Composition for resist pattern metallization process

Abstract

The present invention provides a composition and a method for metallizing a resist pattern using the composition, which can improve the roughness or collapse of the resist pattern and improve the etching resistance by metallizing the resist of the resist pattern. The present invention is a composition for a resist pattern metallization process and a method for metallizing a resist pattern using the composition to provide a resist pattern in which the resist is infiltrated with the composition components, wherein the composition contains (A) component: at least one selected from a metal oxide (1), a hydrolyzable silane compound (2), a hydrolyzate of the hydrolyzable silane compound (3), and a hydrolysis condensate of the hydrolyzable silane compound (4); (B) component: an acid compound that does not contain a carboxyl group (-COOH); and (C) component: an aqueous solvent.

Description

Technical Field

[0001] The present invention relates to a composition for coating on a resist pattern during development or on a resist pattern after development through a photolithography process, and more particularly to a composition for metallization process for penetrating the composition into the resist to obtain a resist pattern infiltrated with the composition components. Background Art

[0002] In the field of manufacturing semiconductor devices, a technique of forming a fine pattern on a substrate and etching the substrate according to the pattern to process the substrate is widely used.

[0003] With the development of photolithography technology, fine patterning has made progress, and KrF excimer laser and ArF excimer laser are used, and further research is conducted on exposure technology using electron beam (EB) or EUV (Extreme Ultra violet), as well as self-assembly lithography (DSA: Directed Self-Assembly) and other technologies.

[0004] In recent years, due to miniaturization of patterns, a phenomenon in which pattern collapse occurs during development performed after exposure of a resist in a photolithography step and during a rinsing step with a developer has become a problem.

[0005] As a means of suppressing such pattern collapse, the resist film is being thinned. However, on the other hand, the improvement in the etching resistance of the resist itself cannot be said to have fully caught up with the speed of thinning, and the difficulty of etching the hard mask or the semiconductor substrate is increasing.

[0006] In this case, a method has been proposed in which the exposed resist surface is developed with a developer, then cleaned with a rinse solution, and the rinse solution is replaced with a coating solution containing a polymer component so that the resist pattern is covered with the polymer component, and then the resist is removed by dry etching to form a reverse pattern with the replaced polymer component. For example, a pattern forming method has been disclosed, which is characterized by comprising: a step of forming a resist film on a substrate; a step of selectively irradiating the resist film with energy rays in order to form a latent image on the resist film; a step of supplying a developer (alkaline developer) on the resist film in order to form a resist pattern from the resist film on which the latent image is formed; a step of supplying the rinse liquid on the substrate in order to replace the developer on the substrate with a rinse liquid; a step of supplying a coating film material on the substrate in order to replace the developer on the substrate with a coating film material containing at least a portion of the solvent of the rinse liquid on the substrate and a solute different from that of the resist film; a step of volatilizing the solvent in the coating film material in order to form a coating film covering the resist film on the substrate; a step of retreating at least a portion of the surface of the coating film in order to expose at least a portion of the upper surface of the resist pattern and form a mask pattern composed of the coating film; and a step of processing the substrate using the mask pattern (Patent Document 1).

[0007] Furthermore, as an aqueous composition for coating on a photoresist pattern, a composition containing an amino group-containing water-soluble compound and a carboxyl group-containing compound has been proposed (Patent Document 2).

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2005-277052

[0011] Patent Document 2: Japanese Patent Application No. 2013-536463 Summary of the invention

[0012] In the prior art disclosed in Patent Document 1, when a resist is removed using a developer or a rinse solution to form a resist pattern, pattern collapse may occur.

[0013] Furthermore, when the composition disclosed in Patent Document 2 is applied on a resist pattern, a uniform coating cannot always be obtained.

[0014] The present invention has been made in view of the above-mentioned situation, and its object is to improve the collapse and roughness of the resist pattern by metallizing the resist in the resist pattern, and to provide a composition capable of achieving improved etching resistance, and a method for metallizing the resist pattern using the composition.

[0015] After repeated intensive research to achieve the aforementioned purpose, the present inventors have discovered that a composition composed of a metal oxide, or a hydrolyzable silane compound and its hydrolyzate, hydrolysis-condensation product, and an acid compound containing no carboxyl group can be applied to a resist pattern during or after development and heated to obtain a resist pattern infiltrated with the components of the aforementioned composition. The present inventors have also discovered that the resist pattern infiltrated with the components of the composition can suppress pattern collapse and improve etching resistance, thereby completing the present invention.

[0016] That is, as a first aspect, the present invention relates to a composition for a resist pattern metallization process, comprising:

[0017] (A) component: 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 hydrolysis-condensation product of the hydrolyzable silane compound (a4);

[0018] (B) component: an acid compound that does not contain a carboxyl group (-COOH); and

[0019] (C) Component: aqueous solvent.

[0020] As a second aspect, the present invention relates to the composition according to the first aspect, wherein the component (B) contains an acid compound having a sulfonic acid group (—SO 3 H).

[0021] As a third aspect, the present invention relates to a composition as described in the first aspect or the second aspect, wherein the hydrolyzable silane compound (a2) contains at least one selected from a hydrolyzable silane (i) containing an organic group containing an amino group and a hydrolyzable silane (ii) containing an organic group having an ionic functional group.

[0022] As a fourth aspect, the present invention relates to a composition as described in the first aspect or the second aspect, wherein the hydrolyzable silane compound (a2) contains at least one selected from the group consisting of a hydrolyzable silane represented by the following formula (1) and a hydrolyzable silane represented by the following formula (1-1);

[0023] [R 1 a0 Si(R 2 ) 3-a0 ] b0 R 3 c0 Formula (1)

[0024] C〔Si(R 10 )2O〕 n0 Si(R 20 )2]R 30 2 Formula (1-1)

[0025] In formula (1),

[0026] R 3 represents an organic group containing an amino group or an organic group having an ionic functional group, and R 3 The R 3 When there are multiple 3 It represents a group that can also form a ring and bind to the Si atom;

[0027] R 1 represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and R 1 Bonded to silicon atoms via Si-C bonds;

[0028] R 2 represents an alkoxy, acyloxy or halogen group;

[0029] a0 represents an integer of 0 or 1;

[0030] b0 represents an integer from 1 to 3;

[0031] c0 represents an integer of 1 or 2;

[0032] In formula (1-1),

[0033] R 10 and R 20 represent a hydroxyl group, an alkoxy group, an acyloxy group, or a halogen group respectively;

[0034] R 30 represents an organic group containing an amino group or an organic group having an ionic functional group, and R 30 The R 30 When there are multiple 30 It represents a group that can also form a ring and bind to the Si atom;

[0035] n0 represents an integer from 1 to 10.

[0036] As a fifth aspect, the present invention relates to the composition according to the first aspect or the second aspect, wherein 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.

[0037] According to a sixth aspect, in the composition according to any one of the first to fifth aspects, the component (B) is contained in an amount of 0.5 to 15 parts by mass based on 100 parts by mass of the component (A).

[0038] As a seventh aspect, the present invention relates to the composition according to any one of the first aspect to the sixth aspect, further comprising a curing catalyst.

[0039] As an eighth aspect, the present invention relates to the composition according to any one of the first to seventh aspects, further comprising a surfactant.

[0040] 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.

[0041] As a tenth aspect, the present invention relates to a resist pattern metallization method, which is characterized by:

[0042] The step of applying a resist solution on the substrate;

[0043] a step of exposing and developing the resist film;

[0044] A step of applying the composition according to any one of the first aspect to the ninth aspect to the resist pattern during or after the development to form a coating film on the resist pattern; and

[0045] A step of heating the coating film to form a heated coating film;

[0046] A resist pattern is provided in which the composition components are infiltrated into the resist.

[0047] As an eleventh aspect, the present invention relates to a resist pattern metallization method, the characteristics of which include:

[0048] The step of applying a resist solution on the substrate;

[0049] a step of exposing and developing the resist film;

[0050] A step of applying the composition according to any one of the first aspect to the ninth aspect to the resist pattern during or after the development to form a coating film that buries the resist pattern;

[0051] a step of heating the aforementioned coating film to form a heated coating film; and

[0052] The step of removing the heated coating film by water or a developer;

[0053] A resist pattern is provided in which the composition components are infiltrated into the resist.

[0054] As a twelfth aspect, the present invention relates to a method for manufacturing a semiconductor device, the method comprising:

[0055] A step of processing a substrate using the metallization resist pattern obtained by the method according to the tenth aspect or the eleventh aspect.

[0056] Effects of the Invention

[0057] The composition for metallization process of resist pattern of the present invention can form a resist pattern infiltrated with the components of the composition by being applied to the resist pattern. In addition, shape degradation such as peeling or collapse of the resist pattern can be suppressed, the roughness of the line width can be improved, and further, a resist pattern with improved etching resistance can be provided.

[0058] In addition, according to the resist pattern metallization method of the present invention, after mask exposure, the resist surface is brought into contact with the composition during or after the development of the resist and heat-treated, thereby covering the resist pattern or filling the space between the resist patterns to prevent the collapse of the resist pattern. Then, by heating the coating film, a resist pattern in which the composition components are permeated in 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.

[0059] And by using the resist pattern infiltrated with the composition components as an etching mask, the transfer pattern can be etched on the lower layer of the resist pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 is a diagram showing an optical microscope photograph (magnification: 50K) of a Si-containing film in the coating property evaluation [4], and Figure 1 (a) is an optical microscope photograph of a Si-containing film obtained using the composition of Example 4-2, Figure 1 (b) is an optical microscope photograph of a Si-containing film obtained using the composition of Comparative Example 2.

[0061] Figure 2 [5] This is a diagram showing 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 Si components into the resist.

[0062] Figure 3 This is a scanning microscope photograph (magnification: 100K, pattern top, pattern cross section) of a resist pattern to which the composition of Example 4-1 was applied in [6] Preparation of resist pattern by ArF exposure and metallization of resist pattern (1).

[0063] Figure 4 This is a diagram showing a scanning microscope photograph (magnification: 100K, pattern top, pattern cross section) of a comparative resist pattern in [6] Preparation of resist pattern by ArF exposure and metallization of resist pattern (1).

[0064] Figure 5It is a scanning microscope photograph (magnification: 100K, pattern top, pattern cross section) of the resist pattern and the transferred pattern using the composition of Example 4-1 after dry etching in [6] Preparation of resist pattern by ArF exposure and metallization of resist pattern (1).

[0065] Figure 6 This is a scanning microscope photograph (magnification: 100K, pattern top, pattern cross section) of a comparative example resist pattern and a transferred pattern after dry etching in [6] Preparation of resist pattern by ArF exposure and metallization of resist pattern (1).

[0066] Figure 7 [8] This is a scanning microscope photograph (magnification: 200K, upper part of the pattern) of a resist pattern to which the composition of Example 4-1 was applied in the formation of a resist pattern by EUV exposure and metallization of the resist pattern.

[0067] Figure 8 This is a diagram showing a scanning microscope photograph (magnification: 200K, upper part of the pattern) of a comparative example resist pattern in [8] resist pattern formation by EUV exposure and metallization of the resist pattern.

[0068] Fig. 9 This is a schematic diagram showing one embodiment of the resist pattern metallization method of the present invention.

[0069] Fig.10 It is a schematic diagram showing another embodiment of the resist pattern metallization method of the present invention. DETAILED DESCRIPTION

[0070] [Composition for resist pattern metallization process]

[0071] The present invention is a composition for resist pattern metallization process containing the following components (A), (B), and (C), that is, the present invention contains:

[0072] (A) component: 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 hydrolysis-condensation product of the hydrolyzable silane compound (a4) (also referred to as polysiloxane);

[0073] (B) component: an acid compound that does not contain a carboxyl group (-COOH); and

[0074] Component (C): a composition of an aqueous solvent.

[0075] The composition for metallization of resist pattern of the present invention can be applied to a resist pattern as described below to obtain a resist pattern in which the components of the composition are permeated in the resist. In the present invention, "metallization" refers to a process in which the components in the composition, particularly the silane component or metal component 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, hydrolysis condensate (a4) of the hydrolyzable silane compound) are permeated into the resist pattern.

[0076] The concentration of the solid content in the composition may be, for example, 0.01 to 50 mass %, 0.01 to 20.0 mass %, or 0.01 to 10.0 mass % relative to the total mass of the composition. The solid content refers to the components other than the solvent contained in the composition.

[0077] The proportion of the aforementioned component (A), i.e., at least one selected from the group consisting of the metal oxide (a1), the hydrolyzable silane compound (a2), the hydrolyzate of the aforementioned hydrolyzable silane compound (a3), and the hydrolysis-condensation product of the aforementioned hydrolyzable silane compound (a4), in the aforementioned solid content may be 50 to 99.9% by mass, or 80 to 99.9% by mass.

[0078] The concentration of the component (B), ie, the acid compound having no carboxyl group (—COOH), in the solid content may be 0.1% by mass to 50% by mass, or 0.1% by mass to 20% by mass.

[0079] In addition, the aforementioned component (A) (selected from at least one of the metal oxide (a1), the hydrolyzable silane compound (a2), the hydrolyzate of the aforementioned hydrolyzable silane compound (a3), and the hydrolysis condensate of the aforementioned hydrolyzable silane compound (a4)) may be contained in a ratio 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 aforementioned component (A) in the composition may generally be 0.001 to 50.0% by mass, preferably 0.001 to 20.0% by mass.

[0080] The concentration of the component (B) (the acid compound not containing a carboxyl group (—COOH)) in the composition may be 0.0001 to 2.0% by mass.

[0081] [(A) Ingredient]

[0082] The component (A) is 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-condensation product (a4) of the hydrolyzable silane compound (also referred to as polysiloxane).

[0083] In addition, when the component (A) is classified into the component (A1) and the component (A2) (the component (A1) is a metal oxide (a1); the component (A2) is a hydrolyzable silane compound (a2), a hydrolyzate (a3) ​​of the hydrolyzable silane compound, and a hydrolysis condensate (a4) of the hydrolyzable silane compound), there are cases where the component (A1) is used alone, where the component (A2) is used alone, and where the component (A1) and the component (A2) are used in combination. When the component (A1) and the component (A2) are used in combination, the ratio thereof is usually (A1):(A2)=50:1 to 0.05:1 in terms of mass ratio.

[0084] 〔Metal oxide (a1)〕

[0085] 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.

[0086] The aforementioned metal oxides may 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. may be cited. Metal oxides or partial metal oxides may be obtained as hydrolysis condensates of metal alkoxides, and partial metal oxides may contain alkoxy groups.

[0087] [Hydrolyzable silane compound (a2), hydrolyzate of the aforementioned hydrolyzable silane compound (a3), and hydrolysis-condensation product of the aforementioned hydrolyzable silane compound (a4)]

[0088] As the component (A), at least one selected from the group consisting of a hydrolyzable silane compound (a2), a hydrolyzate (a3) ​​of the above hydrolyzable silane compound, and a hydrolysis-condensation product (a4) of the above hydrolyzable silane compound can be used, and these can also be used as a mixture.

[0089] In addition, as described later, the hydrolyzable silane compound (a2) can be hydrolyzed and the resulting hydrolyzate (a3) ​​can be condensed to form a hydrolysis condensate (a4). When the hydrolysis condensate (a4) is obtained, in the case where the partial hydrolyzate in which the hydrolysis is not completely completed or the unreacted silane compound is mixed in the hydrolysis condensate, the mixture can also be used. This hydrolysis condensate (a4) includes not only polymers having a polysiloxane structure that have been completely hydrolyzed and condensed, but also polymers having a polysiloxane structure that are obtained by hydrolysis and condensation of a silane compound but in which part of the condensation is not completed and Si-OH groups remain.

[0090] As the hydrolyzable silane compound (a2), at least one selected from the group consisting of the hydrolyzable silanes represented by the above formula (1) and the above formula (1-1) can be preferably used.

[0091] The hydrolyzate (a3) ​​of the hydrolyzable silane compound corresponds to the hydrolyzate of the hydrolyzable silane compound (a2).

[0092] The hydrolysis condensate (a4) of the hydrolyzable silane compound is a condensate of the hydrolyzate (a3) ​​of the hydrolyzable silane compound (a2). (a4) is also referred to as polysiloxane.

[0093] In formula (1), R 3 is an organic group containing an amino group or an organic group having an ionic functional group, and R 3 The R 3 When there are multiple 3 It represents a group which can be bonded to the Si atom to form a ring.

[0094] R 1 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and R 1 Bonded to silicon atoms through Si-C bonds.

[0095] R 2 represents an alkoxy group, an acyloxy group, or a halogen group.

[0096] a0 represents an integer of 0 or 1, b0 represents an integer of 1 to 3, and c0 represents an integer of 1 or 2.

[0097] In formula (1-1), R 10 and R 20 They respectively represent a hydroxyl group, an alkoxy group, an acyloxy group, or a halogen group.

[0098] R 30 represents an organic group containing an amino group or an organic group having an ionic functional group, and R30 The R 30 When there are multiple 30 It represents a group which can be bonded to the Si atom to form a ring.

[0099] n0 represents an integer of 1 to 10, and examples thereof include an integer of 1 to 5, or an integer of 1.

[0100] As R in formula (1) 3 Or R in formula (1-1) 30 , examples include amino-containing organic groups.

[0101] As the amino group, a primary amino group, a secondary amino group, or a tertiary amino group may be used, and the molecule may have one amino group or a plurality of (two or three) amino groups. As these, an aliphatic amino group, an aromatic amino group, or the like may be used.

[0102] In addition, as R in formula (1) 3 Or R in formula (1-1) 30 , organic groups having ionic functional groups can be listed. Examples of ionic functional groups include ammonium cations, carboxylic acid anions, sulfonic acid anions, nitrate anions, phosphate anions, sulfonium cations, and alkoxide anions. Examples of ammonium cations include primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium.

[0103] The counter ion of the ionic functional group may be a chloride anion, a fluoride anion, a bromide anion, an iodide anion, a nitrate anion, a sulfate anion, a phosphate anion, a formate anion, an acetate anion, a propionate anion, a maleate anion, an oxalate anion, a malonic acid anion, a methylmalonic acid anion, a succinate anion, a malate anion, a tartaric acid anion, a phthalate anion, a citrate anion, a glutarate anion, a lactate anion, ions, salicylic acid anions, methanesulfonic acid anions, octanoic acid anions, decanoic acid anions, octanoic acid anions, decanoic acid anions, dodecylbenzenesulfonic acid anions, phenolsulfonic acid anions, sulfosalicylic acid anions, camphorsulfonic acid anions, nonafluorobutanesulfonic acid anions, toluenesulfonic acid anions, isopropylbenzenesulfonic acid anions, p-octylbenzenesulfonic acid anions, p-decylbenzenesulfonic acid anions, 4-octyl-2-phenoxybenzenesulfonic acid anions, 4-carboxybenzenesulfonic acid anions, etc. In addition, the unit structure may be 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.

[0104] In addition, the counter ions of the ionic functional groups include hydrogen cations, ammonium cations, sulfonium cations, iodine cations, cation, Cations, oxygen Cations, etc.

[0105] Examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl-n-propyl, etc.

[0106] In addition, a cyclic alkyl group can also be used. For example, a cyclic alkyl group having 3 to 10 carbon atoms can be listed, and specifically, a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl -cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, etc.

[0107] Examples of the aryl group include aryl groups having 6 to 20 carbon atoms. Specifically, the aryl group includes phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-mercaptophenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl.

[0108] Examples of the halogenated alkyl group and the halogenated aryl group include groups in which one or more hydrogen atoms of the alkyl group and the aryl group are substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

[0109] Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms. Specifically, the alkenyl group includes 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, 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-isopropylvinyl, 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, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl -4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-dimethyl -1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, etc.

[0110] Furthermore, the alkenyl group may have one or more hydrogen atoms substituted by a halogen atom such as fluorine, chlorine, bromine or iodine (halogenated alkenyl group).

[0111] Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.

[0112] Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.

[0113] Examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.

[0114] Examples of the organic group having a mercapto group include an ethylmercapto group, a butylmercapto group, a hexylmercapto group, and an octylmercapto group.

[0115] Examples of the organic group having a cyano group include a cyanoethyl group and a cyanopropyl group.

[0116] As R in the above formula (1) 2 And R in formula (1-1) 10 With R 20The alkoxy group in the alkoxy group includes, for example, an alkoxy group having a linear, branched, or cyclic alkyl moiety having 1 to 20 carbon atoms. Specifically, the alkoxy group includes a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentoxy group, a 2-methyl-n-pentoxy group, a 3-methyl-n-pentoxy group, a 4-methyl-n-pentoxy group, a 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy; cyclopropyloxy, cyclobutyloxy, 1-methyl-cyclopropyloxy, 2-methyl-cyclopropyloxy, cyclopropyloxy, cyclobutyloxy, cyclopropyl ...propyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, cyclopropyloxy, oxy, cyclopentyloxy, 1-methyl-cyclobutyloxy, 2-methyl-cyclobutyloxy, 3-methyl-cyclobutyloxy, 1,2-dimethyl-cyclopropyloxy, 2,3-dimethyl-cyclopropyloxy, 1-ethyl-cyclopropyloxy, 2-ethyl-cyclopropyloxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutyloxy, 2-ethyl-cyclobutyloxy, 3-ethyl-cyclobutyloxy, 1,2-dimethyl-cyclobutyloxy, 1,3-dimethyl-cyclobutyloxy, 2,2-dimethyl-cyclobutyloxy, 2,3-dimethyl-cyclobutyloxy, 2,4-dimethyl-cyclobutyloxy, 3,3-dimethyl-cyclobutyloxy, 1-n-propyl-cyclopropyloxy, 2-n-propyl-cyclopropyloxy, 1-isopropyl-cyclopropyloxy, 2-isopropyl-cyclopropyloxy, 1,2,2-trimethyl-cyclopropyloxy, 1,2,3-trimethyl-cyclopropyloxy, 2,2,3-trimethyl-cyclopropyloxy, 1-ethyl-2-methyl-cyclopropyloxy, 2-ethyl-1-methyl-cyclopropyloxy, 2-ethyl-2-methyl-cyclopropyloxy and 2-ethyl-3-methyl-cyclopropyloxy, etc.

[0117] As R in the above formula (1) 2 And R in formula (1-1) 10 With R 20Examples of the acyloxy group include acyloxy groups having 1 to 20 carbon atoms. Specifically, the acyloxy group includes methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methylcarbonyloxy, The invention also includes 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and tosylcarbonyloxy.

[0118] As R in the above formula (1) 2 , R in formula (1-1) 10 and R 20 and R in the formula (3) described later 7 Examples of the halogen group include fluorine, chlorine, bromine, and iodine.

[0119] The following shows the R in the hydrolyzable silane represented by the formula (1): 3 Examples of silanes in the case of an amino group-containing organic group include, but are not limited to, these.

[0120] 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 particularly preferably an alkoxy group such as a methoxy group or an ethoxy group.

[0121] [Chemistry 1]

[0122]

[0123] [Chemistry 2]

[0124]

[0125] [Chemistry 3]

[0126]

[0127] [Chemistry 4]

[0128]

[0129] [Chemistry 5]

[0130]

[0131] [Chemistry 6]

[0132]

[0133] [Chemistry 7]

[0134]

[0135] [Chemistry 8]

[0136]

[0137] [Chemistry 9]

[0138]

[0139] [Chemistry 10]

[0140]

[0141] [Chemistry 11]

[0142]

[0143] [Chemistry 12]

[0144]

[0145] [Chemistry 13]

[0146]

[0147] [Chemistry 14]

[0148]

[0149] [Chemistry 15]

[0150]

[0151] [Chemistry 16]

[0152]

[0153] [Chemistry 17]

[0154]

[0155] [Chemistry 18]

[0156]

[0157] [Chemistry 19]

[0158]

[0159] [Chemistry 20]

[0160]

[0161] [Chemistry 21]

[0162]

[0163] [Chemistry 22]

[0164]

[0165] [Chemistry 23]

[0166]

[0167] [Chemistry 24]

[0168]

[0169] [Chemistry 25]

[0170]

[0171] [Chemistry 26]

[0172]

[0173] [Chemistry 27]

[0174]

[0175] [Chemistry 28]

[0176]

[0177] [Chemistry 29]

[0178]

[0179] [Chemistry 30]

[0180]

[0181] [Chemistry 31]

[0182]

[0183] [Chemistry 32]

[0184]

[0185] [Chemistry 33]

[0186]

[0187] [Chemistry 34]

[0188]

[0189] [Chemistry 35]

[0190]

[0191] [Chemistry 36]

[0192]

[0193] The following shows the R in the hydrolyzable silane represented by the formula (1): 3 Examples of silanes when R is an organic group having an ionic functional group, and in the hydrolyzable silane represented by formula (1-1), 30 Examples of silanes in the case of an organic group having an ionic functional group are provided, but the examples are not limited thereto.

[0194] 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 particularly preferably an alkoxy group such as a methoxy group or an ethoxy group.

[0195] In the following formula, X and Y mean the counter ion of the ionic functional group, and specific examples thereof include the anions and cations described above as the counter ions of the ionic functional group. - , Y + They are represented as monovalent anions and monovalent cations, respectively. However, when X - , Y + In the above-mentioned example of ions, when a divalent ion is represented, the coefficient before the ion representation becomes a value of 1 / 2 times, and similarly, when a trivalent ion is represented, the coefficient of the ion representation becomes a value of 1 / 3 times.

[0196] [Chemistry 37]

[0197]

[0198] [Chemistry 38]

[0199]

[0200] [Chemistry 39]

[0201]

[0202] [Chemistry 40]

[0203]

[0204] [Chemistry 41]

[0205]

[0206] [Chemistry 42]

[0207]

[0208] [Chemistry 43]

[0209]

[0210] [Chemistry 44]

[0211]

[0212] [Chemistry 45]

[0213]

[0214] [Chemistry 46]

[0215]

[0216] [Chemistry 47]

[0217]

[0218] [Chemistry 48]

[0219]

[0220] [Chemistry 49]

[0221]

[0222] [Chemistry 50]

[0223]

[0224] [Chemistry 51]

[0225]

[0226] [Chemistry 52]

[0227]

[0228] [Chemistry 53]

[0229]

[0230] [Chemistry 54]

[0231]

[0232] [Chemistry 55]

[0233]

[0234] [Chemistry 56]

[0235]

[0236] [Chemistry 57]

[0237]

[0238] [Chemistry 58]

[0239]

[0240] [Chemistry 59]

[0241]

[0242] [Chemistry 60]

[0243]

[0244] [Chemistry 61]

[0245]

[0246] [Chemistry 62]

[0247]

[0248] [Chemistry 63]

[0249]

[0250] [Chemistry 64]

[0251]

[0252] [Chemistry 65]

[0253]

[0254] [Chemistry 66]

[0255]

[0256] [Chemistry 67]

[0257]

[0258] [Chemistry 68]

[0259]

[0260] [Chemistry 69]

[0261]

[0262] [Chemistry 70]

[0263]

[0264] [Chemistry 71]

[0265]

[0266] [Chemistry 72]

[0267]

[0268] [Chemistry 73]

[0269]

[0270] [Chemistry 74]

[0271]

[0272] [Chemistry 75]

[0273]

[0274] [Chemistry 76]

[0275]

[0276] [Chemistry 77]

[0277]

[0278] [Chemistry 78]

[0279]

[0280] The hydrolyzable silane compound (a2) in the composition of the present invention may be used in combination with at least one hydrolyzable silane compound (b) selected from the hydrolyzable silane represented by the formula (1) and the hydrolyzable silane represented by the formula (1-1).

[0281] Preferred specific examples of the hydrolyzable silane compound (b) used in the present invention include at least one selected from the group consisting of a hydrolyzable silane represented by the following formula (2) and a hydrolyzable silane represented by the following formula (3).

[0282] R 4 a Si(R 6 ) 4-aFormula (2)

[0283] In formula (2), R 4 represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and R 4 Bonded to silicon atoms through Si-C bonds.

[0284] R 5 represents an alkoxy group, an acyloxy group, or a halogen group.

[0285] a represents an integer from 0 to 3.

[0286] [R 6 c Si(R 7 ) 3-c ]2Z b Formula (3)

[0287] In formula (3), R 6 It represents an alkyl group.

[0288] R 7 represents an alkoxy group, an acyloxy group, or a halogen group.

[0289] Z represents an alkylene group or an arylene group.

[0290] b represents an integer of 0 or 1, and c represents an integer of 0 or 1.

[0291] In formula (2), R 4 The alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group, organic group having acryloyl group, methacryloyl group, mercapto group or cyano group and R 6 Specific examples of the alkyl group in include 1 The example described in is the same.

[0292] In formula (2), R 5 And R in formula (3) 7 Specific examples of the alkoxy group, acyloxy group and halogen group in the formula (A) include the following: 2 The example described in is the same.

[0293] Examples of the alkylene group or arylene group in Z include divalent organic groups derived from the above-mentioned alkyl groups or aryl groups.

[0294] Specific examples of the alkylene group include a methylene group, an ethylene group, a triethylene group, and the like, but the alkylene group is not limited to these.

[0295] Specific examples of the arylene group include p-phenylene, m-phenylene, o-phenylene, biphenyl-4,4′-diyl, and the like, but are not limited thereto.

[0296] As the hydrolyzable silane compound (b), it is preferable to use a hydrolyzable silane represented by the formula (2).

[0297] As the hydrolyzable silane compound (a2), a hydrolyzable silane containing a hydrolyzable silane represented by formula (1) and formula (1-1) and a hydrolyzable silane (b) (selected from at least one of the hydrolyzable silanes represented by formula (2) and formula (3)) can be used, and the molar ratio of hydrolyzable silane represented by formula (1) and formula (1-1): hydrolyzable silane (b) is 3:97 to 100:0, or 30:70 to 100:0, or 50:50 to 100:0, or 70:30 to 100:0, or 97:3 to 100:0.

[0298] Specific examples of the hydrolyzable silane represented by the formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltripenzyloxysilane, methyltriphenethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, Silane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, etc.

[0299] Specific examples of the hydrolyzable silane represented by formula (3) include: methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane, phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxydisilane,

[0300] Furthermore, in addition to the above examples, the hydrolyzable silane compound (a2) may contain other hydrolyzable silanes than those exemplified above, within a range not impairing the effects of the present invention.

[0301] In a preferred embodiment of the present invention, the composition contains at least a hydrolysis condensate (a4) of the hydrolyzable silane compound (a2). In this case, the composition may contain an uncondensed (partial) hydrolyzate or an unreacted silane compound in addition to the hydrolysis condensate (a4) of the polysiloxane.

[0302] In a preferred embodiment of the present invention, the hydrolysis-condensation product (a4) contains: a hydrolysis-condensation product obtained by using at least one of the hydrolyzable silanes represented by the formula (1) and the hydrolyzable silanes represented by the formula (1-1), and at least one of the hydrolyzable silanes represented by the formula (2) and the hydrolyzable silanes represented by the formula (3), and other desired hydrolyzable silanes.

[0303] The hydrolysis condensate (also referred to as 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 the 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; from the viewpoint of achieving both storage stability and coating properties, the weight average molecular weight is preferably 700 or more, and more preferably 1,000 or more.

[0304] These weight average molecular weights are molecular weights obtained by GPC analysis in terms of polystyrene, and molecular weights obtained by GFC (aqueous GPC) analysis in terms of PEG / PEO.

[0305] GPC analysis can be performed, for example, using a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex KF803L, KF802, KF801, manufactured by Showa Denko KK), setting the column temperature to 40°C, using tetrahydrofuran as the eluent (elution solvent), setting the flow rate (flow velocity) to 1.0 ml / min, and using polystyrene (manufactured by Showa Denko KK) as a standard sample for analysis.

[0306] In addition, GFC analysis can be performed, for example, using a GFC device (trade name RID-10A, manufactured by Shimadzu Corporation), a GFC column (trade name Shodex SB-803HQ, manufactured by Showa Denko), setting the column temperature to 40°C, using water and 0.5M acetic acid and 0.5M sodium nitrate aqueous solution as eluents (elution solvents), setting the flow rate (flow velocity) to 1.0 ml / min, and using pullulan and PEG / PEO (manufactured by Showa Denko K.K.) as standard samples for analysis.

[0307] The hydrolysis-condensation products preferably used in the present invention are exemplified below, but are not limited to these.

[0308] [Chemistry 79]

[0309]

[0310] [Chemistry 80]

[0311]

[0312] [Chemistry 81]

[0313]

[0314] [Chemistry 82]

[0315]

[0316] [Chemistry 83]

[0317]

[0318] [Chemistry 84]

[0319]

[0320] [Chemistry 85]

[0321]

[0322] [Chemistry 86]

[0323]

[0324] Examples of silsesquioxane (also referred to as polysilsesquioxane) type polysiloxanes include formula (2-1-4), formula (2-2-4), and formula (2-3-4).

[0325] Formula (2-1-4) represents a ladder-type semi-siloxane, and n represents 1 to 1000, or 1 to 200. Formula (2-2-4) represents a cage-type semi-siloxane. Formula (2-3-4) represents an irregular semi-siloxane. In formula (2-1-4), formula (2-2-4), and formula (2-3-4), R is an organic group containing an amino group, or an organic group having an ionic functional group, and R is bonded to a silicon atom via a Si-C bond or a Si-N bond. As examples of these groups, the aforementioned examples can be shown.

[0326] The hydrolyzate (a3) ​​or hydrolysis-condensation product (a4) of the hydrolyzable silane compound (a2) can be obtained by hydrolyzing and condensing the hydrolyzable silane compound (a2).

[0327] 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, contains an alkoxysilyl group, an acyloxysilyl group or a halogenated silyl group as a hydrolyzable group.

[0328] For the hydrolysis and condensation of these hydrolyzable groups, usually 0.5 to 100 mol of water, preferably 1 to 10 mol of water, is used per 1 mol of the hydrolyzable groups.

[0329] In addition, during hydrolysis and condensation, a hydrolysis catalyst may be used for the purpose of promoting hydrolysis and condensation, or hydrolysis and condensation may be performed without using a hydrolysis catalyst. When a hydrolysis catalyst is used, usually 0.0001 to 10 moles of a hydrolysis catalyst may be used per 1 mole of the hydrolyzable group, preferably 0.001 to 1 mole of a hydrolysis catalyst may be used.

[0330] The reaction temperature for hydrolysis and condensation is usually above room temperature and below the reflux temperature of the organic solvent used for hydrolysis at normal pressure, for example, 20 to 110°C, for example, 20 to 80°C.

[0331] The hydrolysis may be complete, that is, all the hydrolyzable groups may be converted into silanol groups, or partial hydrolysis, that is, unreacted hydrolyzable groups may remain. That is, after the hydrolysis and condensation reaction, uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) or monomers (hydrolyzable silane compounds) may remain in the hydrolysis-condensation product. In addition, in the present invention, as mentioned above, the hydrolysis-condensation product also includes polymers obtained by hydrolysis and condensation of silane compounds, but some of them have not been condensed and Si-OH groups remain.

[0332] Examples of the hydrolysis catalyst that can be used in the hydrolysis condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples thereof are listed below, and these may be used alone or in combination of two or more.

[0333] Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-isopropoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-tert-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di-isopropoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium Titanium, di-sec-butoxy·bis(acetylacetonate)titanium, di-tert-butoxy·bis(acetylacetonate)titanium, monoethoxy·tri(acetylacetonate)titanium, mono-n-propoxy·tri(acetylacetonate)titanium, monoisopropoxy·tri(acetylacetonate)titanium, mono-n-butoxy·tri(acetylacetonate)titanium, mono-sec-butoxy·tri(acetylacetonate)titanium, mono-tert-butoxy·tri(acetylacetonate)titanium, tetra(acetylacetonate)titanium, triethoxy·mono(ethyl acetoacetate)titanium, tri-n-propoxy·mono(ethyl acetoacetate)titanium, triisopropoxy· Titanium chelate compounds such as mono(ethyl acetoacetate)titanium, tri-n-butoxy mono(ethyl acetoacetate)titanium, tri-sec-butoxy mono(ethyl acetoacetate)titanium, tri-tert-butoxy mono(ethyl acetoacetate)titanium, diethoxy bis(ethyl acetoacetate)titanium, di-n-propoxy bis(ethyl acetoacetate)titanium, di-isopropoxy bis(ethyl acetoacetate)titanium, di-n-butoxy bis(ethyl acetoacetate)titanium, di-sec-butoxy bis(ethyl acetoacetate)titanium, di-tert-butoxy bis(ethyl acetoacetate)titanium, monoethoxy tri(ethyl acetoacetate)titanium, mono-n-propoxy tri(ethyl acetoacetate)titanium, mono-isopropoxy tri(ethyl acetoacetate)titanium, mono-n-butoxy tri(ethyl acetoacetate)titanium, mono-sec-butoxy tri(ethyl acetoacetate)titanium, mono-tert-butoxy tri(ethyl acetoacetate)titanium, tetra(ethyl acetoacetate), mono(acetylacetonate)tri(ethyl acetoacetate)titanium, bis(acetylacetonate)bis(ethyl acetoacetate)titanium, and tri(acetylacetonate)mono(ethyl acetoacetate)titanium;Triethoxy zirconium mono(acetylacetonate), tri-n-propoxy zirconium mono(acetylacetonate), tri-isopropoxy zirconium mono(acetylacetonate), tri-n-butoxy zirconium mono(acetylacetonate), tri-sec-butoxy zirconium mono(acetylacetonate), tri-tert-butoxy zirconium mono(acetylacetonate), diethoxy zirconium bis(acetylacetonate), di-n-propoxy zirconium bis(acetylacetonate), di-isopropoxy zirconium bis(acetylacetonate), di-n-butoxy zirconium bis(acetylacetonate), di-sec-butoxy zirconium bis(acetylacetonate), di-tert-butoxy zirconium bis(acetylacetonate) Zirconium tetrakis(acetylacetonate), zirconium tri ... Zirconium chelate compounds such as sec-butoxy mono(ethyl acetoacetate) zirconium, tri-tert-butoxy mono(ethyl acetoacetate) zirconium, diethoxy bis(ethyl acetoacetate) zirconium, di-n-propoxy bis(ethyl acetoacetate) zirconium, diisopropoxy bis(ethyl acetoacetate) zirconium, di-n-butoxy bis(ethyl acetoacetate) zirconium, di-sec-butoxy bis(ethyl acetoacetate) zirconium, di-tert-butoxy bis(ethyl acetoacetate) zirconium, monoethoxy tris(ethyl acetoacetate) zirconium, mono-n-propoxy tris(ethyl acetoacetate) zirconium, monoisopropoxy tris(ethyl acetoacetate) zirconium, mono-n-butoxy tris(ethyl acetoacetate) zirconium, mono-sec-butoxy tris(ethyl acetoacetate) zirconium, mono-tert-butoxy tris(ethyl acetoacetate) zirconium, tetrakis(ethyl acetoacetate) zirconium, mono(acetylacetonate) tris(ethyl acetoacetate) zirconium, bis(acetylacetonate) bis(ethyl acetoacetate) zirconium, tris(acetylacetonate) mono(ethyl acetoacetate) zirconium; aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethyl acetoacetate)aluminum; and the like. ;

[0334] Examples of organic acids used as the hydrolysis catalyst include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric 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, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and trifluoromethanesulfonic acid.

[0335] Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, etc., but the inorganic acid is not limited to these.

[0336] Examples of the organic base as the hydrolysis catalyst 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.

[0337] Examples of the inorganic base as the hydrolysis catalyst include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like, but the present invention is not limited thereto.

[0338] 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.

[0339] As an example, in the present invention, the hydrolyzate (a3) ​​of the hydrolyzable silane compound (a2) (selected from the hydrolyzable silane represented by the formula (1) and the hydrolyzable silane represented by the formula (1-1), further selected from the hydrolyzable silane represented by the formula (2) and the hydrolyzable silane represented by the formula (3), and further other desired hydrolyzable silanes) is obtained by hydrolyzing the aforementioned hydrolyzable silane compound (a2) in the presence of an alkaline substance, particularly in the presence of an organic base, and preferably further condensing these hydrolyzates to form a hydrolysis condensate (a4) (polysiloxane).

[0340] Here, the basic substance is a basic catalyst added when the hydrolyzable silane is hydrolyzed, or an amino group present in the molecule of the hydrolyzable silane itself.

[0341] When the basic substance is an amino group present in the hydrolyzable silane molecule, examples thereof include silanes having an amino group on the side chain among the hydrolyzable silane compounds (a2) represented by the formula (1) or (1-1) exemplified above.

[0342] When a basic catalyst is added, the inorganic bases and organic bases described above as the hydrolysis catalysts may be mentioned, and organic bases are particularly preferred.

[0343] The hydrolyzate of the hydrolyzable silane is preferably hydrolyzed in the presence of a basic substance.

[0344] The above-mentioned composition may further contain a hydrolyzable silane, a hydrolyzate obtained by hydrolyzing the hydrolyzable silane in the presence of a basic substance, or a mixture thereof.

[0345] In addition, in the present invention, silsesquioxane obtained by hydrolyzing a silane having three hydrolyzable groups can be used. This silsesquioxane is a hydrolysis-condensation product (a4) obtained by hydrolyzing and condensing a 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.

[0346] As the hydrolysis condensate (a4), irregular type, ladder type, or cage type silsesquioxane can be used.

[0347] In addition, an organic solvent may be used as a solvent during the hydrolysis and condensation, and specific examples thereof include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentylnaphthalene; Methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, octanol, 2-ethylhexanol, sec-octanol, nonanol, 2,6-dimethyl-4-heptanol, decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methyl Monohydric alcohol solvents such as 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, etc.; acetone, methyl ethyl ketone, methyl-n-propyl Ketone solvents such as ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone acetone, diacetone alcohol, acetophenone, and fenchone; ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, di Alkane, dimethyl Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxylated triethylene glycol, 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, di Ether solvents such as propylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl 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 monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, lactic acid Ester solvents such as methyl ester, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc.; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, etc.; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, cyclopentane, 1,3-propane sultone, etc., but not limited to these. These solvents can be used alone or in combination of two or more.

[0348] After the hydrolysis reaction is completed, the reaction solution may be left as is, diluted, or concentrated, and if necessary, neutralized, or treated with an ion exchange resin to remove the hydrolysis catalyst such as the acid or base used for the hydrolysis and condensation. In addition, before or after such treatment, alcohol or water as a by-product, the used hydrolysis catalyst, etc. may be removed from the reaction solution by reduced pressure distillation or the like.

[0349] The hydrolysis condensate (a4) (polysiloxane) thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and this can be used as a composition for a resist pattern metallization process described later.

[0350] [(B): Acid compound not containing a carboxyl group (-COOH)]

[0351] The composition of the present invention contains an acid compound having no carboxyl group (—COOH) as the component (B).

[0352] The acid compound is preferably an acid compound containing a sulfonic acid group (-SO3H). Examples thereof include methanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecylbenzenesulfonic acid, phenolsulfonic acid, sulfosalicylic acid, camphorsulfonic acid, nonafluorobutanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, p-octylbenzenesulfonic acid, p-decylbenzenesulfonic acid, 4-octyl 2-phenoxybenzenesulfonic acid, and 4-carboxybenzenesulfonic acid.

[0353] The component (B) is preferably contained in a ratio of 0.5 to 15 parts by mass relative to 100 parts by mass of the component (A).

[0354] [Component (C): aqueous solvent]

[0355] 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 contains 100% water, that is, the aqueous solvent is composed of only water. In this case, it is not denied that when water is intended to be used as an aqueous solvent, there is a trace amount of organic solvents etc. contained in the water as impurities.

[0356] In addition, since the composition of the present invention is applied on the 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 the aqueous solvent and does not dissolve the resist pattern, such as an alcohol solvent or an ether solvent.

[0357] As such a solvent that does not dissolve the resist pattern, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; glycols such as ethyl cellosolve, butyl cellosolve, ethylene glycol, and diethylene glycol; glycol ethers such as propylene glycol monomethyl ether; ethers such as tetrahydrofuran (THF), etc., but not limited thereto. These water-soluble organic solvents may be used alone or in combination of two or more.

[0358] In addition, the water-soluble organic solvent may 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, for example, in terms of mass ratio, water:water-soluble organic solvent=0.1:99.9 to 99.9:0.1.

[0359] Furthermore, in addition to the water-soluble organic solvent, an organic solvent that is sparingly soluble in water or a hydrophobic organic solvent may be used in combination within a range not impairing the effects of the present invention.

[0360] [Preparation of composition]

[0361] The resist pattern metallization process composition of the present invention contains the aforementioned (A) component, (B) component, and (C) component.

[0362] The aforementioned composition, when containing the aforementioned (A) to (C) components and other desired components, can be produced by mixing the other components. In this case, a solution containing the (A) component (e.g., hydrolysis condensate (a4) etc.) can be prepared in advance, and the solution can be mixed with a solvent or other components.

[0363] The mixing order is not particularly limited. For example, components (B) and (C) may be added to a solution containing component (A) (e.g., a hydrolysis condensate (a4), etc.), and other components may be added to the mixture; or a solution containing component (A) (e.g., a hydrolysis condensate (a4), etc.), a solvent, and other components may be mixed simultaneously.

[0364] Alternatively, filtration may be performed using a submicron filter or the like during the production of the composition or after all components are mixed.

[0365] In the composition for resist pattern metallization process of the present invention, when the hydrolysis condensate (a4) is contained as the component (A), in particular, in order to stabilize 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. In addition, even when a component other than (a4) is contained as the component (A), the following components may be contained as long as the effects of the present invention are not impaired.

[0366] Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid.

[0367] 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, and salicylic acid. Among them, oxalic acid and maleic acid are preferred.

[0368] When these acids are added, the amount thereof added may be 0.5 to 15 parts by mass based on 100 parts by mass of the component (A).

[0369] However, since the addition of an acid containing a carboxyl group (—COOH) may cause deterioration in the coating properties of the composition of the present invention, it is preferably not incorporated into the composition of the present invention.

[0370] The alcohol is preferably one that is easily dispersed by heating after coating, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, etc. When an alcohol is added, the amount thereof added may be 0.001 to 20 parts by mass relative to 100 parts by mass of the composition of the present invention.

[0371] 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, N,N,N',N'-tetraethyl-1,2-propylenediamine, 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-butanediamine, N, N,N',N'-tetraethyl-1,2-butanediamine, N,N,N',N'-tetrapropyl-1,2-butanediamine, N,N,N',N'-tetraisopropyl-1,2-butanediamine, N,N,N',N'-tetrabutyl-1,2-butanediamine, N,N,N',N'-tetraisobutyl-1,2-butanediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-tetraethyl-1,3-butanediamine, N,N,N',N'-tetrapropyl-1,3-butanediamine, N,N,N',N'-tetraisopropyl-1,3-butanediamine, N,N,N',N'-tetrabutyl The organic amine may be added in an amount of 0.001 to 20 parts by mass relative to 100 parts by mass of the composition of the present invention.

[0372] Examples of the photoacid generator include: Salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, etc., but are not limited to these.

[0373] As Specific examples of salt compounds include diphenyl iodide Hexafluorophosphate, diphenyl iodide Trifluoromethanesulfonate, diphenyl iodide Nonafluorobutanesulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Camphorsulfonate and bis(4-tert-butylphenyl)iodide Iodine triflate The invention also includes sulfonium salt compounds, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butylsulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium 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, but are not limited to these.

[0374] Specific examples of the sulfonyl imide compound include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0375] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-ditoluenesulfonyl)diazomethane, and methanesulfonyl-p-toluenesulfonyldiazomethane.

[0376] The photoacid generators mentioned above may be used alone or in combination of two or more.

[0377] When a photoacid generator is used, the ratio thereof is 0.01 to 30 parts by mass, or 0.1 to 20 parts by mass, or 0.5 to 10 parts by mass relative to 100 parts by mass of the component (A).

[0378] Examples of the surfactant include nonionic surfactants, anionic surfactants, fluorine-based surfactants, cationic surfactants, silicone-based surfactants, and UV-curable surfactants.

[0379] Examples thereof include 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 octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate; esters, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and the like; trade names EFTOP EF301, EF303, EF352 (Mitsubishi Material Electronics Chemicals Co., Ltd. (formerly TOHKEM PRODUCTS)), trade names Megafac F171, F173, R-08, R-30, R-40, R-40N (DIC Co., Ltd.), FLORADO FC430, FC431 (Sumitomo 3M Co., Ltd.), trade names ASHIGADO AG710, Surflon Fluorine-based surfactants such as S-382, SC101, SC102, SC103, SC104, SC105, and 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, and BYK348 (manufactured by BYK Co., Ltd., trade name). In addition, cationic surfactants such as distearyldimethylammonium chloride, alkyldimethylbenzylammonium chloride, benzethonium chloride, cetylpyridinium chloride, cetyltrimethylammonium bromide, and dequalinium chloride; anionic surfactants such as octanoate, decanoate, octylsulfonate, decanoic acid sulfonate, palmitate, perfluorobutanesulfonate, and dodecylbenzenesulfonate; and UV-curable surfactants such as BYK307, BYK333, BYK381, BYK-UV-3500, BYK-UV-3510, and BYK-UV-3530 (manufactured by BYK, trade names) can be listed.

[0380] These surfactants may be used alone or in combination of two or more. When a surfactant is used, the ratio 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, relative to 100 parts by mass of component (A).

[0381] [Resist pattern metallization method]

[0382] The composition for metallization of resist pattern of the present invention can form a resist pattern in which the composition components are permeated in the resist by contacting the resist pattern surface after mask exposure. In this way, a method of making the composition permeate into the resist, especially metallizing the resist pattern by the metal components in the composition, is also the object of the present invention.

[0383] More specifically, the present invention is directed to a resist pattern metallization method that includes the following steps [a1] to [d1] and can provide a resist pattern in which the composition component is permeated into the resist.

[0384] [a1] Step of applying a resist solution on a substrate

[0385] [b1] Step of exposing and developing the resist film

[0386] [c1] A step of applying the resist pattern metallization composition of the present invention to the resist pattern during or after development to form a coating film on the resist pattern

[0387] [d1] A step of heating the coating film to form a heated coating film

[0388] As the substrate used in step [a1], there can be listed substrates used in the manufacture of semiconductor devices, for example: silicon wafer substrates, substrates covered with silicon / silicon dioxide, silicon nitride substrates, glass substrates, ITO substrates, polyimide plates, and substrates covered with low dielectric constant materials (low-k materials), etc.

[0389] 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: a positive photoresist composed of a novolac resin and 1,2-naphthoquinone diazosulfonate; a chemically amplified photoresist composed of a binder having a group that increases the alkali dissolution rate by acid decomposition and a photoacid generator; a chemically amplified photoresist composed of a low molecular weight compound that increases the alkali dissolution rate of the photoresist by acid decomposition, an alkali-soluble binder, and a photoacid generator; and a chemically amplified photoresist composed of a binder having a group that increases the alkali dissolution rate by acid decomposition, a low molecular weight compound that increases the alkali dissolution rate of the photoresist by acid decomposition, and a photoacid generator.

[0390] Specific examples of commercially available products include, but are not limited to, APEX-E manufactured by Shiplay Co., Ltd., PAR710 manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. In addition, for example, fluorine-containing polymer photoresists described in Proc. SPIE, Vol. 3999, 300-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), or Proc. SPIE, Vol. 3999, 365-374 (2000) can be cited.

[0391] Furthermore, a resist for electron beam lithography (also referred to as electron beam resist) or a resist for EUV lithography (also referred to as EUV resist) may be used instead of the aforementioned photoresist.

[0392] As the electron beam resist, either negative type or positive type can be used. Specific examples thereof include: a chemically amplified resist composed of an acid generator and a binder having a group that changes the alkali dissolution rate by acid decomposition; a chemically amplified resist composed of an alkali-soluble binder, an acid generator, and a low molecular compound that changes the alkali dissolution rate of the resist by acid decomposition; a chemically amplified resist composed of an acid generator, a binder having a group that changes the alkali dissolution rate by acid decomposition, and a low molecular compound that changes the alkali dissolution rate of the resist by acid decomposition; a non-chemically amplified resist composed of a binder having a group that changes the alkali dissolution rate by electron beam decomposition; a non-chemically amplified resist composed of a binder having a portion where the alkali dissolution rate changes by electron beam cutting, etc. When these electron beam resists are used, a resist pattern can be formed in the same manner as when a photoresist is used with an electron beam as an irradiation source.

[0393] In addition, as the EUV resist, a methacrylate resin-based resist can be used.

[0394] After applying the resist solution, the resist (film) having a film thickness of, for example, 10 to 1000 nm can be obtained by firing at, for example, a firing temperature of 70 to 150° C. and a firing time of 0.5 to 5 minutes.

[0395] The resist solution, developer or the coating material described below can be applied or coated by spin coating, dipping, spraying or the like, and spin coating is particularly preferred.

[0396] Furthermore, the method may include a step [a1-0] of forming a resist underlayer film on the substrate before the step [a1]. The resist underlayer film has an antireflection function and an organic hard mask function.

[0397] Specifically, before applying the resist solution in step [a1], step [a1-0] of forming a resist underlayer film on the substrate is performed, and step [a1] of applying the resist solution on the resist underlayer film may be performed. In step [a1-0], a resist may be formed on the resist underlayer film (also referred to as an organic underlayer film) after forming the resist on the semiconductor substrate, or a silicon hard mask may be further formed on the resist underlayer film, and the resist may be formed on the resist underlayer film.

[0398] The resist underlayer film used in the above step [a1-0] can be used to prevent diffuse reflection when the upper resist film is exposed and to improve the 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 film with a film thickness of 1 to 1000 nm on the semiconductor substrate.

[0399] In addition, the resist underlayer film used in the above step [a1-0] may be a hard mask using an organic resin, and in this case, a material with a high carbon content and a low hydrogen content is used. Examples thereof include polyethylene naphthalene resins, carbazole novolac resins, phenol novolac resins, naphthol novolac resins, etc. These can be formed into a film with a thickness of 5 to 1,000 nm on a semiconductor substrate.

[0400] In addition, as a silicon hard mask used in the above step [a1-0], a polysiloxane obtained by hydrolyzing a hydrolyzable silane can be used. For example, polysiloxane obtained by hydrolyzing tetraethoxysilane, methyltrimethoxysilane, and phenyltriethoxysilane can be used. These can be formed into a film with a thickness of 5 to 200 nm on the above resist underlayer film.

[0401] In step [b1], exposure of the resist film is performed through a designated mask.

[0402] During exposure, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), EUV light (wavelength 13.5nm), electron beam, etc. can be used. After exposure, post-exposure baking (PEB: Post Exposure Bake) can be performed as needed. The post-exposure baking temperature can be appropriately selected from 70°C to 150°C and the heating time can be appropriately selected from 0.3 to 10 minutes.

[0403] Next, the photoresist is developed with a developer. In this way, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed to form a photoresist pattern.

[0404] At this time, as a developer, for example, there can be mentioned: an aqueous solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, etc.; an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc.; an alkaline aqueous solution (alkaline developer) such as an aqueous solution of an amine such as ethanolamine, propylamine, ethylenediamine, etc. Furthermore, a surfactant, etc. may also be added to these developers. As the conditions for development, a temperature of 5 to 50° C. and a time of 10 to 600 seconds are appropriately selected.

[0405] In the present invention, an organic solvent may be used as a developer. After exposure, the photoresist is developed with a developer (solvent). In this way, when a positive photoresist is used, for example, the photoresist in the unexposed portion is removed to form a photoresist pattern.

[0406] At this time, examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, 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, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, ethyl 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, and the like. Furthermore, a surfactant or the like may be added to these developing solutions. As the development conditions, the temperature is appropriately selected from 5 to 50° C. and the time is appropriately selected from 10 to 600 seconds.

[0407] As step [c1], the composition of the present invention is applied to the resist pattern during or after development, preferably on the resist pattern after development, to form a coating film on the surface of the resist pattern. Here, the coating film is formed by covering the resist pattern, that is, the coating film is formed by covering the upper part, sidewalls and bottom of the resist pattern.

[0408] At this time, the thickness of the coating film is appropriately determined in consideration of the reduction in film thickness due to the height or space width of the resist pattern, evaporation of the solvent, etc., and the target thickness of the coating film after heating.

[0409] Step [d1] is a step of heating the aforementioned coating film to form a heated coating film. The heating is preferably performed at a firing temperature of 80 to 200° C. for 0.5 to 5 minutes. During the heating process, the composition components of the present invention penetrate into the resist pattern.

[0410] By the method described above, a resist pattern in which the composition components are permeated in the resist can be obtained, and at the same time, a heated coating film is formed on the surface of the resist pattern. The thickness of the heated coating film measured from the surface of the resist pattern varies depending on the height or space width of the resist pattern and cannot be generally specified, but can be, for example, about 1 nm to 20 nm.

[0411] Furthermore, the method of the present invention is aimed at a resist pattern metallization method comprising the following steps [a2] to [e2] and providing a resist pattern in which the composition component is infiltrated into the resist.

[0412] [a2] Step of applying a resist solution on a substrate

[0413] [b2] Step of exposing and developing the resist film

[0414] [c2] A step of applying the resist pattern metallization process composition of the present invention to the resist pattern during or after development to form a coating film on the resist pattern

[0415] [d2] A step of heating the coating film to form a heated coating film

[0416] [e2] A step of removing the heated coating film by water or a developer

[0417] Here, steps [a2], [b2], and [d2] can be performed in the same order as described in the aforementioned steps [a1] (including [a1-0]), [b1], and [d1], respectively.

[0418] In step [c2], the composition of the present invention is applied to the resist pattern during or after development, preferably on the resist pattern after development. In this case, the difference from step [c1] is that the resist pattern is buried to form a coating film. That is, a coating film having a thickness from the bottom of the resist pattern exceeding 100% of the height of the pattern is formed. 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] (removal solution for removing the unnecessary heated coating film or other various conditions).

[0419] Thereafter, step [e2] is a step of removing the heated coating film obtained by heating in step [d2] with water or a developer. As the developer, the same developer as that used in the previous step [b2] can be used. As water, ion exchange water, ultrapure water, etc. used in this field can be used.

[0420] Through this step, the unnecessary heated coating film can be removed and a resist pattern infiltrated with the composition components of the present invention can be obtained. However, depending on the conditions for removing the heated coating film, the heated coating film may be completely removed from the surface of the resist pattern, or the heated coating film may remain on the surface of the resist pattern. The thickness of the heated coating film remaining on the surface of the resist pattern varies depending on the height or spatial width of the resist pattern, the conditions of step [e2] (the removal liquid used to remove the unnecessary heated coating film, or other various conditions), so it cannot be generally specified, but is usually less than 20 nm. The thickness of the heated coating film calculated from the surface of the resist pattern can be adjusted by changing the conditions of step [e2]. In addition, depending on the conditions of step [e2], the heated coating film may be completely removed from the surface of the resist pattern, and the resist pattern itself may be further thinned.

[0421] In addition, after the aforementioned step [d1], the process may include a step of removing the coating film subjected to the heating step [d1] with water or a developer, for example, in order to thin the heated coating film formed on the surface of the resist pattern, as in the aforementioned step [d2]. The water and developer used here may be the same as those used in the aforementioned step [b1].

[0422] Respectively Fig. 9 A schematic diagram showing an example of a resist pattern metallization method including steps [a1] to [d1], Fig.10 Schematic diagram showing an example of a method for metallizing a resist pattern including steps [a2] to [e2] (in addition, these figures also include the steps of processing a substrate in the [method for manufacturing a semiconductor device] described later ([f1], [f2] in the figure)). The present invention is not limited to the steps shown in these figures.

[0423] In the figure, Sub represents a substrate; UC represents an underlayer film of the resist (carbon-containing layer (SOC), an organic anti-reflection film (BARC), an inorganic anti-reflection film (Si-HM), etc.); and PR represents a resist film.

[0424] [Method for manufacturing semiconductor device]

[0425] The present invention is also directed to a method for manufacturing a semiconductor device, and the method for manufacturing a semiconductor device is a step of processing a substrate using the metallized resist pattern obtained by the method, following the aforementioned "resist pattern metallization method".

[0426] In addition, when a resist underlayer film (carbon-containing layer (SOC), organic anti-reflection film (BARC), inorganic anti-reflection 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 layers (films) thereunder. Hereinafter, a detailed description will be given in conjunction with the case where a resist underlayer film is formed, but the present invention is not limited to the following.

[0427] When a resist underlayer film is formed, first, the metalized resist pattern (upper layer) is used as a protective film to remove (pattern) the resist underlayer film ( Fig. 9 and Fig.10 f1 and f2 in the figure).

[0428] The removal of the resist underlayer is performed 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.

[0429] At this time, the removal of the resin-based lower film (organic lower film) is preferably carried out by dry etching based on oxygen-based gas. This is because the metallized resist pattern of the present invention is difficult to remove by dry etching based on oxygen-based gas. In addition, nitrogen-based gas can also be mixed in oxygen-based gas for dry etching.

[0430] In addition, in the case of providing a silicon hard mask, it is preferred to use a halogen-based gas, such as a fluorine-based gas, for example, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but not limited to these.

[0431] Through the above-mentioned dry etching, a patterned resist underlayer film and a patterned silicon hard mask can be obtained.

[0432] Next, the semiconductor substrate is processed using the metalized resist pattern as a protective film, or, if a resist underlayer film is provided, using the metalized resist pattern and the patterned resist underlayer film as protective films. The semiconductor substrate is preferably processed by dry etching using a fluorine-based gas.

[0433] Examples of the fluorine-based gas include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0434] [Example]

[0435] Hereinafter, the present invention will be described in more detail with reference to synthesis examples and working examples, but the present invention is not limited to the following.

[0436] 〔1〕Synthesis of polymer (hydrolysis condensation product)

[0437] (Synthesis example 1)

[0438] 5.89 g of water and 120.54 g of tetrahydrofuran were placed in a 500 ml flask, and while the mixed solution was stirred with a magnetic stirrer, 40.18 g of aminopropyltriethoxysilane (100 mol % in all silanes) was added dropwise to the mixed solution.

[0439] 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, 120.54 g of water was added to the reaction solution, and ethanol, tetrahydrofuran and water as reaction by-products were distilled off under reduced pressure, and concentrated to obtain an aqueous solution of a hydrolysis condensate (polysiloxane).

[0440] Water was further added to make the solvent ratio of water 100% (solvent consisting of only water), and the concentration was adjusted so that the solid residue at 140° C. was 20% by mass. The obtained polymer corresponded to the formula (2-1-1).

[0441] (Synthesis example 2)

[0442] 89.99 g of water was put into a 500 ml flask, and while the mixed solution was stirred with a magnetic stirrer, 30.00 g (100 mol % in all silanes) of 3-(N,N-dimethylaminopropyl)trimethoxysilane was added dropwise to the mixed solution.

[0443] After the dropwise addition, the flask was transferred to an oil bath adjusted to 40° C. and reacted for 240 minutes. The reaction solution was then cooled to room temperature, 179.98 g of water was added to the reaction solution, and methanol and water as reaction by-products were distilled off under reduced pressure, followed by concentration to obtain an aqueous solution of a hydrolysis condensate (polysiloxane).

[0444] Water was further added to make the solvent ratio of water 100% (solvent consisting of only water), and the concentration was adjusted so that the solid residue at 140° C. was 20% by mass. The obtained polymer corresponded to the formula (2-4-1).

[0445] (Synthesis example 3)

[0446] 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 nitric acid aqueous solution.

[0447] After adding 1M nitric acid aqueous 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, 179.98 g of water was added to the reaction solution, and methanol, acetone and water as reaction by-products were distilled off under reduced pressure, and concentrated to obtain an aqueous solution of a hydrolysis condensate (polysiloxane).

[0448] Water was further added to make the solvent ratio of water 100% (solvent consisting of only water), and the concentration was adjusted so that the solid residue at 140° C. was converted to 20 mass %. The obtained polymer corresponded to the formula (2-9-2).

[0449] (Synthesis Example 4)

[0450] 91.16 g of water was placed in a 500 ml flask, and while the mixed solution was stirred with a magnetic stirrer, 22.23 g of dimethylaminopropyltrimethoxysilane and 8.16 g of triethoxysilylpropylsuccinic anhydride were added dropwise to the mixed solution.

[0451] 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, 91.16 g of water was added to the reaction solution, and methanol, ethanol and water as reaction byproducts were distilled off under reduced pressure, and concentrated to obtain an aqueous solution of a hydrolysis condensate (polysiloxane).

[0452] Water was further added to make the solvent ratio of water 100% (solvent consisting of only water), and the concentration was adjusted so that the solid residue at 140° C. was converted to 20% by mass. The obtained polymer corresponded to the formula (2-10-2).

[0453] (Synthesis Example 5)

[0454] 93.13 g of a 0.5 M hydrochloric acid aqueous solution was placed in a 300 ml flask, and while the mixed solution was stirred with a magnetic stirrer, 6.87 g of aminopropyltriethoxysilane (100 mol % in all silanes) was added dropwise to the mixed solution.

[0455] After the dropwise addition, the flask was transferred to an oil bath adjusted to 23° C. and reacted for 5 days. Thereafter, ethanol and water produced as by-products of the reaction were distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensate (polysiloxane).

[0456] Water was further added to make the solvent ratio of water 100% (solvent consisting of only water), and the concentration was adjusted so that the solid residue at 140° C. was 20 mass %. The obtained polymer was equivalent to the formula (2-1-4) as a ladder-type silsemioxane, and R was ammonium chloride propyl group (R=C3H6NH3+Cl-).

[0457] Thereafter, 6.8 g of anion exchange resin was added to remove chloride ions. The resulting polymer corresponded to the formula (2-1-4) which is a ladder-type silsesquioxane, and R was an aminopropyl group (R = C3H6NH2).

[0458] (Synthesis Example 6)

[0459] 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 all silanes) was added dropwise to the mixed solution. After stirring at room temperature for 5 minutes, 8.73 g of tetraethoxysilane (70 mol % of all silanes) was added dropwise to the aqueous solution.

[0460] After the dropwise addition, the flask was transferred to an oil bath adjusted to 23°C and reacted for 2 hours. Thereafter, methanol, ethanol and water as reaction by-products were distilled off under reduced pressure, and the mixture was concentrated to obtain a hydrolysis condensate (polysiloxane). Thereafter, ethanol and water as reaction by-products were distilled off under reduced pressure at 50°C and then at 100°C, and the mixture was concentrated to obtain a hydrolysis condensate (polysiloxane).

[0461] Thereafter, water was added to make the solvent ratio of water 100% (solvent consisting of only water), and the concentration was adjusted so that the solid residue at 140° C. was converted to 20% by mass. The obtained polymer corresponds to the formula (2-5-5).

[0462] [2] Preparation of composition

[0463] 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 polymer-containing coating solutions. The amounts of each additive in Table 1 are expressed in parts by mass.

[0464] In addition, the addition amount of the polymer (polysiloxane) in Table 1 indicates the addition amount of the polymer itself, not the addition amount of the polymer solution.

[0465] In Table 1, NfA represents nonafluorobutanesulfonic acid, DBSA represents dodecylbenzenesulfonic acid, and Ac represents acetic acid.

[0466] [Table 1]

[0467] Polysiloxane additive Solvents Example 1-1 Synthesis example 1 Nf water (parts by mass) 0.5 0.005 100 Example 2-1 Synthesis example 2 Nf water (parts by mass) 0.5 0.005 100 Example 3-1 Synthesis example 3 Nf water (parts by mass) 0.5 0.005 100 Example 4-1 Synthesis example 4 Nf water (parts by mass) 0.5 0.005 100 Example 5-1 Synthesis example 5 DBSA water (parts by mass) 0.5 0.005 100 Example 6-1 Synthesis example 6 Nf water (parts by mass) 0.5 0.005 100 Example 1-2 Synthesis example 1 Nf water (parts by mass) 5 0.05 100 Example 2-2 Synthesis example 2 Nf water (parts by mass) 5 0.05 100 Example 3-2 Synthesis example 3 Nf water (parts by mass) 5 0.05 100 Example 4-2 Synthesis example 4 Nf water (parts by mass) 5 0.05 100 Example 5-2 Synthesis example 5 Nf water (parts by mass) 5 0.05 100 Example 6-2 Synthesis example 6 DBSA water (parts by mass) 5 0.05 100 Comparative Example 1 Synthesis example 2 water (parts by mass) 0.5 100 Comparative Example 2 Synthesis example 2 Ac water (parts by mass) 0.5 0.05 100

[0468] [3] Preparation of organic resist underlayer film-forming composition

[0469] Under nitrogen, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a 100 ml four-necked flask, and 1,4-dihydro-1,4-dione was added. Alkane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was stirred and heated to 100°C to dissolve the mixture and initiate polymerization. After 24 hours, the mixture was left to cool to 60°C.

[0470] Chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added to the reaction mixture after cooling, and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to cause precipitation.

[0471] The obtained precipitate was filtered and dried in a reduced pressure dryer at 80° C. for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL).

[0472] In addition, the measurement results of 1H-NMR of PCzFL are as follows:

[0473] 1H-NMR (400MHz, DMSO-d6): δ7.03-7.55 (br, 12H), δ7.61-8.10 (br, 4H), δ11.18 (br, 1H).

[0474] The weight average molecular weight Mw of PCzFL was 2,800 in terms of polystyrene by GPC, and the polydispersity Mw / Mn was 1.77.

[0475]

[0476] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluril (manufactured by Nippon Science Instruments Co., Ltd. (formerly Mitsui Science Co., Ltd.), trade name: Pawdalen 1174) as a crosslinking agent, and pyridinium p-toluenesulfonate as a catalyst were mixed. 0.30 g of propylene glycol monomethyl ether acetate (DIC Corporation), 0.06 g of Megaffac R-30 (trade name) as a surfactant was mixed, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate. Thereafter, the mixture was filtered using a polyethylene microfilter having a pore size of 0.10 μm, and further filtered using a polyethylene microfilter having a pore size of 0.05 μm, thereby preparing an organic resist underlayer film-forming composition used in a photolithography process through a multilayer film.

[0477] 〔4〕Applicability evaluation test

[0478] The compositions obtained in Examples 1-1 to 6-1, Examples 1-2 to 6-2, and Comparative Examples 1 and 2 were respectively applied on a silicon wafer to form a coating film using a spinner, and heated on a hot plate at 100°C for 1 minute to form a Si-containing film (film thickness of 20 nm).

[0479] The obtained Si-containing film was observed using an optical microscope. As a result of the observation, the film having uniform film formation was evaluated as "good", and the film having a stripe pattern and not uniform film formation was evaluated as "poor". The obtained results are shown in Table 2. In addition, optical micrographs (magnification: 50K) of the Si-containing films obtained in Example 4-2 and Comparative Example 2 are shown in Table 2. Figure 1 ((a) Example 4-2, (b) Comparative Example 2).

[0480] [Table 2]

[0481] Observation results of optical microscope Example 1-1 good Example 2-1 good Example 3-1 good Example 4-1 good Example 5-1 good Example 6-1 good Example 1-2 good Example 2-2 good Example 3-2 good Example 4-2 good Example 5-2 good Example 6-2 good Comparative Example 1 bad Comparative Example 2 bad

[0482] [5] Test to confirm the penetration of Si component into resist

[0483] An EUV resist solution (methacrylate resin 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 film thickness of 30 nm.

[0484] Thereafter, the composition obtained in Example 4-2 was applied to a photoresist film using a spinner to form a coating film, and heated on a hot plate at 100° C. for 1 minute, thereby forming a film containing Si (film thickness of 100 nm) while allowing the aforementioned composition components (particularly silane components) to penetrate into the EUV resist. Thereafter, ultrapure water was used to remove the composition components that did not penetrate into the resist, and an EUV resist film infiltrated with the aforementioned composition components was obtained. Thereafter, the EUV resist film was evaluated by TOF-SIMS to confirm whether the Si component was confirmed in the film.

[0485] In addition, as a comparative example, the EUV resist film was directly evaluated by TOF-SIMS.

[0486] The obtained results are shown in Table 3. In addition, TOF-SIMS data of the EUV resist film to which the composition of Example 4-2 was applied are shown in Figure 2 .

[0487] In addition, the measurement conditions of TOF-SIMS are as follows.

[0488] Primary Ion: Bi 3++

[0489] Sputtering ions: Cs

[0490] Area (measurement area): 50×50μm 2

[0491] Sputtering area: 250×250μm 2

[0492] Polarity: Nega

[0493] [Table 3]

[0494] TOF-SIMS measurement results Example 4-2 Contains Si Comparative Example No Si component

[0495] [6] Fabrication of resist pattern by ArF exposure and metallization of resist pattern (1)

[0496] (Resist patterning evaluation: Evaluation via a PTD (positive tone alkaline development) step of performing alkaline development)

[0497] The organic resist underlayer film-forming composition 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 film thickness of 200 nm.

[0498] A commercially available ArF resist solution (manufactured by JSR Corporation, trade name: AR2772JN) was applied on the A layer using a spinner and heated at 110° C. for 1 minute to form a photoresist film (B layer) having a thickness of 100 nm on a hot plate.

[0499] The photoresist film was exposed using a Nikon NSR-S307E scanner (wavelength 193 nm, NA, σ: 0.85, 0.93 / 0.85) through a mask set so that the line width of the photoresist after development and the width between the lines were 0.062 μm, that is, through a mask set so that a dense line with a line / space (L / S) of 0.062 μm = 1 / 1 was formed after development. Thereafter, the film was baked on a hot plate at 100° C. for 60 seconds, cooled, and developed with a 2.38% alkaline aqueous solution for 60 seconds to form a resist pattern.

[0500] Then, the compositions (coating solutions) of Examples 1-1 to 6-1 were applied to the resist pattern (film thickness 5 nm), and the 2.38 mass % tetramethylammonium aqueous solution used for development was replaced with the compositions of these Examples. In addition, 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.

[0501] Thereafter, the silicon wafer was rotated 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 heated coating film and to allow the composition components to penetrate from the sidewalls and upper portion of the resist pattern.

[0502] The photoresist pattern obtained in this way was observed in cross section and on top of the pattern to confirm and evaluate the pattern shape and line width roughness.

[0503] When observing the pattern shape, those without major pattern peeling, undercut, or thickening of the line bottom (footing) were evaluated as "good", while those with undercut or footing were evaluated as "poor (undercut)", "poor (footing)", etc.

[0504] Regarding line width roughness, a line width 3 sigma value of 6.0 nm or more was evaluated as “poor”, and a line width 3 sigma value of less than 6.0 nm was evaluated as “good”.

[0505] The obtained results are shown in Table 4. In addition, scanning microscope photographs (magnification: 100K, pattern top, pattern cross section) of the resist pattern to which the composition of Example 4-1 was applied and the resist pattern of the comparative example are shown in Figure 3 (Example 4-1) and Figure 4 (Comparative example).

[0506] Further thereafter, using the resist pattern infiltrated with the composition components as a mask, dry etching is performed using O 2 and N 2 gases, and the pattern is transferred to the organic lower layer film (layer A).

[0507] The obtained patterns were evaluated as “poor” if the line width variation value before and after dry etching was 10 nm or more, and “good” if it was less than 10 nm.

[0508] The obtained results are shown in Table 4. In addition, scanning microscope photographs (magnification: 100K, pattern top, pattern cross section) of the resist pattern and transfer pattern of the composition of Application Example 4-1 after dry etching and the resist pattern and transfer pattern of the comparative example after dry etching are shown in Table 4. Figure 5 (Example 4-1) and Figure 6 (Comparative example).

[0509] [Table 4]

[0510]

[0511] [7] Fabrication of resist pattern by ArF exposure and metallization of resist pattern (2)

[0512] (Resist patterning evaluation: evaluation via PTD step with alkaline development)

[0513] The organic resist underlayer film-forming composition 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 film thickness of 200 nm.

[0514] A commercially available ArF resist solution (manufactured by JSR Corporation, trade name: AR2772JN) was applied on 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 film thickness of 100 nm.

[0515] The photoresist film was exposed using a Nikon NSR-S307E scanner (wavelength 193 nm, NA, σ: 0.85, 0.93 / 0.85) through a mask set so that the line width and the width between lines of the photoresist after development were 0.062 μm, that is, through a mask set so that a dense line with a line / space (L / S) of 0.062 μm = 1 / 1 was formed after development. Thereafter, the film was baked on a hot plate at 100° C. for 60 seconds, cooled, and developed with a 2.38% alkaline aqueous solution for 60 seconds to form a resist pattern.

[0516] Then, the compositions (coating solutions) of Examples 1-2 to 6-2 were applied to the 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. In addition, 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.

[0517] Thereafter, the silicon wafer was rotated 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 heated coating film and to allow the composition components (particularly the silane component) to penetrate from the sidewalls and upper portion of the resist pattern.

[0518] Thereafter, a 2.38 mass % tetramethylammonium aqueous solution was applied again to remove the composition components that had not penetrated into the resist pattern.

[0519] The photoresist pattern obtained in this way was observed in cross section and on top of the pattern to confirm and evaluate the pattern shape and line width roughness.

[0520] When observing the pattern shape, those without major pattern peeling, undercutting, or thickening (hemming) of the line bottom were evaluated as "good", while those with undercutting or hemming were evaluated as "poor (undercut)", "poor (hem)", etc.

[0521] In addition, regarding line width roughness, a line width 3 sigma value of 6.0 nm or more was evaluated as “poor”, and a line width 3 sigma value of less than 6.0 nm was evaluated as “good”.

[0522] The obtained results are shown in Table 5.

[0523] Further thereafter, using the resist pattern infiltrated with the composition components as a mask, dry etching is performed with O 2 and N 2 gases, and the pattern is transferred to the organic lower layer film (layer A).

[0524] The obtained patterns were evaluated as “poor” if the line width variation value before and after dry etching was 10 nm or more, and “good” if it was less than 10 nm.

[0525] The obtained results are shown in Table 5.

[0526] [Table 5]

[0527]

[0528] In Example 4-2, the line pattern size before dry etching changed from 62 nm to 72 nm, which means that the composition components covered both sides and the upper side of the resist line with a film thickness of 5 nm.

[0529] 〔8〕Resist patterning by EUV exposure and metallization of resist patterns: positive alkaline development

[0530] The organic resist underlayer film-forming composition 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 film thickness of 90 nm.

[0531] The EUV resist layer (B) was formed by spin-coating an EUV resist solution (methacrylate resin resist) thereon and heating at 130° C. for 1 minute. This was exposed using an EUV exposure apparatus (NXE3300) under the conditions of NA=0.33, σ=0.90 / 0.67, dipole 45 (exposure amount 49 mJ, line and space of pattern: 22 mm).

[0532] After exposure, post-exposure heating (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).

[0533] Then, the composition (coating liquid) of Example 4-1 was coated on the resist pattern (film thickness 5 nm), and the 2.38 mass % tetramethylammonium aqueous solution used for development was replaced with the composition of Example 4-1. In addition, 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.

[0534] Thereafter, the silicon wafer was rotated 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 heated coating film and to allow the composition components (particularly the silane component) to penetrate from the sidewalls and upper portion of the resist pattern.

[0535] Thereafter, a 2.38 mass % tetramethylammonium aqueous solution was applied again to remove the composition components that had not penetrated into the resist pattern.

[0536] The photoresist pattern obtained in this way was evaluated by observing the pattern cross section and the pattern top to confirm the pattern shape.

[0537] When observing the pattern shape, a pattern without major peeling, undercutting, or thickening (hemming) of the line bottom was evaluated as "good", while an undesirable state in which the resist pattern peeled and collapsed was evaluated as "collapsed".

[0538] The obtained results are shown in Table 6. In addition, scanning microscope photographs (magnification: 200K, upper part of the pattern) of the resist pattern to which the composition of Example 4-1 was applied and the resist pattern of the comparative example are shown in Table 6. Figure 7 (Example 4-1) and Figure 8 (Comparative example).

[0539] [Table 6]

[0540] 22nm line Example 4-1 good Comparative Example 1 collapse

Claims

1. A method for manufacturing a semiconductor device, comprising: The step of applying a resist solution on the substrate; a step of exposing and developing the resist film; A step of applying a composition on the resist pattern during or after the development to form a coating film on the resist pattern; The step of heating the coating film to form a heated coating film, thereby providing a resist pattern in which the composition components are permeated in the resist; as well as a step of processing a lower layer of the resist pattern using the resist pattern as a protective film, The composition contains: 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 of the hydrolyzable silane compound, wherein the metal oxide a1 is an oxide of at least one metal selected from the group consisting of germanium, indium, tin, and vanadium; Component B: an acid compound that does not contain a carboxyl group (-COOH); and Ingredient C: Aqueous solvent.

2. A method for manufacturing a semiconductor device, comprising: The step of applying a resist solution on the substrate; a step of exposing and developing the resist film; A step of applying a composition on the resist pattern during or after the development to form a coating film that buries the resist pattern; heating the coating film to form a heated coating film; The step of removing the heated coating film with water or a developer to provide a resist pattern in which the composition components are permeated in the resist; as well as a step of processing a lower layer of the resist pattern using the resist pattern as a protective film, The composition contains: 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 of the hydrolyzable silane compound, wherein the metal oxide a1 is an oxide of at least one metal selected from the group consisting of germanium, indium, tin, and vanadium; Component B: an acid compound that does not contain a carboxyl group (-COOH); and Ingredient C: Aqueous solvent.

3. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the component B is an acid compound containing a sulfonic acid group (-SO3H).

4. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the hydrolyzable silane compound a2 contains a compound selected from A hydrolyzable silane containing an amino group-containing organic group, and Hydrolyzable silane containing an organic group having an ionic functional group At least one of .

5. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the hydrolyzable silane compound a2 contains at least one selected from the group consisting of a hydrolyzable silane represented by the following formula (1) and a hydrolyzable silane represented by the 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 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 R 3 The R 3 When there are multiple 3 It represents a group that can also form a ring and bind to the Si atom; R 1 represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and R 1 Bonded to silicon atoms via Si-C bonds; 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 represent a hydroxyl group, an alkoxy group, an acyloxy group, or a halogen group respectively; R 30 represents an organic group containing an amino group or an organic group having an ionic functional group, and R 30 The R 30 When there are multiple 30 It represents a group that can also form a ring and bind to the Si atom; n0 represents an integer from 1 to 10. 6 . The method for manufacturing a semiconductor device according to claim 5 , wherein the amino group-containing organic group contains a group selected from a primary amino group, a secondary amino group, and a tertiary amino group. 7 . The method for manufacturing a semiconductor device according to claim 5 , wherein the amino group-containing organic group is selected from the group consisting of an aliphatic amino group and an aromatic amino group.

8. The method for manufacturing a semiconductor device according to claim 5, wherein the ionic functional group is selected from the group consisting of primary ammonium cations, secondary ammonium cations, tertiary ammonium cations, quaternary ammonium cations, carboxylate anions, sulfonate anions, nitrate anions, phosphate anions, sulfonium cations, and alkoxide anions. 9 . The method for manufacturing a semiconductor device according to claim 5 , wherein the ionic functional group has a counter ion.

10. The method for manufacturing a semiconductor device according to claim 9, wherein the counter ion is selected from the group consisting of 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, tartaric acid anion, phthalate anion, citrate anion, glutarate anion, anion, lactic acid anion, salicylic acid anion, methanesulfonic acid anion, octanoic acid anion, decanoic acid anion, octylsulfonic acid anion, decylsulfonic acid anion, dodecylbenzenesulfonic acid anion, phenolsulfonic acid anion, sulfosalicylic acid anion, camphorsulfonic acid anion, nonafluorobutanesulfonic acid anion, toluenesulfonic acid anion, isopropylbenzenesulfonic acid anion, p-octylbenzenesulfonic acid anion, p-decylbenzenesulfonic acid anion, 4-octyl-2-phenoxybenzenesulfonic acid anion, 4-carboxybenzenesulfonic acid anion. 11 . The method for manufacturing a semiconductor device according to claim 1 , wherein in the composition, the component B is present in a ratio of 0.5 to 15 parts by mass based on 100 parts by mass of the component A.

12. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the composition further contains a curing catalyst.

13. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the composition further contains a surfactant.

14. The method for manufacturing a semiconductor device according to claim 1 or 2, wherein the composition further contains a photoacid generator.

15. The method for manufacturing a semiconductor device according to any one of claims 1 to 14, wherein the substrate is processed by a resist pattern.

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