liquid on the substrate with a coating film material containing at least a part of the solvent and a solute different from the resist film, a step of volatilizing a solvent in the coating film material to form a coating film covering the resist film on the substrate, a step of receding at least a part of the surface of the coating film to expose at least a part of the upper surface of the resist pattern and to form a mask pattern composed of the coating film, and a step of processing the substrate using the mask pattern (Patent Document 1). Furthermore, a composition containing a water-soluble compound having an amino group and a compound containing a carboxylic acid group has been proposed as an aqueous composition for coating on a photoresist pattern (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2005-277052 A [Patent Document 2] Special Publication No. 2013-536463 Summary of the Invention [Problem to be solved by the invention]

[0005] The conventional technique disclosed in the above-mentioned Patent Document 1 removes the resist with a developing solution and a rinsing solution. When forming the pattern, there is a possibility that the pattern may collapse. Furthermore, when the composition disclosed in Patent Document 2 is applied onto a resist pattern, there are cases in which a uniform coating cannot be obtained.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition that can improve collapse and roughness of a resist pattern and improve etching resistance by metallizing the resist in a resist pattern, and a method for metallizing a resist pattern that uses the composition. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted extensive research in order to achieve the above-mentioned object, and as a result have found that a composition comprising a metal oxide, a hydrolyzable silane compound, or a hydrolysate or hydrolyzed condensate thereof, and an acid compound not containing a carboxylic acid group can be applied to a resist pattern during or after development, and then heated to obtain a resist pattern in which the components of the composition have permeated into the resist, and that the resist pattern in which the components of the composition have permeated can be prevented from collapsing and has improved etching resistance, thereby completing the present invention.

[0008] That is, the present invention provides, as a first aspect, Component (A): at least one selected from the group consisting of a metal oxide (a1), a hydrolyzable silane compound (a2), a hydrolyzate (a3) ​​of the hydrolyzable silane compound, and a hydrolyzed condensate (a4) of the hydrolyzable silane compound; Component (B): an acid compound that does not contain a carboxylic acid group (-COOH), and Component (C): Aqueous solvent The present invention relates to a composition for a resist pattern metallization process comprising: As a second aspect, the present invention relates to the composition according to the first aspect, in which the component (B) is an acid compound containing a sulfonic acid group (—SO3H). As a third aspect, the present invention relates to the composition according to the first or second aspect, in which the hydrolyzable silane compound (a2) includes at least one selected from the group consisting of hydrolyzable silanes (i) containing an organic group containing an amino group and hydrolyzable silanes (ii) containing an organic group having an ionic functional group. As a fourth aspect, the present invention relates to the composition according to the first or second aspect, in which the hydrolyzable silane compound (a2) includes at least one selected from the group consisting of hydrolyzable silanes represented by the following formula (1) and hydrolyzable silanes represented by the following formula (1-1): [R 1 a0 Si(R 2 ) 3-a0 〕 b0 R 3 c0 Formula (1) [〔Si(R 10 )2O〕 n0 Si(R 20 )2]R 30 2 types (1-1) (In formula (1), R 3 represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R 3 If there are multiple R 3 represents a group which may be bonded to the Si atom by forming a ring, R 1 represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and is bonded to a silicon atom via a Si-C bond; R 2 represents an alkoxy group, an acyloxy group, or a halogen group; a0 represents an integer of 0 or 1; b0 represents an integer from 1 to 3; c0 represents an integer of 1 or 2. In formula (1-1), R 10 and R20 are each a hydroxy group, an alkoxy group, an acyloxy group, or a halo group. Represents the gen group, R 30 represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R 30 If there are multiple R 30 represents a group which may be bonded to the Si atom by forming a ring, n0 represents an integer from 1 to 10. As a fifth aspect, the present invention relates to the first aspect or the composition according to the first aspect, in which the metal oxide (a1) is an oxide of at least one metal selected from the group consisting of titanium, hafnium, zirconium, germanium, aluminum, indium, tin, tungsten, and vanadium. According to a sixth aspect, the composition according to any one of the first to fifth aspects, in which the component (B) is contained in an amount of 0.5 to 15 parts by mass per 100 parts by mass of the component (A). As a seventh aspect, the present invention relates to the composition according to any one of the first to sixth aspects, further comprising a curing catalyst. According to an eighth aspect, the present invention relates to the composition according to any one of the first to seventh aspects, further comprising a surfactant. As a ninth aspect, the present invention relates to the composition according to any one of the first to eighth aspects, further comprising a photoacid generator. As a tenth aspect, a step of applying a resist solution onto a substrate; a step of exposing and developing the resist film; applying the composition according to any one of the first to ninth aspects to the resist pattern during or after the development to form a coating film on the resist pattern; and A step of heating the coating film to form a post-heating coating film, The present invention relates to a resist pattern metallization method that provides a resist pattern in which the components of the composition are permeated into the resist. As an eleventh aspect, a step of applying a resist solution onto a substrate; a step of exposing and developing the resist film; applying a composition according to any one of the first to ninth aspects to the resist pattern during or after the development to form a coating film in which the resist pattern is embedded; A step of heating the coating film to form a post-heating coating film; and A step of removing the coating film after heating with water or a developer, The present invention relates to a resist pattern metallization method that provides a resist pattern in which the components of the composition are permeated into the resist. As a twelfth aspect, the present invention includes a step of processing a substrate with a metallized resist pattern obtained by the method according to the tenth or eleventh aspect. The present invention relates to a method for manufacturing a semiconductor device. The present specification also includes the aspect of the invention described below in [1]. [1] Component (A): at least one selected from the group consisting of a hydrolyzable silane compound (a2), a hydrolyzate (a3) ​​of the hydrolyzable silane compound, and a hydrolyzed condensate (a4) of the hydrolyzable silane compound; Component (B): an acid compound that does not contain a carboxylic acid group (-COOH), and Component (C): Aqueous solvent Including, The hydrolyzable silane compound (a2) contains at least one selected from the group consisting of hydrolyzable silanes represented by the following formula (1) and hydrolyzable silanes represented by the following formula (1-1): [R 1 a0 Si(R 2 ) 3-a0 〕 b0 R 3 c0 Formula (1) [〔Si(R 10 )2O〕 n0 Si(R 20 )2]R 30 2 types (1-1) (In formula (1), R 3represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R 3 If there are multiple R 3 represents a group which may be bonded to the Si atom by forming a ring, R 1 represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and is bonded to a silicon atom via a Si-C bond; R 2 represents an alkoxy group, an acyloxy group, or a halogen group; a0 represents an integer of 0 or 1; b0 represents an integer from 1 to 3; c0 represents an integer of 1 or 2. In formula (1-1), R 10 and R 20 each represents a hydroxy group, an alkoxy group, an acyloxy group, or a halogen group, R 30 represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R 30 If there are multiple R 30 represents a group which may be bonded to the Si atom by forming a ring, n0 represents an integer from 1 to 10; The hydrolyzable silane compound (a2) contains the hydrolyzable silanes represented by the formulas (1) and (1-1) and another hydrolyzable silane compound (b) in a molar ratio of 3:97 to 100:0. Compositions for resist pattern metallization processes. Effect of the Invention

[0009] By applying the composition for resist pattern metallization process of the present invention to a resist pattern, a resist pattern can be formed in which the components of the composition have penetrated, thereby making it possible to suppress shape deterioration such as peeling or collapse of the resist pattern, improve line width roughness, and provide a resist pattern with improved etching resistance. According to the resist pattern metallization method of the present invention, after mask exposure, the resist surface is contacted with the composition during or after resist development, and heat-treated to coat the resist pattern, fill in gaps between the resist patterns, and prevent the resist pattern from collapsing. Then, by heating the coating, a resist pattern in which the composition components have permeated into the resist can be obtained, and as a result, the collapse of the resist pattern can be suppressed and the etching resistance can be improved. By using the resist pattern permeated with the composition components as an etching mask, the pattern can be transferred by etching to the layer below the resist pattern. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 shows optical microscope photographs (magnification: 50K) of the Si-containing film in the [4] Coatability evaluation, where FIG. 1(a) shows an optical microscope photograph of the Si-containing film obtained using the composition of Example 4-2, and FIG. 1(b) shows an optical microscope photograph of the Si-containing film obtained using the composition of Comparative Example 2. [Diagram 2] FIG. 2 shows TOF-SIMS data of an EUV resist film to which the composition of Example 4-2 was applied in a test to confirm the penetration of the Si component into the resist [5]. [Diagram 3] FIG. 3 is a scanning microscope photograph (magnification: 100K, top of pattern, cross section of pattern) of a resist pattern to which the composition of Example 4-1 was applied in [6] Preparation of a resist pattern by ArF exposure and metallization of the resist pattern (1). [Figure 4]FIG. 4 shows scanning microscope photographs (magnification: 100K, pattern top and pattern cross section) of a resist pattern of a comparative example in [6] Preparation of a resist pattern by ArF exposure and metallization of the resist pattern (1). [Diagram 5] FIG. 5 shows scanning microscope photographs (magnification: 100K, top of pattern, cross section of pattern) of a resist pattern and a transfer pattern to which the composition of Example 4-1 was applied after dry etching in [6] Preparation of a resist pattern by ArF exposure and metallization of the resist pattern (1). [Figure 6] FIG. 6 shows scanning microscope photographs (magnification: 100K, pattern top and pattern cross section) of a comparative resist pattern and a transferred pattern after dry etching in [6] Preparation of a resist pattern by ArF exposure and metallization of the resist pattern (1). [Figure 7] FIG. 7 is a diagram showing a scanning microscope photograph (magnification: 200K, upper part of pattern) of a resist pattern to which the composition of Example 4-1 was applied in the preparation of a resist pattern by EUV exposure and metallization of the resist pattern [8]. [Figure 8] FIG. 8 is a scanning microscope photograph (magnification: 200K, upper part of pattern) of a resist pattern of a comparative example in [8] preparation of a resist pattern by EUV exposure and metallization of the resist pattern. [Figure 9] FIG. 9 is a schematic diagram showing one embodiment of the resist pattern metallization method of the present invention. [Figure 10] FIG. 10 is a schematic diagram showing another embodiment of the resist pattern metallization method of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Composition for resist pattern metallization process] The present invention relates to a composition for resist pattern metallization process comprising the following components (A), (B), and (C): component (A): at least one selected from the group consisting of a metal oxide (a1), a hydrolyzable silane compound (a2), a hydrolyzate (a3) ​​of the hydrolyzable silane compound, and a hydrolysis condensate (a4) (also referred to as polysiloxane) of the hydrolyzable silane compound; component (B): an acid compound not containing a carboxylic acid group (-COOH); and component (C): an aqueous solvent. The composition for resist pattern metallization process of the present invention, as described below, can be applied to a resist pattern to obtain a resist pattern in which the components of the composition have permeated into the resist. In the present invention, "metallization" refers to a process in which the components in the composition, particularly the silane components or metal components in the composition (i.e., the component (A) contained in the composition: metal oxide (a1), hydrolyzable silane compound (a2), hydrolyzate (a3) ​​of the hydrolyzable silane compound, and hydrolysis condensate (a4) of the hydrolyzable silane compound) permeate into the resist pattern.

[0012] The concentration of the solid content in the composition can be, for example, 0.01 to 50 mass%, 0.01 to 20.0 mass%, or 0.01 to 10.0 mass%, based on the total mass of the composition. The solid content refers to components other than the solvent contained in the composition. The proportion of the component (A) which is at least one selected from the group consisting of the metal oxide (a1), the hydrolyzable silane compound (a2), the hydrolyzate (a3) ​​of the hydrolyzable silane compound, and the hydrolyzed condensate (a4) of the hydrolyzable silane compound in the solid content can be 50 to 99.9 mass %, or 80 to 99.9 mass %. The concentration of the component (B): the acid compound not containing a carboxylic acid group (-COOH) in the solid content can be 0.1% by mass to 50% by mass, or 0.1% by mass to 20% by mass.

[0013] The component (A) (at least one selected from the group consisting of metal oxide (a1), hydrolyzable silane compound (a2), hydrolyzate (a3) ​​of the hydrolyzable silane compound, and hydrolyzed condensate (a4) of the hydrolyzable silane compound) may be contained in an amount of 0.001 to 50.0 parts by mass relative to 100 parts by mass of the composition of the present invention. That is, the concentration of the component (A) in the composition may be usually 0.001 to 50.0% by mass, and preferably 0.001 to 20.0% by mass. The concentration of the component (B) (an acid compound not containing a carboxylic acid group (-COOH)) in the composition can be 0.0001 to 2.0% by mass.

[0014] [Component (A)] The component (A) is at least one selected from the group consisting of a metal oxide (a1), a hydrolyzable silane compound (a2), a hydrolyzate of the hydrolyzable silane compound (a3), and a hydrolyzed condensate of the hydrolyzable silane compound (a4) (also referred to as polysiloxane). In addition, when the component (A) is classified into the component (A1) as a metal oxide (a1) and the component (A2) as a hydrolyzable silane compound (a2), the hydrolyzate (a3) ​​of the hydrolyzable silane compound, and the hydrolysis condensate (a4) of the hydrolyzable silane compound, the component (A1) may be used alone, the component (A2) may be used alone, or the components (A1) and (A2) may be used in combination. When the components (A1) and (A2) are used in combination, the ratio thereof is usually (A1):(A2)=50:1 to 0.05:1 by mass ratio.

[0015] [Metal oxide (a1)] The metal oxide (a1) may be, for example, an oxide of at least one metal selected from the group consisting of titanium, hafnium, zirconium, germanium, aluminum, indium, tin, tungsten, and vanadium.

[0016] The above metal oxides can also be used as partial metal oxides. For example, hydrolysis condensates containing TiOx (titanium oxide, x=1 to 2), hydrolysis condensates containing HfOx (hafnium oxide, x=1 to 2), hydrolysis condensates containing ZrOx (zirconium oxide, x=1 to 2), hydrolysis condensates containing GeOx (germanium oxide, x=1 to 2), hydrolysis condensates containing AlOx (aluminum oxide, x=1 to 1.5), hydrolysis condensates containing InOx (indium oxide, x=1 to 1.5), hydrolysis condensates containing SnOx (tin oxide, x=1 to 3), hydrolysis condensates containing WOx (tungsten oxide, x=1 to 3), hydrolysis condensates containing VOx (vanadium oxide, x=1 to 2.5), etc. can be mentioned. Metal oxides or partial metal oxides can be obtained as hydrolysis condensates of metal alkoxides, and partial metal oxides may contain alkoxide groups.

[0017] [Hydrolyzable silane compound (a2), hydrolyzate (a3) ​​of the above hydrolyzable silane compound, and hydrolysis condensate (a4) of the above hydrolyzable silane compound] As the component (A), at least one selected from the group consisting of hydrolyzable silane compounds (a2), hydrolysates of the above hydrolyzable silane compounds (a3), and hydrolyzed condensates of the above hydrolyzable silane compounds (a4) can be used, and these can also be used as a mixture. As described later, the hydrolyzable silane compound (a2) can be hydrolyzed and the obtained hydrolyzate (a3) ​​can be condensed to obtain a hydrolyzed condensate (a4). When obtaining the hydrolyzed condensate (a4), a partial hydrolyzate in which hydrolysis is not completely completed or an unreacted silane compound can be mixed in the hydrolyzed condensate and used in the form of a mixture. The hydrolyzed condensate (a4) can be not only a polymer having a polysiloxane structure in which hydrolysis and condensation are completely completed, but also a polymer obtained by hydrolysis and condensation of a silane compound. It is a polymer having a polysiloxane structure in which condensation is partially incomplete, and the concept also includes those in which Si-OH groups remain.

[0018] As the hydrolyzable silane compound (a2), at least one selected from the group consisting of hydrolyzable silanes represented by the above formula (1) and the above formula (1-1) can be suitably used. The hydrolyzate (a3) ​​of the hydrolyzable silane compound corresponds to the hydrolyzate of the hydrolyzable silane compound (a2). The hydrolysis condensation product (a4) of the hydrolyzable silane compound is a condensation product of the hydrolysis product (a3) ​​of the hydrolyzable silane compound (a2). Note that (a4) is also called polysiloxane.

[0019] In formula (1), R 3 represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R 3 If there are multiple R 3 represents a group which may form a ring and be bonded to a Si atom. R 1 represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and is bonded to a silicon atom via a Si-C bond. R 2 represents an alkoxy group, an acyloxy group, or a halogen group. a0 represents an integer of 0 or 1; b0 represents an integer of 1 to 3; c0 represents an integer of 1 or 2.

[0020] In formula (1-1), R 10 and R 20 respectively represent a hydroxyl group, an alkoxy group, an acyloxy group, or a halogen group. R 30 represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R 30 If there are multiple R 30 represents a group which may form a ring and be bonded to a Si atom. n0 represents an integer of 1 to 10, and examples thereof include an integer of 1 to 5, or an integer of 1.

[0021] R in formula (1) 3 Or R in formula (1-1) 30 Examples of the organic group include an organic group containing an amino group. The amino group can be a primary amino group, a secondary amino group, or a tertiary amino group, and the molecule can have one or more (two or three) amino groups. These can be aliphatic amino groups, aromatic amino groups, etc.

[0022] In addition, R in formula (1) 3 Or R in formula (1-1) 30 Examples of the ionic functional group include an organic group having an ionic functional group. Examples of the ionic functional group include an ammonium cation, a carboxylate anion, a sulfonate anion, a nitrate anion, a phosphate anion, a sulfonium anion, and an alcoholate anion. Examples of the ammonium cation include primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium. The counter ions of the ionic functional groups are, as anions, chloride anion, fluoride anion, bromide anion, iodide anion, nitrate anion, sulfate anion, phosphate anion, formate anion, acetate anion, propionate anion, maleate anion, oxalate anion, malonate anion, methylmalonate anion, succinate anion, malate anion, tartrate anion, phthalate anion, citrate anion, glutarate anion, citrate anion, lactate anion, salicylate anion, methanesulfonate anion, Examples of the anion include an anion of octanoic acid, an anion of decanoic acid, an anion of octanesulfonic acid, an anion of decane sulfonic acid, an anion of dodecylbenzenesulfonic acid, an anion of phenolsulfonic acid, an anion of sulfosalicylic acid, an anion of camphorsulfonic acid, an anion of nonafluorobutanesulfonic acid, an anion of toluenesulfonic acid, an anion of cumenesulfonic acid, an anion of p-octylbenzenesulfonic acid, an anion of p-decylbenzenesulfonic acid, an anion of 4-octyl 2-phenoxybenzenesulfonic acid, an anion of 4-carboxybenzenesulfonic acid, etc. Also, the unit structure of a silane having an anionic functional group, a polysiloxane having an anionic functional group, or a polysiloxane having an anionic functional group for forming an intramolecular salt may be used. The counter ion of the ionic functional group may be a cation, such as a hydrogen cation, an ammonium cation, a sulfonium cation, an iodonium cation, a phosphonium cation, or an oxonium cation.

[0023] The alkyl group mentioned above may be a straight-chain or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl -n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group and 1-ethyl-2-methyl-n-propyl group.

[0024] Cyclic alkyl groups can also be used, and examples of such cyclic alkyl groups include those having 3 to 10 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethyl -cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group.

[0025] The above-mentioned aryl group includes, for example, an aryl group having 6 to 20 carbon atoms. Specific examples thereof include a phenyl group, an o-methylphenyl group, a m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, a m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-mercaptophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-aminophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β- Examples of the alkyl group include a naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0026] Furthermore, the above-mentioned halogenated alkyl groups and halogenated aryl groups include the above-mentioned alkyl groups and aryl groups in which one or more hydrogen atoms have been substituted with halogen atoms such as fluorine, chlorine, bromine, or iodine.

[0027] Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms. Specific examples include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 1 ...2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl, 1-ethyl-2-propenyl -propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl nyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1- pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl Examples of the aryl group include propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group. In addition, in the above alkenyl group, one or more hydrogen atoms may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine (halogenated alkenyl group).

[0028] Examples of the organic group having an epoxy group include glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and epoxycyclohexyl groups. Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group. Examples of the organic group having a methacryloyl group include methacryloylmethyl, methacryloylethyl, and methacryloylpropyl groups. Examples of the organic group having a mercapto group include an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, and an octyl mercapto group. Examples of the organic group having a cyano group include a cyanoethyl group and a cyanopropyl group.

[0029] R in the above formula (1) 2 And R in formula (1-1) 10 and R 20Examples of the alkoxy group in the formula (I) include alkoxy groups having a straight-chain, branched or cyclic alkyl moiety having 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2- Methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, Examples of cyclic alkoxy groups include 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy groups, and examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, cyclohexyloxy, 2-ethylcyclopropoxy, cyclohexyloxy, 1-methylcyclopentyloxy, 2-methylcyclopentyloxy, 3-methylcyclopentyloxy, 1-ethylcyclobutoxy, 2-ethylcyclobutoxy, 3-ethylcyclobutoxy, 1,2-dimethylcyclobutoxy, 1,3-dimethylcyclobutoxy, 2,2-dimethylcyclobutoxy, 2,3-dimethylcyclobutoxy, 2,4-dimethylcyclobutoxy, 3,Examples of the cyclopropoxy group include 3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group, and 2-ethyl-3-methyl-cyclopropoxy group.

[0030] R in the above formula (1) 2 And R in formula (1-1) 10 and R 20 The acyloxy group in the formula (I) is, for example, an acyloxy group having 1 to 20 carbon atoms. Specific examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, and an n-propylcarbonyloxy group. , i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, Examples of the alkylcarbonyloxy group include a 1,1-dimethyl-n-butylcarbonyloxy group, a 1,2-dimethyl-n-butylcarbonyloxy group, a 1,3-dimethyl-n-butylcarbonyloxy group, a 2,2-dimethyl-n-butylcarbonyloxy group, a 2,3-dimethyl-n-butylcarbonyloxy group, a 3,3-dimethyl-n-butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a 1,2,2-trimethyl-n-propylcarbonyloxy group, a 1-ethyl-1-methyl-n-propylcarbonyloxy group, a 1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group, and a tosylcarbonyloxy group.

[0031] R in the above formula (1) 2 , R in formula (1-1) 10 and R 20 And R in formula (3) 7 Examples of the halogen group in include fluorine, chlorine, bromine, and iodine.

[0032] In the hydrolyzable silane represented by formula (1), R 3 Non-limiting examples of silanes where is an organic group containing an amino group are shown below. In the following exemplary compounds, T represents a hydrolyzable group, such as an alkoxy group, an acyloxy group, or a halogen group, and specific examples of these groups include the above-mentioned examples. T is preferably an alkoxy group such as a methoxy group or an ethoxy group.

[0033] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0034] In the hydrolyzable silane represented by formula (1), R 3 is an organic group having an ionic functional group, and in the hydrolyzable silane represented by formula (1-1), R 30 Non-limiting examples of silanes in which is an organic group having an ionic functional group are shown below. In the following exemplary compounds, T represents a hydrolyzable group, such as an alkoxy group, an acyloxy group, or a halogen group, and specific examples of these groups include the above-mentioned examples. T is preferably an alkoxy group, such as a methoxy group or an ethoxy group. In the following formula, X and Y represent counter ions of the ionic functional group, and specific examples include the anions and cations as counter ions of the ionic functional groups described above. - , Y + are shown as monovalent anions and monovalent cations, respectively, but X - , Y + If the above ion examples indicate a divalent ion, the coefficient in front of the ion designation is multiplied by 1 / 2, and if the above examples indicate a trivalent ion, the coefficient in front of the ion designation is multiplied by 1 / 3.

[0035] [ka] [ka] [ka] [ka] [ka]

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[0036] The hydrolyzable silane compound (a2) in the composition of the present invention can be used in combination with at least one selected from the group consisting of hydrolyzable silanes represented by formula (1) and formula (1-1) and other hydrolyzable silane compounds (b). A preferred specific example of the hydrolyzable silane compound (b) used in the present invention is at least one selected from the group consisting of hydrolyzable silanes represented by the following formula (2) and hydrolyzable silanes represented by the following formula (3).

[0037] R 4 a Si(R 5 ) 4-a Formula (2) In formula (2), R 4 represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and is bonded to a silicon atom via a Si-C bond. R 5 represents an alkoxy group, an acyloxy group, or a halogen group. a represents an integer of 0 to 3.

[0038] [R 6 c Si(R 7 ) 3-c 〕2Z b Formula (3) In formula (3), R 6 represents an alkyl group. R 7 represents an alkoxy group, an acyloxy group, or a halogen group. Z represents an alkylene group or an arylene group. b represents an integer of 0 or 1; c represents an integer of 0 or 1;

[0039] R in Equation (2) 4 In the alkyl group, aryl group, halogenated alkyl group, halogen R is an organic group having an aryl group, an alkenyl group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group; 6 Specific examples of the alkyl group in R 1 The same as those mentioned above can be mentioned. R in Equation (2) 5 and R in formula (3) 7 Specific examples of the alkoxy group, acyloxy group and halogen group in R 2 The same as those mentioned above can be mentioned. The alkylene group or arylene group for Z includes the divalent organic groups derived from the above-mentioned alkyl group or aryl group. Specific examples of the alkylene group include, but are not limited to, a methylene group, an ethylene group, and a triethylene group. Specific examples of the arylene group include, but are not limited to, a paraphenylene group, a metaphenylene group, an orthophenylene group, and a biphenyl-4,4'-diyl group.

[0040] As the hydrolyzable silane compound (b), it is preferable to use a hydrolyzable silane represented by the formula (2).

[0041] As the hydrolyzable silane compound (a2), a hydrolyzable silane containing hydrolyzable silanes represented by formulas (1) and (1-1) and hydrolyzable silane (b) (at least one selected from the group consisting of hydrolyzable silanes represented by formulas (2) and (3)) in a molar ratio of hydrolyzable silanes represented by formulas (1) and (1-1):hydrolyzable silane (b)=3:97 to 100 to 0, or 30:70 to 100:0, or 50:50 to 100:0, or 70:30 to 100:0, or 97:3 to 100:0 can be used.

[0042] Specific examples of hydrolyzable silanes represented by formula (2) include, for example, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltrippropoxysilane, methyltriacetylsilane, methyltributoxysilane, methyltrippropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, and vinyltriethoxysilane. , vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and the like.

[0043] Specific examples of the hydrolyzable silane represented by formula (3) include, for example, methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxysilane, ethylene bistriethoxysilane, ethylene bistrichlorosilane, ethylene bistriacetoxysilane, propylene bistriethoxysilane, butylene bistrimethoxysilane, phenylene bistrimethoxysilane, phenylene bistriethoxysilane, phenylene bismethyldiethoxysilane, phenylene bismethyldimethoxysilane, naphthylene bistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, and bisethyl. Examples of the disilane include diethoxydisilane and bismethyldimethoxydisilane.

[0044] In addition to the above examples, the hydrolyzable silane compound (a2) may contain other hydrolyzable silanes besides the above examples, so long as the effects of the present invention are not impaired.

[0045] In a preferred embodiment of the present invention, the composition contains at least the hydrolysis condensation product (a4) of the hydrolyzable silane compound (a2). In this case, the composition may contain a non-condensed (partial) hydrolysis product or an unreacted silane compound in addition to the hydrolysis condensation product (a4) which is the polysiloxane. In a preferred embodiment of the present invention, the hydrolyzed condensate (a4) includes a hydrolyzed condensate obtained using at least one selected from the group consisting of hydrolyzable silanes represented by formula (1) and formula (1-1), at least one selected from the group consisting of hydrolyzable silanes represented by formula (2) and formula (3), and, if desired, other hydrolyzable silanes.

[0046] The hydrolysis condensate (also called polysiloxane) (a4) of the hydrolyzable silane compound (a2) may have a weight average molecular weight of, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation of the hydrolysis condensate in the composition, the weight average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less, and from the viewpoint of achieving both storage stability and coatability, the weight average molecular weight is preferably 700 or more, more preferably 1,000 or more. These weight average molecular weights are the molecular weights obtained by GPC analysis in terms of polystyrene, and the molecular weights obtained by GFC (aqueous GPC) analysis in terms of PEG / PEO. The GPC analysis can be carried out, for example, using a GPC apparatus (product name HLC-8220GPC, manufactured by Tosoh Corporation) and a GPC column (product names Shodex KF803L, KF802, KF801, manufactured by Showa Denko K.K.), setting the column temperature at 40°C, using tetrahydrofuran as an eluent (elution solvent), setting the flow rate (flow velocity) at 1.0 ml / min, and using polystyrene (manufactured by Showa Denko K.K.) as a standard sample. GFC analysis can be performed, for example, using a GFC apparatus (product name: RID-10A, manufactured by Shimadzu Corporation) and a GFC column (product name: Shodex SB-803HQ, manufactured by Showa Denko K.K.) at a column temperature of 40°C, using water and 0.5 M acetic acid / 0.5 M sodium nitrate aqueous solution as an eluent (elution solvent), at a flow rate (flow rate) of 1.0 ml / min, and using pullulan and PEG / PEO (manufactured by Showa Denko K.K.) as standard samples.

[0047] Examples of the hydrolysis condensation product preferably used in the present invention include, but are not limited to, the following. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0048] Examples of silsesquioxane (also called polysilsesquioxane) type polysiloxanes include those represented by formulae (2-1-4), (2-2-4), and (2-3-4). Formula (2-1-4) represents a ladder-type silsesquioxane, and n is 1 to 1000, or 1 to 200. Formula (2-2-4) represents a cage-type silsesquioxane. Formula (2-3-4) represents a random-type silsesquioxane. In formulas (2-1-4), (2-2-4), and (2-3-4), R represents an organic group containing an amino group, or an organic group having an ionic functional group, and is a group bonded to a silicon atom by a Si-C bond or a Si-N bond, and examples of these groups include those listed above.

[0049] The hydrolyzate (a3) ​​and hydrolyzed condensate (a4) of the hydrolyzed silane compound (a2) can be obtained by hydrolyzing and condensing the hydrolyzable silane compound (a2). The hydrolyzable silane compound (a2) used in the present invention has an alkoxy group, an acyloxy group, or a halogen group directly bonded to a silicon atom, that is, it includes an alkoxysilyl group, an acyloxysilyl group, or a halogenated silyl group, which are hydrolyzable groups. For the hydrolysis and condensation of these hydrolyzable groups, usually 0.5 to 100 mol, preferably 1 to 10 mol, of water is used per 1 mol of the hydrolyzable group. In addition, during the hydrolysis and condensation, a hydrolysis catalyst may be used for the purpose of promoting the hydrolysis and condensation, or the hydrolysis may be performed without using a hydrolysis catalyst. When a hydrolysis catalyst is used, the amount of the hydrolysis catalyst that can be used is usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, per 1 mol of the hydrolyzable group. The reaction temperature during hydrolysis and condensation is usually in the range of room temperature or higher and the reflux temperature at normal pressure of the organic solvent that can be used for hydrolysis, for example, 20 to 110° C., or for example, 20 to 80° C. Hydrolysis may be performed completely, i.e., all hydrolyzable groups may be converted to silanol groups, or may be performed partially, i.e., unreacted hydrolyzable groups may remain. That is, after the hydrolysis and condensation reaction, uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and / or monomers (hydrolyzable silane compounds) may remain in the hydrolysis condensate. As described above, in the present invention, the hydrolysis condensate is a polymer obtained by hydrolysis and condensation of a silane compound, but it is a concept that includes those that are not partially condensed and have remaining Si-OH groups. Examples of hydrolysis catalysts that can be used in hydrolysis and condensation include metal chelate compounds, Examples of the acid include organic acids, inorganic acids, organic bases, and inorganic bases. Examples are shown below, and these may be used alone or in combination of two or more.

[0050] Metal chelate compounds as hydrolysis catalysts include, for example, triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di -i-propoxy bis(acetylacetonate) titanium, di-n-butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, mono-n-propoxy tris(acetylacetonate) titanium, mono-i-propoxy tris(acetylacetonate) titanium, mono-n-butoxy tris(acetylacetonate) titanium, mono-sec-butoxy tris(acetylacetonate) titanium titanium acetate, titanium mono-t-butoxy tris(acetylacetonate), titanium tetrakis(acetylacetonate), titanium triethoxy mono(ethylacetoacetate), titanium tri-n-propoxy mono(ethylacetoacetate), titanium tri-i-propoxy mono(ethylacetoacetate), titanium tri-n-butoxy mono(ethylacetoacetate), titanium tri-sec-butoxy mono(ethylacetoacetate), titanium tri-t-butoxy mono(ethylacetoacetate), titanium diethoxy bis(ethoxy) di-n-propoxy bis(ethylacetoacetate) titanium, di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate) titanium,Titanium chelates such as mono-n-butoxy tris(ethylacetoacetate)titanium, mono-sec-butoxy tris(ethylacetoacetate)titanium, mono-t-butoxy tris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonato) tris(ethylacetoacetate)titanium, bis(acetylacetonato) bis(ethylacetoacetate)titanium, and tris(acetylacetonato) mono(ethylacetoacetate)titanium. Compounds; Triethoxy mono(acetylacetonate)zirconium, Tri-n-propoxy mono(acetylacetonate)zirconium, Tri-i-propoxy mono(acetylacetonate)zirconium, Tri-n-butoxy mono(acetylacetonate)zirconium, Tri-sec-butoxy mono(acetylacetonate)zirconium, Tri-t-butoxy mono(acetylacetonate)zirconium, Diethoxy bis(acetylacetonate)zirconium, Di-n-propoxy di-i-propoxy bis(acetylacetonate)zirconium, di-n-butoxy bis(acetylacetonate)zirconium, di-sec-butoxy bis(acetylacetonate)zirconium, di-t-butoxy bis(acetylacetonate)zirconium, monoethoxy tris(acetylacetonate)zirconium, mono-n-propoxy tris(acetylacetonate)zirconium, mono-i-propoxy tris (acetylacetonate)zirconium, mono-n-butoxy tris(acetylacetonate)zirconium, mono-sec-butoxy tris(acetylacetonate)zirconium, mono-t-butoxy tris(acetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxy mono(ethylacetoacetate)zirconium, tri-n-propoxy mono(ethylacetoacetate)zirconium, tri-i-propoxy mono(ethylacetoacetate, acetate)zirconium, tri-n-butoxy mono(ethylacetoacetate)zirconium, tri-sec-butoxy mono(ethylacetoacetate)zirconium, tri-t-butoxy mono(ethylacetoacetate)zirconium, diethoxy bis(ethylacetoacetate)zirconium, di-n-propoxy bis(ethylacetoacetate)zirconium, di-i-propoxy bis(ethylacetoacetate)zirconium, di-n-butoxy bis(ethylacetoacetate)zirconium, di-sec-butoxy bis(ethylacetoacetate)zirconium, di-t-butoxy bis(ethylacetoacetate)zirconium, monoethoxy tris(ethylacetoacetate)zirconium, mono-n-propoxy tris(ethylacetoacetate)zirconium, mono-i chelate compounds such as mono-propoxy tris(ethylacetoacetate)zirconium, mono-n-butoxy tris(ethylacetoacetate)zirconium, mono-sec-butoxy tris(ethylacetoacetate)zirconium, mono-t-butoxy tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato) tris(ethylacetoacetate)zirconium, bis(acetylacetonato) bis(ethylacetoacetate)zirconium, and tris(acetylacetonato) mono(ethylacetoacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonato) aluminum and tris(ethylacetoacetate) aluminum, but are not limited to these.

[0051] Examples of organic acids as hydrolysis catalysts include, but are not limited to, 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, mellitic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic 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 trifluoromethanesulfonic acid.

[0052] Examples of inorganic acids as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0053] Examples of organic bases as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide. Examples of inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

[0054] Among these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0055] As an example, in the present invention, the hydrolyzable silane compound (a2) (selected from the group consisting of hydrolyzable silanes represented by formula (1) and hydrolyzable silanes represented by formula (1-1)) The hydrolyzable silane (a3) ​​selected from the group consisting of hydrolyzable silanes represented by formula (2) and formula (3), and optionally other hydrolyzable silanes) is obtained by hydrolyzing the hydrolyzable silane compound (a2) in the presence of an alkaline substance, particularly in the presence of an organic base, and it is preferable to further condense the hydrolyzed silane to form a hydrolyzed condensate (a4) (polysiloxane). The alkaline substance here is either an alkaline catalyst added during the hydrolysis of the hydrolyzable silane, or an amino group present in the molecule of the hydrolyzable silane itself. When the alkaline substance is an amino group present in a hydrolyzable silane molecule, examples thereof include silanes containing an amino group in a side chain among the above-mentioned examples of the hydrolyzable silane compound (a4) represented by the above-mentioned formula (1) or formula (1-1). When an alkaline catalyst is added, the inorganic bases and organic bases described above as the hydrolysis catalyst are included, with the organic bases being particularly preferred. The hydrolyzate of the hydrolyzable silane is preferably one which has been hydrolyzed in the presence of an alkaline substance.

[0056] The composition may further contain a hydrolyzable silane, a hydrolyzate obtained by hydrolyzing the hydrolyzable silane in the presence of an alkaline substance, or a mixture thereof.

[0057] In addition, in the present invention, silsesquioxane obtained by hydrolyzing silane having three hydrolyzable groups can be used. This silsesquioxane is a hydrolysis condensate (a4) obtained by hydrolyzing and condensing silane having three hydrolyzable groups in the presence of an acidic substance. The acidic substance used here can be an acidic catalyst among the above-mentioned hydrolysis catalysts. The hydrolysis condensate (a4) may be a random-type, ladder-type or cage-type silsesquioxane.

[0058] In addition, when carrying out the hydrolysis and condensation, an organic solvent may be used as a solvent. Specific examples of such an organic solvent include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, and triethylbenzene. Aromatic hydrocarbon solvents such as benzene, di-i-propylbenzene, n-amylnaphthalene, and 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- Monoalcohol solvents such as 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, phenylmethylcarbinol, diacetone alcohol, and cresol; ethylene glycol, Polyhydric alcohol solvents such as 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, and glycerin; acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, etc. Ketone solvents such as 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 dibutyl ether, di ... ether solvents such as ethylene 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, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;Diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, i-propyl acetate, 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, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol mono Examples of suitable solvents include, but are not limited to, ester-based solvents such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents may be used alone or in combination of two or more.

[0059] After completion of the hydrolysis reaction, the reaction solution may be used as is or after dilution or concentration, and then neutralized as necessary, or treated with an ion exchange resin to remove the hydrolysis catalyst, such as an acid or a base, used in the hydrolysis and condensation. Before or after such treatment, by-products such as alcohol and water, and the hydrolysis catalyst used may be removed from the reaction solution by vacuum distillation or the like. The hydrolysis condensation product (a4) (polysiloxane) thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and this can be used as is in the process described below. It can be used as a composition for a resist pattern metallization process.

[0060] [(B): Acid compounds not containing a carboxylic acid group (-COOH)] The composition of the present invention contains an acid compound that does not contain a carboxylic acid group as component (B). The acid compound is preferably an acid compound containing a sulfonic acid group (-SO3H), such as methanesulfonic acid, octane sulfonic acid, decane sulfonic acid, dodecylbenzene sulfonic acid, phenolsulfonic acid, sulfosalicylic acid, camphorsulfonic acid, nonafluorobutanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, p-octylbenzenesulfonic acid, p-decylbenzenesulfonic acid, 4-octyl 2-phenoxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. The (B) component is preferably used in an amount of 0.5 to 15 parts by mass per 100 parts by mass of the (A) component.

[0061] [Component (C): Aqueous Solvent] The composition of the present invention contains an aqueous solvent as component (C). The aqueous solvent preferably contains water, and more preferably, the aqueous solvent is 100% water, i.e., consists of only water. In this case, the presence of trace amounts of organic solvents and the like contained in water as impurities when water is used intentionally as an aqueous solvent is not denied. Since the composition of the present invention is applied to a resist pattern, a solvent that may dissolve the resist pattern cannot be used. However, the composition of the present invention may contain a water-soluble organic solvent that is miscible with an aqueous solvent and does not dissolve the resist pattern, such as an alcohol-based solvent or an ether-based solvent. Examples of such solvents that do not dissolve the resist pattern include, but are not limited to, alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, and isobutyl alcohol; glycols such as ethyl cellosolve, butyl cellosolve, ethylene glycol, and diethylene glycol; glycol ethers such as propylene glycol monomethyl ether; and ethers such as tetrahydrofuran (THF). These water-soluble organic solvents may be used alone or in combination of two or more. The water-soluble organic solvent can also be used as a mixed solvent with water. In this case, the mixing ratio of water to the water-soluble organic solvent is not particularly limited, but for example, the mass ratio of water:water-soluble organic solvent is 0.1:99.9 to 99.9:0.1. In addition to the water-soluble organic solvent, an organic solvent that is poorly soluble in water or a hydrophobic organic solvent may be used in combination within a range that does not impair the effects of the present invention.

[0062] [Preparation of Composition] The composition for resist pattern metallization process of the present invention contains the above-mentioned components (A), (B) and (C). The composition can be produced by mixing the components (A) to (C) and, if desired, other components. In this case, a solution containing the component (A) (e.g., the hydrolysis-condensation product (a4)) may be prepared in advance, and this solution may be mixed with a solvent and other components. The order of mixing is not particularly limited. For example, the (B) and (C) components may be added to and mixed with a solution containing the (A) component (e.g., the hydrolysis-condensation product (a4) etc.), and other components may be added to the mixture, or a solution containing the (A) component (e.g., the hydrolysis-condensation product (a4) etc.), a solvent, and other components may be mixed simultaneously. In addition, during the production of the composition, or after all the components are mixed, the composition may be filtered using a submicrometer filter or the like.

[0063] In the composition for resist pattern metallization process of the present invention, the component (A) is a water-soluble When the hydrolysis condensate (a4) is contained, in particular for stabilizing the hydrolysis condensate contained therein, an inorganic acid, an organic acid, an alcohol, an organic amine, a photoacid generator, a metal oxide, a surfactant, or a combination thereof may be added. Even when a component other than (a4) is contained as the (A) component, the following components may be contained as long as the effects of the present invention are not impaired.

[0064] Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Examples of the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, salicylic acid, etc. Among these, oxalic acid and maleic acid are preferred. When these acids are added, the amount added may be 0.5 to 15 parts by mass per 100 parts by mass of the component (A). However, since the addition of an acid containing a carboxylic acid group (-COOH) can be a factor in deteriorating the coatability of the composition of the present invention, it is preferable that such an acid not be added to the composition of the present invention.

[0065] The alcohol is preferably one that is easily dispersed by heating after application, such as methanol, ethanol, propanol, i-propanol, butanol, etc. When alcohol is added, the amount of alcohol added may be 0.001 to 20 parts by mass relative to 100 parts by mass of the composition of the present invention.

[0066] Examples of the organic amine include aminoethanol, methylaminoethanol, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetrapropylethylenediamine, N,N,N',N'-tetraisopropylethylenediamine, N,N,N',N'-tetrabutylethylenediamine, N,N,N',N'-tetraisobutylethylenediamine, N,N,N',N'-tetramethyl-1,2-propylenediamine, and N,N,N',N'-tetraethyl-1,2-propylenediamine. Diamines, N,N,N',N'-tetrapropyl-1,2-propylenediamine, N,N,N',N'-tetraisopropyl-1,2-propylenediamine, N,N,N',N'-tetrabutyl-1,2-propylenediamine, N,N,N',N'-tetraisobutyl-1,2-propylenediamine, N,N,N',N'-tetramethyl-1,3-propylenediamine, N,N,N',N'-tetraethyl-1,3-propylenediamine, N,N,N',N'-tetrapropyl-1,3-propylenediamine, N,N,N',N'-tetraisopropyl- 1,3-Propylenediamine, N,N,N',N'-Tetrabutyl-1,3-propylenediamine, N,N,N',N'-Tetraisobutyl-1,3-propylenediamine, N,N,N',N'-Tetramethyl-1,2-butylenediamine, N,N,N',N'-Tetraethyl-1,2-butylenediamine, N,N,N',N'-Tetrapropyl-1,2-butylenediamine, N,N,N',N'-Tetraisopropyl-1,2-butylenediamine, N,N,N',N'-Tetrabutyl-1,2-butylenediamine, N,N,N',N'-Tetraisobutyl N,N,N',N'-tetramethyl-1,3-butylenediamine, N,N,N',N'-tetraethyl-1,3-butylenediamine, N,N,N',N'-tetrapropyl-1,3-butylenediamine, N,N,N',N'-tetraisopropyl-1,3-butylenediamine, N,N,N',N'-tetrabutyl-1,3-butylenediamine, N,N,N',N'-tetraisobutyl-1,3-butylenediamine, N,N,N',N'-tetramethyl-1,4-butylenediamine, N,N,N',N'-tetraethyl-1,4-butylenediamine, N,N,N',N'-tetrapropyl-1,4-butylenediamine, N,N,N',N'-tetraisopropyl-1,4-butylenediamine, N,N,N',N'-tetrabutyl-1,4-butylenediamine, N,N,N',N'-tetraisobutyl-1,4-butylenediamine, N,N,N',N'-tetramethyl-1,5-pentylene, Examples of the organic amine include N,N,N',N'-tetraethyl-1,5-pentylenediamine, etc. The amount of the organic amine added may be 0.001 to 20 parts by mass based on 100 parts by mass of the composition of the present invention.

[0067] Examples of the photoacid generator include, but are not limited to, an onium salt compound, a sulfonimide compound, a disulfonyldiazomethane compound, and the like.

[0068] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate. Examples of sulfonium salt compounds include, but are not limited to, phenylsulfonium trifluoromethanesulfonate, triphenylsulfonium adamantanecarboxylate trifluoroethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium phenolsulfonate, triphenylsulfonium nitrate, triphenylsulfonium maleate, bis(triphenylsulfonium)maleate, triphenylsulfonium hydrochloride, triphenylsulfonium acetate, triphenylsulfonium trifluoroacetate, triphenylsulfonium salicylate, triphenylsulfonium benzoate, and triphenylsulfonium hydroxide.

[0069] Specific examples of the sulfonimide compound include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0070] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0071] The above photoacid generators may be used alone or in combination of two or more. When a photoacid generator is used, the proportion thereof per 100 parts by mass of the component (A) is 0.01 to 30 parts by mass, or 0.1 to 20 parts by mass, or 0.5 to 10 parts by mass.

[0072] Examples of the surfactant include nonionic surfactants, anionic surfactants, fluorine-based surfactants, cationic surfactants, silicon-based surfactants, and UV-curable surfactants. For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbita nonionic surfactants such as sorbitan fatty acid esters, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; trade names: F-TOP EF301, EF303, and EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Product Co., Ltd.) fluorine-based surfactants such as trade names Megafac F171, F173, R-08, R-30, R-40, R-40N (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), trade names Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.); and silicone-based surfactants such as organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), BYK302, BYK307, BYK333, BYK341, BYK345, BYK346, BYK347, BYK348 (manufactured by BYK, trade names). Further examples include cationic surfactants such as distearyldimethylammonium chloride, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, hexadecyltrimethylammonium bromide, and dequalinium chloride; anionic surfactants such as octanoate, decanoate, octane sulfonate, decanoic acid sulfonate, palmitate, perfluorobutane sulfonate, and dodecylbenzene sulfonate; and UV-curable surfactants such as BYK307, BYK333, BYK381, BYK-UV-3500, BYK-UV-3510, and BYK-UV-3530 (manufactured by BYK, product names). These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is 0.0001 to 5 parts by mass, or 0.001 to 5 parts by mass, or 0.01 to 5 parts by mass, per 100 parts by mass of component (A).

[0073] [Method of metallizing resist pattern] The composition for resist pattern metallization process of the present invention can be brought into contact with the surface of a resist pattern after exposure to a mask to form a resist pattern in which the components of the composition have permeated into the resist. Thus, the present invention also covers a method in which the composition is permeated into the resist and the resist pattern is metallized, particularly by the metal components in the composition.

[0074] More specifically, the present invention relates to a resist pattern metallization method that provides a resist pattern in which the above-mentioned composition components have been permeated into the resist, the method comprising the following steps [a1] to [d1]: [a1] A process of applying a resist solution onto a substrate [b1] The process of exposing and developing the resist film [c1] A step of applying the composition for resist pattern metallization process of the present invention to a resist pattern during or after development to form a coating film on the resist pattern. [d1] A step of heating the coating film to form a post-heating coating film.

[0075] The substrate used in step [a1] may be a substrate used in the manufacture of a semiconductor device, such as a silicon wafer substrate, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, or a low dielectric constant material (low-k material) coated substrate.

[0076] The resist used in step [a1] is not particularly limited as long as it is sensitive to the light used for exposure. Either a negative photoresist or a positive photoresist can be used. For example, there are positive photoresists made of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists made of a binder having a group that is decomposed by acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresists made of a low molecular compound that is decomposed by acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresists made of a binder having a group that is decomposed by acid to increase the alkaline dissolution rate, a low molecular compound that is decomposed by acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator. Specific examples of commercially available photoresists include, but are not limited to, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. In addition, examples of such photoresists include fluorine-containing polymer photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0077] Moreover, instead of the above photoresist, a resist for electron beam lithography (also called electron beam resist) or a resist for EUV lithography (also called EUV resist) can be used. The electron beam resist can be either negative or positive.Specific examples thereof include a chemically amplified resist consisting of an acid generator and a binder having a group that decomposes with an acid to change the alkaline dissolution rate, a chemically amplified resist consisting of an alkali-soluble binder, an acid generator, and a low molecular compound that decomposes with an acid to change the alkaline dissolution rate of the resist, a chemically amplified resist consisting of an acid generator, a binder having a group that decomposes with an acid to change the alkaline dissolution rate, and a low molecular compound that decomposes with an acid to change the alkaline dissolution rate of the resist, a non-chemically amplified resist consisting of a binder having a group that decomposes with an electron beam to change the alkaline dissolution rate, and a non-chemically amplified resist consisting of a binder having a site that is cut by an electron beam to change the alkaline dissolution rate.When using these electron beam resists, a resist pattern can be formed in the same way as when using a photoresist with an electron beam as the irradiation source. As the EUV resist, a methacrylate resin-based resist can be used.

[0078] After coating the resist solution, baking is performed, for example, at a baking temperature of 70 to 150° C. for a time of 0.5 to 5 minutes, to obtain a resist (film) having a thickness of, for example, 10 to 1000 nm. The resist solution, developer, and coating materials described below can be applied or coated by spin coating, dipping, spraying, etc., with the spin coating being particularly preferred.

[0079] The method may further include a step [a1-0] of forming a resist underlayer film on the substrate prior to the step [a1]. The resist underlayer film has an anti-reflection function and an organic hard mask function. Specifically, before applying the resist solution in step [a1], a step [a1-0] of forming a resist underlayer film on the substrate can be performed, and then a step [a1] of applying the resist solution thereon can be performed. In step [a1-0], a resist underlayer film (also called an organic underlayer film) can be formed on the semiconductor substrate, and a resist can be formed thereon, or a silicon hard mask can be further formed on the resist underlayer film, and a resist can be formed thereon.

[0080] The resist underlayer film used in the above step [a1-0] is used to prevent diffuse reflection during exposure of the upper resist film and to improve adhesion with the resist film. For example, an acrylic resin or a novolac resin can be used. The resist underlayer film can be formed as a coating having a thickness of 1 to 1000 nm on a semiconductor substrate. The resist underlayer film used in the above step [a1-0] can be a hard mask using an organic resin, in which case a material with a high carbon content and a low hydrogen content is used. Examples include polyvinylnaphthalene resins, carbazole novolac resins, phenol novolac resins, naphthol novolac resins, etc. These can be formed as a coating film with a thickness of 5 to 1,000 nm on a semiconductor substrate.

[0081] In addition, the silicon hard mask used in the above step [a1-0] can be a polysiloxane obtained by hydrolyzing a hydrolyzable silane. For example, polysiloxanes obtained by hydrolyzing tetraethoxysilane, methyltrimethoxysilane, and phenyltriethoxysilane can be exemplified. These can be formed as a coating having a thickness of 5 to 200 nm on the above resist underlayer film.

[0082] In step [b1], the resist film is exposed through a predetermined mask. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), EUV light (wavelength 13.5 nm), an electron beam, etc. can be used. After the exposure, a post-exposure bake (PEB) can be performed as necessary. The heating temperature for the post-exposure bake is appropriately selected from 70°C to 150°C and the heating time from 0.3 to 10 minutes.

[0083] Next, development is performed with a developer, whereby, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed, and a photoresist pattern is formed. In this case, examples of the developer include an aqueous alkaline solution (alkaline developer) such as an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline, or an aqueous solution of an amine such as ethanolamine, propylamine, or ethylenediamine. Furthermore, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

[0084] In the present invention, an organic solvent can be used as a developer. After exposure, development is performed with the developer (solvent). As a result, when a positive photoresist is used, the photoresist in the unexposed area is removed, and a photoresist pattern is formed. In this case, examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, Ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate , 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. can be mentioned as examples. Furthermore, surfactants and the like can be added to these developers. The development conditions are suitably selected from the range of a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

[0085] In step [c1], the composition of the present invention is applied to the resist pattern during or after development, preferably to the resist pattern after development, to form a coating film on the surface of the resist pattern. Here, the coating film is formed so as to cover the resist pattern, i.e., to cover the top, sidewalls and bottom of the resist pattern. In this case, the thickness of the coating film is appropriately determined taking into consideration the height and space width of the resist pattern, the film thickness reduction due to evaporation of the solvent, etc., and the intended thickness of the coating film after heating.

[0086] The step [d1] is a step of heating the coating film to form a post-heating coating film. The heating is preferably carried out at a baking temperature of 80 to 200° C. for 0.5 to 5 minutes. During this heating, the composition components of the present invention permeate into the resist pattern. The above-described method can obtain a resist pattern in which the composition components are permeated into the resist, and at the same time, a post-heating coating film is formed on the surface of the resist pattern. The thickness of the post-heating coating film from the surface of the resist pattern cannot be generally defined because it varies depending on the height and space width of the resist pattern, but can be, for example, about 1 nm to 20 nm.

[0087] The method of the present invention is also directed to a resist pattern metallization method which provides a resist pattern in which the above-mentioned composition components have been permeated into the resist, comprising the following steps [a2] to [e2]: [a2] A process of applying a resist solution onto a substrate [b2] The process of exposing and developing the resist film [c2] A step of applying the composition for resist pattern metallization process of the present invention to a resist pattern during or after development to form a coating film on the resist pattern. [d2] A step of heating the coating film to form a post-heating coating film. [e2] A step of removing the coating film after heating with water or a developer. Here, steps [a2], [b2] and [d2] can be carried out in the same manner as described above for steps [a1] (including [a1-0]), [b1] and [d1], respectively.

[0088] Step [c2] differs from step [c1] in that the composition of the present invention is applied to the resist pattern during or after development, and a coating film is formed so that the resist pattern is buried. That is, the coating film is formed so that the thickness of the coating film from the bottom of the resist pattern is more than 100% of the height of the pattern. In this case, the thickness of the coating film from the bottom of the resist pattern is appropriately determined in consideration of the conditions of step [e2] (the removal solution used to remove the unnecessary coating film after heating and other various conditions), etc.

[0089] Then, in step [e2], the heated coating film obtained by the heating in step [d2] is removed with water or a developer. The developer used in the previous step [b2] is preferably the same as that used in the previous step [b2]. The same type of developer as the developer used in the present invention can be used. As for water, ion-exchanged water, ultrapure water, or the like, which is used in this field, can be used. This step can remove unnecessary post-heat coating films and obtain a resist pattern in which the composition components of the present invention are permeated. However, depending on the conditions for removing the post-heat coating film, the post-heat coating film may be completely removed from the resist pattern surface or may remain on the resist pattern surface. The thickness of the post-heat coating film remaining on the resist pattern surface varies depending on the height and space width of the resist pattern, and the conditions of step [e2] (the removal solution used to remove unnecessary post-heat coating films and other conditions), so it cannot be generally specified, but is usually 20 nm or less. The thickness of the post-heat coating film from the resist pattern surface can be adjusted by changing the conditions of step [e2]. Depending on the conditions of step [e2], the post-heat coating film may be completely removed from the resist pattern surface, and the resist pattern itself may become thinner.

[0090] After the above-mentioned step [d1], a step of removing the coating film that has been subjected to the heating step [d1] with water or a developer may be included, for example, for the purpose of thinning the post-heating coating film formed on the surface of the resist pattern, as in the above-mentioned step [d2]. The water and developer used here may be the same type of water and developer as those used in the previous step [b1].

[0091] Fig. 9 is a schematic diagram of an example of a resist pattern metallization method including steps [a1] to [d1], and Fig. 10 is a schematic diagram of an example of a resist pattern metallization method including steps [a2] to [e2] (note that these figures also show the steps of processing a substrate ([f1] and [f2] in the figures) in the [Method of manufacturing a semiconductor device] described later). Note that the present invention is not limited to the steps shown in these figures. In the figure, Sub indicates the substrate, UC indicates the underlayer of the resist (carbon-containing layer (SOC), organic antireflective coating (BARC), inorganic antireflective coating (Si-HM), etc.), and PR indicates the resist film.

[0092] [Method of manufacturing semiconductor device] The present invention also relates to a method for manufacturing a semiconductor device, which comprises, following the above-mentioned "resist pattern metallization method," a step of processing a substrate with a metallized resist pattern obtained through the method. In addition, when a resist underlayer film (carbon-containing layer (SOC), organic anti-reflective film (BARC), inorganic anti-reflective film (Si-HM), etc.) is formed between the substrate and the resist, the metallized resist pattern can be used as a protective film to sequentially process the layer (film) underneath. The following will provide a detailed explanation, including the case where a resist underlayer film, etc. is formed, but the present invention is not limited to the following.

[0093] When a resist underlayer film has been formed, the resist underlayer film is first removed (patterned) using the metallized resist pattern (upper layer) as a protective film ([f1] and [f2] in Figures 9 and 10). The resist underlayer film is removed by dry etching, and gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. In this case, the resin-based underlayer film (organic underlayer film) is preferably removed by dry etching using an oxygen-based gas. This is because the metallized resist pattern according to the present invention is difficult to remove by dry etching using an oxygen-based gas. Note that a nitrogen-based gas may be mixed with the oxygen-based gas for dry etching. Also, when a silicon hard mask is provided, it is preferable to use a halogen-based gas. For example, a fluorine-based gas is used, such as tetrafluoromethane (CF4), Examples include, but are not limited to, perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), and the like. By the above-mentioned dry etching, a patterned resist underlayer film and a patterned silicon hard mask can be obtained.

[0094] Next, the semiconductor substrate is processed using the metallized resist pattern as a protective film, and in the case where a resist underlayer film or the like is provided, using the metallized resist pattern and the patterned resist underlayer film or the like as protective films. The semiconductor substrate is preferably processed by dry etching using a fluorine-based gas. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2). EXAMPLES

[0095] The present invention will be described in more detail below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following.

[0096] [1] Synthesis of polymer (hydrolysis condensation product) (Synthesis Example 1) 5.89 g of water and 120.54 g of tetrahydrofuran were placed in a 500 ml flask, and 40.18 g of aminopropyltriethoxysilane (100 mol % of all silanes) was added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the dropwise addition, the flask was transferred to an oil bath adjusted to 40°C and reacted for 240 minutes. Thereafter, the reaction solution was cooled to room temperature, and 120.54 g of water was added to the reaction solution, and the reaction by-products, ethanol, tetrahydrofuran, and water, were distilled off under reduced pressure, and the solution was concentrated to obtain an aqueous solution of a hydrolysis condensate (polysiloxane). Water was further added to adjust the concentration to 20 mass percent in terms of solid residue at 140° C., with the solvent ratio being 100% water (solvent containing only water). The obtained polymer corresponded to the formula (2-1-1).

[0097] (Synthesis Example 2) 89.99 g of water was placed in a 500 ml flask, and 30.00 g of 3-(N,N-dimethylaminopropyl)trimethoxysilane (100 mol % of all silanes) was added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the dropwise addition, the flask was transferred to an oil bath adjusted to 40°C and reacted for 240 minutes. Thereafter, the reaction solution was cooled to room temperature, and 179.98 g of water was added to the reaction solution, and the reaction by-products, methanol and water, were distilled off under reduced pressure, and the solution was concentrated to obtain an aqueous solution of hydrolysis condensation product (polysiloxane). Water was further added to adjust the concentration to 20 mass percent in terms of solid residue at 140° C., with the solvent ratio being 100% water (solvent containing only water). The obtained polymer corresponded to the formula (2-4-1).

[0098] (Synthesis Example 3) 4.69 g of water and 89.99 g of acetone were placed in a 500 ml flask, and while the mixed solution was stirred with a magnetic stirrer, 30.00 g of dimethylaminopropyltrimethoxysilane was added dropwise to the mixed solution, followed by the addition of 7.23 g of a 1 M aqueous solution of nitric acid. After the addition of the 1M aqueous nitric acid solution, the flask was transferred to an oil bath adjusted to 40° C. and reacted for 240 minutes. Thereafter, the reaction solution was cooled to room temperature, and 179.98 g of water was added to the reaction solution. The reaction by-products, methanol, acetone, and water, were distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensation product. An aqueous (polysiloxane) solution was obtained. Water was further added to adjust the concentration to 20 mass percent in terms of solid residue at 140° C., with the solvent ratio being 100% water (solvent containing only water). The obtained polymer corresponded to the formula (2-9-2).

[0099] (Synthesis Example 4) 91.16 g of water was placed in a 500 ml flask, and 22.23 g of dimethylaminopropyltrimethoxysilane and 8.16 g of triethoxysilylpropylsuccinic anhydride were added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the dropwise addition, the flask was transferred to an oil bath adjusted to 40°C and reacted for 240 minutes. Thereafter, the reaction solution was cooled to room temperature, and 91.16 g of water was added to the reaction solution, and the reaction by-products, methanol, ethanol, and water, were distilled off under reduced pressure, and the solution was concentrated to obtain an aqueous solution of a hydrolysis condensate (polysiloxane). Water was further added to adjust the concentration to 20 mass percent in terms of solid residue at 140° C., with the solvent ratio being 100% water (solvent containing only water). The obtained polymer corresponded to the formula (2-10-2).

[0100] (Synthesis Example 5) 93.13 g of a 0.5 M aqueous hydrochloric acid solution was placed in a 300 ml flask, and 6.87 g of aminopropyltriethoxysilane (100 mol % of all silanes) was added dropwise to the mixed solution while stirring the mixed solution with a magnetic stirrer. After the dropwise addition, the flask was transferred to an oil bath adjusted to 23°C and reacted for 5 days. After that, the reaction by-products ethanol and water were distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensation product (polysiloxane). After that, the reaction by-products ethanol and water were distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensation product (polysiloxane). Further water was added to adjust the concentration to 20 mass percent in terms of solid residue at 140°C, assuming a solvent ratio of 100% water (solvent containing only water). The resulting polymer was a ladder-type silsesquioxane represented by formula (2-1-4), where R was an ammonium chloride propyl group. (R=C3H6NH3 + Cl - ). Then, 6.8 g of anion exchange resin was added to remove the chloride ions. The resulting polymer was a ladder-type silsesquioxane represented by formula (2-1-4), where R was an aminopropyl group. (R=C3H6NH2)

[0101] (Synthesis Example 6) 5.39 g of acetic acid and 179.58 g of ultrapure water were placed in a 300 ml flask, and while the mixed solution was stirred with a magnetic stirrer, 3.72 g of dimethylaminopropyltrimethoxysilane (30 mol % of the total silanes) was added dropwise to the mixed solution. After stirring for 5 minutes at room temperature, the aqueous solution was added dropwise to 8.73 g of tetraethoxysilane (70 mol % of the total silanes). After the dropwise addition, the flask was transferred to an oil bath adjusted to 23°C and reacted for 2 hours. After that, the reaction by-products methanol, ethanol, and water were distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensation product (polysiloxane). After that, the reaction by-products ethanol and water were distilled off under reduced pressure at 50°C and then at 100°C, and the mixture was concentrated to obtain a hydrolysis condensation product (polysiloxane). Water was then added to adjust the concentration to 20 mass percent in terms of solid residue at 140° C., with a solvent ratio of 100% water (solvent containing only water). The resulting polymer corresponded to formula (2-5-5).

[0102] [2] Preparation of the composition The polysiloxane (polymer) obtained in the above synthesis example, additives, and solvent were mixed in the ratios shown in Table 1, and filtered through a 0.1 μm fluororesin filter to prepare each polymer-containing coating liquid. The amount of each additive in Table 1 is shown in parts by mass. The amount of polymer (polysiloxane) added in Table 1 indicates the amount of the polymer itself added, not the amount of the polymer solution added. In Table 1, NfA stands for nonafluorobutanesulfonic acid, DBSA stands for dodecylbenzenesulfonic acid, and Ac stands for acetic acid.

[0103] [Table 1]

[0104] [3] Preparation of composition for forming organic resist underlayer film Under nitrogen, carbazole (6.69 g, 0.040 mol, Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, Tokyo Chemical Industry Co., Ltd.) and 100 mL of 10-chloro-2,2-diphenyl-2,4-tetrafluoroethylene (1.0 g, 0.040 mol, Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL four-neck flask. To the mixture, paratoluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) were added and stirred. The mixture was heated to 100°C to dissolve and initiate polymerization. After 24 hours, the mixture was allowed to cool to 60°C. The stirred reaction mixture was diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to cause precipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 80° C. for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL). In addition, PCzFL 1 The H-NMR measurement results were as follows: 1 H-NMR(400MHz,DMSO-d6):δ7.03-7.55(br,12H),δ7.61-8.10(br,4H),δ11.18(br,1H) The weight average molecular weight Mw of PCzFL was 2,800 and the polydispersity Mw / Mn was 1.77 as calculated using polystyrene standards by GPC. [ka]

[0105] 20 g of PCzFL was mixed with 3.0 g of tetramethoxymethylglycoluril (trade name Powder Link 1174, manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.)) as a crosslinking agent, 0.30 g of pyridinium paratoluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (trade name, manufactured by DIC Corporation) as a surfactant, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate. Thereafter, the mixture was filtered using a polyethylene microfilter with a pore size of 0.10 μm, and further filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare an organic resist underlayer film forming composition for use in a multilayer lithography process.

[0106] [4] Coating property evaluation test The compositions obtained in Examples 1-1 to 6-1, Examples 1-2 to 6-2, and Comparative Examples 1 and 2 were each applied onto a silicon wafer using a spinner to form a coating film, which was then heated on a hot plate at 100°C for 1 minute to form a Si-containing film (film thickness: 20 nm). The obtained Si-containing films were observed using an optical microscope. As a result of the observation, films that were formed uniformly were rated as "good", and films that had stripes and were not formed uniformly were rated as "bad". The obtained results are shown in Table 2. Optical microscope photographs (magnification: 50K) of the Si-containing films obtained in Example 4-2 and Comparative Example 2 are shown in Figure 1 ((a) Example 4-2, (b) Comparative Example 2).

[0107] [Table 2]

[0108] [5] Test to confirm penetration of silicon components into resist An EUV resist solution (methacrylate resin-based resist) was applied onto a silicon wafer using a spinner and heated on a hot plate at 110°C for 1 minute to form a photoresist film with a thickness of 30 nm. The composition obtained in Example 4-2 was then applied to the photoresist film using a spinner to form a coating film, and heated on a hot plate at 100°C for 1 minute to form a Si-containing film (film thickness 100 nm) while allowing the composition components (particularly the silane components) to penetrate into the EUV resist. Ultrapure water was then used to remove the composition components that had not penetrated into the resist, yielding an EUV resist film into which the composition components had penetrated. The EUV resist film was then evaluated by TOF-SIMS to confirm whether the Si components were present in the film. As a comparative example, a TOF-SIMS evaluation was performed directly on the EUV resist film. The results obtained are shown in Table 3. Furthermore, the TOF-SIMS data of the EUV resist film to which the composition of Example 4-2 was applied is shown in FIG. The TOF-SIMS measurement conditions are as follows: Primary Ion: Bi 3++ Sputter Ion: Cs Area (measurement area): 50×50μm 2 Sputter Area: 250×250μm 2 Polarity: Negative

[0109] [Table 3]

[0110] [6] Resist pattern preparation by ArF exposure and metallization of resist patterns (1) (Resist patterning evaluation: Evaluation via the PTD (positive alkaline development) process, which involves alkaline development) The above composition for forming an organic resist underlayer film was applied onto a silicon wafer using a spinner and baked on a hot plate at 240° C. for 60 seconds to obtain an organic underlayer film (layer A) having a thickness of 200 nm. A commercially available ArF resist solution (manufactured by JSR Corporation, product name: AR2772JN) was applied onto the A layer using a spinner and heated on a hot plate at 110° C. for 1 minute to form a photoresist film (B layer) with a thickness of 100 nm. Using a Nikon Corporation NSR-S307E scanner (wavelength 193 nm, NA, σ: 0.85, 0.93 / 0.85), the photoresist film was exposed through a mask set so that after development, the photoresist line width and the width between the lines were 0.062 μm, i.e., a dense line of 0.062 μm line and space (L / S) = 1 / 1 was formed. Then, the photoresist film was baked on a hot plate at 100°C for 60 seconds, and after cooling, it was developed for 60 seconds using a 2.38% alkaline aqueous solution to form a resist pattern. Next, the compositions (coating solutions) of Examples 1-1 to 6-1 were applied (film thickness 5 nm) to this resist pattern, and the 2.38 mass% tetramethylammonium aqueous solution used for development was replaced with the compositions of these Examples. As a comparative example, water was applied to the resist pattern, and the 2.38 mass% tetramethylammonium aqueous solution used for development was replaced with water. The silicon substrate was then spun at 1,500 rpm for 60 seconds to dry the solvent in the composition, and then heated at 100°C for 60 seconds to form a post-heating coating film, allowing the composition components to penetrate from the side walls and top of the resist pattern. The photoresist patterns thus obtained were examined and evaluated for their pattern shape and line width roughness by observing the cross section and the top of the patterns. In observing the pattern shape, those that did not have significant pattern peeling, undercut, or thickening at the bottom of the line (footing) were rated as "good," and those that had undercut or footing were rated as "poor (undercut)" or "poor (footing)." Regarding line width roughness, a line width 3 sigma value of 6.0 nm or more was evaluated as "poor", and a line width of less than 6.0 nm was evaluated as "good". The results are shown in Table 4. Scanning microscope photographs (magnification: 100K, pattern top, pattern cross section) of the resist pattern using the composition of Example 4-1 and the resist pattern of the comparative example are shown in Figure 3 (Example 4-1) and Figure 4 (Comparative Example).

[0111] Furthermore, after that, using the resist pattern permeated with the composition components as a mask, dry etching was performed with O2 and N2 gases to transfer the pattern to the organic underlayer film (layer A). The obtained patterns were evaluated as "poor" when the line width variation before and after dry etching was 10 nm or more, and as "good" when it was less than 10 nm. The results are also shown in Table 4. Scanning microscope photographs (magnification: 100K, pattern) of the resist pattern and transfer pattern to which the composition of Example 4-1 was applied after dry etching, and the resist pattern and transfer pattern of the comparative example after dry etching are also shown. The upper part, pattern cross section) is shown in FIG. 5 (Example 4-1) and FIG. 6 (Comparative Example).

[0112] [Table 4]

[0113] [7] Resist pattern preparation by ArF exposure and metallization of resist patterns (2) (Resist patterning evaluation: Evaluation via PTD process using alkaline development) The above composition for forming an organic resist underlayer film was applied onto a silicon wafer using a spinner and baked on a hot plate at 240° C. for 60 seconds to obtain an organic underlayer film (layer A) having a thickness of 200 nm. A commercially available ArF resist solution (manufactured by JSR Corporation, product name: AR2772JN) was applied onto the A layer using a spinner and heated on a hot plate at 110° C. for 1 minute to form a photoresist film (B layer) with a thickness of 100 nm. Using a Nikon Corporation NSR-S307E scanner (wavelength 193 nm, NA, σ: 0.85, 0.93 / 0.85), the photoresist film was exposed through a mask set so that after development, the photoresist line width and the width between the lines were 0.062 μm, i.e., a dense line of 0.062 μm line and space (L / S) = 1 / 1 was formed. Then, the photoresist film was baked on a hot plate at 100°C for 60 seconds, and after cooling, it was developed for 60 seconds using a 2.38% alkaline aqueous solution to form a resist pattern. Next, the compositions (coating solutions) of Examples 1-2 to 6-2 were applied to this resist pattern (film thickness 120 nm), and the 2.38 mass% tetramethylammonium aqueous solution used for development was replaced with the compositions of these Examples. As a comparative example, water was applied to the resist pattern, and the 2.38 mass% tetramethylammonium aqueous solution used for development was replaced with water. The silicon substrate was then spun at 1,500 rpm for 60 seconds to dry the solvent in the composition, and then heated at 100°C for 60 seconds to form a post-heating coating film, allowing the composition components (particularly the silane components) to penetrate from the side walls and top of the resist pattern. Thereafter, a 2.38 mass % aqueous solution of tetramethylammonium was applied again to remove the composition components that had not permeated into the resist pattern. The photoresist patterns thus obtained were examined and evaluated for their pattern shape and line width roughness by observing the cross section and the top of the patterns. In observing the pattern shape, those that did not suffer from significant pattern peeling, undercut, or thickening at the bottom of the line (footing) were rated as "good," while those that suffered from undercut or footing were rated as "poor (undercut)" or "poor (footing)." In addition, regarding line width roughness, the 3 sigma value of the line width is 6.0 nm or more. those less than 6.0 nm were rated as "good". The results obtained are shown in Table 5.

[0114] Furthermore, after that, using the resist pattern permeated with the composition components as a mask, dry etching was performed with O2 and N2 gases to transfer the pattern to the organic underlayer film (layer A). The obtained patterns were evaluated as "poor" when the line width variation before and after dry etching was 10 nm or more, and as "good" when it was less than 10 nm. The results are shown in Table 5.

[0115] [Table 5]

[0116] In Example 4-2, the line pattern size before dry etching changed from 62 nm to 72 nm, which means that the composition components were covered with a film thickness of 5 nm on both sides and the upper side of the resist line.

[0117] [8] Resist pattern preparation by EUV exposure and metallization of resist patterns: Positive alkaline development The above composition for forming an organic resist underlayer film was applied onto a silicon wafer using a spinner and baked on a hot plate at 240° C. for 60 seconds to obtain an organic underlayer film (layer A) having a thickness of 90 nm. An EUV resist layer (B) was formed on top of the EUV resist solution (methacrylate resin-based resist) by spin coating and heating at 130°C for 1 minute. This was exposed using an EUV exposure device (NXE3300) under the conditions of NA = 0.33, σ = 0.90 / 0.67, and Dipole 45 (exposure dose 49 mJ, pattern line & space: 22 mm). After exposure, post-exposure baking (PEB, 110° C. for 1 minute) was performed, the film was cooled to room temperature on a cooling plate, and developed for 30 seconds using an alkaline developer (2.38% TMAH aqueous solution). Next, the composition (coating liquid) of Example 4-1 was coated (film thickness 5 nm) on this resist pattern, and the 2.38 mass% tetramethylammonium aqueous solution used for development was replaced with the composition of Example 4-1. As a comparative example, water was coated on the resist pattern, and the 2.38 mass% tetramethylammonium aqueous solution used for development was replaced with water. The silicon substrate was then spun at 1,500 rpm for 60 seconds to dry the solvent in the composition, and then heated at 100°C for 60 seconds to form a post-heating coating film, allowing the composition components (particularly the silane components) to penetrate from the side walls and top of the resist pattern. Then, a 2.38% by mass aqueous solution of tetramethylammonium was applied again to form a resist pattern. The composition components that did not infiltrate the turn were removed. The photoresist patterns thus obtained were examined and evaluated for their pattern shapes by observing the cross section and the top of the patterns. In observing the pattern shape, a state in which there was no significant pattern peeling, undercut, or thickening at the bottom of the line (footing) was rated as "good," while an unfavorable state in which the resist pattern was peeled and collapsed was rated as "collapsed." The results are shown in Table 6. Scanning microscope photographs (magnification: 200K, upper part of pattern) of the resist pattern using the composition of Example 4-1 and the resist pattern of the comparative example are shown in Figure 7 (Example 4-1) and Figure 8 (Comparative Example).

[0118] [Table 6]

Claims

1. Component (A): at least one selected from the group consisting of a hydrolyzable silane compound (a2), a hydrolyzate of the hydrolyzable silane compound (a3), and a hydrolyzed condensate of the hydrolyzable silane compound (a4); Component (B): an acid compound that does not contain a carboxylic acid group (—COOH), and Component (C): Aqueous solvent Including, The hydrolyzable silane compound (a2) contains at least one selected from the group consisting of hydrolyzable silanes represented by the following formula (1) and hydrolyzable silanes represented by the following formula (1-1): [R １ ａ０ Si(R ２ ) ３－ａ０ ｂ０ R ３ ｃ０ Formula (1)​ [[Si(R １０ )( ２ O)]] ｎ０ Si(R ２０ )( ２ )R ３０ ２ Formula (1-1) (In formula (1), R ３ represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R ３ When there are multiple R ３ represents a group which may be bonded to the Si atom by forming a ring, R １ represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and is bonded to a silicon atom via a Si—C bond; R ２ represents an alkoxy group, an acyloxy group, or a halogen group; a0 represents an integer of 0 or 1; b0 represents an integer of 1 to 3; c0 represents an integer of 1 or 2. In formula (1-1), R １０ and R ２０ each represents a hydroxy group, an alkoxy group, an acyloxy group, or a halogen group, R ３０ represents an organic group containing an amino group or an organic group having an ionic functional group and bonded to a silicon atom via a Si-C bond or a Si-N bond, and R ３０ When there are multiple R ３０ represents a group which may be bonded to the Si atom by forming a ring, n0 represents an integer from 1 to 10. The hydrolyzable silane compound (a2) contains the hydrolyzable silanes represented by the formulas (1) and (1-1) and another hydrolyzable silane compound (b) in a molar ratio of 3:97 to 100:

0. Compositions for resist pattern metallization processes.

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