Silicon-containing planarizing coating for pattern reversal

Abstract

To provide a pattern reversal material and a reversal pattern formation method using the material having high etching resistance, and having excellent burying property between resist patterns, and excellent in flattenability at a line part and a space part of a resist pattern and a reversal pattern formation method using a pattern reversal material.SOLUTION: A coating agent for a silicon-containing flattening pattern reversal contains (A) a polysiloxane composed of a hydrolytic condensate of a hydrolyzable silane, a modified polysiloxane wherein at least a portion of the silanol groups thereof is capped; (B) a curing catalyst; and (C) an organic solvent that does not cause damage on the resist film, and a method for forming a reversal pattern using the coating agent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a pattern reversal material and a pattern reversal method using the reversal material, and more particularly to a technique for forming a reversal pattern by coating and filling a resist pattern with the reversal material, and then removing the resist pattern by dry etching and wet etching. [Background technology]

[0002] 2. Description of the Related Art In the field of semiconductor device manufacturing, a technique is widely used in which a fine pattern is formed on a substrate, and the substrate is processed by etching according to this pattern. As lithography technology advances, finer patterns are being produced, and KrF excimer lasers and ArF excimer lasers are being used. Furthermore, exposure techniques using electron beams and EUV (extreme ultraviolet) are being investigated.

[0003] One of the pattern formation techniques is the pattern inversion method. In this technique, a resist pattern is first formed on a semiconductor substrate, the resist pattern is then covered with a silicon-based coating liquid (reversal material), the coating liquid is filled between the resist patterns, and the coating liquid is baked to form a coating film. The upper part of the silicon-containing coating film is then etched back with a fluorine-based gas to expose the upper part of the resist pattern, and the gas is then changed to an oxygen-based gas to remove the resist pattern, leaving a silicon-based pattern derived from the silicon-based coating film in place of the lost resist pattern, thereby inverting the pattern. When the silicon-based film on which the inversion pattern is formed is used as an etching mask to etch the underlying layer or the substrate, the inversion pattern is transferred and a pattern is formed on the substrate. As a material used for forming such a reverse pattern, a composition containing polysiloxane has been proposed (Patent Documents 1 to 4). In addition, a method has been proposed in which a resist pattern is irradiated with light to impart resistance to organic solvents contained in a reversal material to be used later, and then spaces between the resist pattern are filled with a reversal material containing a non-silicone resin, and the upper part of the reversal material is etched back and the resist pattern is removed by alkaline wet etching (Patent Document 5). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 145808 [Patent Document 2] International Publication No. 2017 / 145809 [Patent Document 3] International Publication No. 2018 / 066515 [Patent Document 4] International Publication No. 2018 / 043407 [Patent Document 5] JP 2009-211036 A Summary of the Invention [Problem to be solved by the invention]

[0005] In the pattern reversal technique by dry etching, the silicon-based coating film forming the reversal pattern needs to be resistant to etching gas. A silicon-based coating film lacking in dry etching resistance cannot reverse the pattern, and even if it can be reversed, the sidewall of the reversal pattern is damaged, making it difficult to obtain a rectangular reversal pattern. In addition, if a material with a high silicon content is used to ensure sufficient dry etching resistance, there is a risk that the embedding ability in the resist pattern and the flattening ability of the coating film will be lost. Furthermore, when etching back a reversal material by wet etching, it is necessary to design a special wet chemical and a special reversal material that dissolves in the wet chemical.

[0006] An object of the present invention is to provide a pattern reversal material capable of forming a cured film having high etching resistance, good embedding properties between resist patterns, and excellent planarization properties in line and space portions of a resist pattern, and a method for forming a reversal pattern using the material. [Means for solving the problem]

[0007] The present invention provides, as a first aspect, (A) a modified polysiloxane comprising a hydrolysis condensate of a hydrolyzable silane, at least a portion of the silanol groups of which are capped; (B) a curing catalyst; (C) An organic solvent that does not damage the resist film, and The present invention relates to a silicon-containing planarizing pattern reversal coating. As a second aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to the first aspect, in which the (C) organic solvent contains a hydrophobic alcohol that is poorly soluble in the resist film. As a third aspect, the present invention relates to the coating agent for silicon-containing planarizing pattern reversal according to the second aspect, wherein the (C) organic solvent contains a hydrophobic alcohol such that, when the organic solvent is brought into contact with a resist film made of an ArF resist material for 60 seconds, a reduction rate of the film thickness of the resist film after contact with the resist film relative to the film thickness of the resist film before contact is 10% or less. As a fourth aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to any one of the first to third aspects, in which a ratio of silanol groups to all silicon atoms in the (A) modified polysiloxane is 50 mol % or less. As a fifth aspect, the (A) modified polysiloxane a modified product of the hydrolysis-condensation product in which at least a portion of the silanol groups of the hydrolysis-condensation product are modified with alcohol; A modified product of the hydrolysis condensation product in which at least a part of the silanol groups of the hydrolysis condensation product are acetal-protected, and The hydrolysis condensation product and the alcohol dehydration reaction product are included. The present invention relates to a silicon-containing planarizing pattern reversal coating agent according to any one of the first to fourth aspects. As a sixth aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to the fifth aspect, in which the alcohol is a monohydric alcohol. As a seventh aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to the fifth or sixth aspect, in which the (A) modified polysiloxane contains a dehydration reaction product of the hydrolysis condensate and an alcohol. As an eighth aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to any one of the first to seventh aspects, in which the polysiloxane consisting of a hydrolysis condensation product of the hydrolysis silane is a hydrolysis condensation product of a hydrolysis silane containing at least one hydrolysis silane represented by the following formula (1): [ka] (In the formula, R 1 are groups bonded to silicon atoms, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, a substituted represents an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or represents an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof; R 2 are groups or atoms bonded to a silicon atom, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom; a represents an integer of 0 to 3. As a ninth aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to the eighth aspect, in which the polysiloxane consisting of the hydrolyzed condensate of the hydrolyzable silane is a hydrolyzed condensate of hydrolyzable silane (ii) in which a in the above formula (1) is 1, or a co-hydrolyzed condensate of hydrolyzable silane (i) in which a in the above formula (1) is 0 and hydrolyzable silane (ii) in which a in the above formula (1) is 1. As a tenth aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to the eighth aspect, in which the polysiloxane consisting of the hydrolyzed condensate of the hydrolyzable silane is a co-hydrolyzed condensate having the hydrolyzable silane (i):the hydrolyzable silane (ii) in a molar ratio of 20:80 to 40:60. As an eleventh aspect, the present invention relates to the silicon-containing planarizing pattern reversal coating agent according to any one of the first to tenth aspects, in which the resist film is a film made of an ArF resist material. As a twelfth aspect, a step of forming a resist film on a substrate; A step of forming a resist pattern by irradiation with light or an electron beam and development; A process of applying the silicon-containing planarizing pattern reversal coating agent according to any one of claims 1 to 11 onto a resist film having a pattern formed thereon during or after development, and baking the coating agent to form a hardened film; a step of etching back the surface of the cured film by dry etching to expose a resist pattern surface of the resist film on which a pattern has been formed; and removing the patterned resist film by wet etching to invert the pattern. As a thirteenth aspect, the present invention relates to the method for forming a reversal pattern as defined in the twelfth aspect, wherein in the step of reversing the pattern, the patterned resist film is removed by wet etching using an organic solvent. According to a fourteenth aspect, the present invention relates to the method for forming a reversal pattern according to the twelfth or thirteenth aspect, wherein in the step of forming the cured film, a baking temperature is 80° C. to 180° C. A fifteenth aspect relates to a method for manufacturing a semiconductor device, using the method for forming a reverse pattern according to any one of the twelfth to fourteenth aspects. Effect of the Invention

[0008] According to the present invention, there can be provided a silicon-containing planarizing pattern reversal coating agent which has excellent filling properties between resist patterns, excellent planarizing properties in line and space portions of a resist pattern, and is capable of forming a cured film having high resistance to wet etching of the resist pattern. Furthermore, the silicon-containing planarizing coating agent for pattern reversal of the present invention can form a cured film even under relatively low-temperature baking conditions, and therefore can embed and coat a resist pattern without causing pattern collapse such as dissolution of the underlying resist pattern caused by high-temperature baking, thereby enabling the formation of a well-shaped reversal pattern. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a diagram showing a cross-sectional SEM photograph of the cured film of Example 3 produced from the silicon-containing planarizing pattern reversal coating agent of Example 1 on a stepped substrate. [Diagram 2] FIG. 2 is a diagram showing a cross-sectional SEM photograph of the cured film of Example 4 produced from the silicon-containing planarizing pattern reversal coating agent of Example 2 on a stepped substrate. [Diagram 3] FIG. 3 is a diagram showing a cross-sectional SEM photograph after etch-back (exposing the top of the resist) following coating of a resist pattern with the silicon-containing planarizing pattern reversal coating agent of Example 1 in an evaluation of pattern reversal. [Figure 4] FIG. 4 is a diagram showing a SEM photograph of a cross section of a reversal pattern after the resist pattern is removed by wet etching in the pattern reversal evaluation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] [Silicon-containing planarizing coating for pattern reversal] The present invention is directed to a pattern reversal material used in a pattern formation method utilizing a reversal pattern, and relates to a silicon-containing planarizing coating agent for pattern reversal (hereinafter also simply referred to as "coating agent for pattern reversal") that essentially contains (A) a modified polysiloxane consisting of a hydrolysis condensation product of a hydrolyzable silane, in which at least a portion of the silanol groups thereof are capped, (B) a curing catalyst, and (C) an organic solvent that does not damage a resist film.

[0011] (A) Modified polysiloxane The (A) modified polysiloxane used in the present invention refers to a polysiloxane in which some of the silanol groups in the polysiloxane have been capped (modified), for example, a modified polysiloxane in which some of the silanol groups have been alcohol-modified or acetal-protected. More specifically, the (A) modified polysiloxane is a polysiloxane consisting of a hydrolysis condensate of a hydrolyzable silane (hereinafter, simply referred to as a "hydrolysis condensate" or "condensate"), in which at least a portion of the silanol groups contained therein are capped.

[0012] The modified polysiloxane and the unmodified (unmodified) polysiloxane may have a cage, ladder, straight-chain, or branched main chain structure. Furthermore, commercially available polysiloxanes may be used as these polysiloxanes.

[0013] The weight average molecular weight of the modified polysiloxane may be, for example, in the range of 500 to 1,000,000. From the viewpoint of suppressing precipitation of the modified polysiloxane in the pattern reversal coating agent, the weight average molecular weight may be 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 coatability, the weight average molecular weight may be preferably 700 or more, more preferably 1,000 or more. These weight average molecular weights are molecular weights obtained by GPC analysis in terms of polystyrene. GPC analysis can be performed, for example, using a GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as an eluent (elution solvent), a flow rate (flow velocity) of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as a standard sample.

[0014] In the modified polysiloxane (A), the ratio of silanol groups to all silicon atoms can be 50 mol% or less, for example, 40 mol% or less, or 5 to 40 mol%, or 10 to 25 mol%. That is, the amount of silanol groups can be adjusted by capping the silanol groups so that the ratio of silanol groups to all silicon atoms falls within the above range. By adjusting the amount of silanol groups within the above range, when a resist pattern is coated with the coating agent for pattern reversal of the present invention, a planarized coated surface and cured film can be obtained. In the modified polysiloxane (A), the proportion of capping (proportion of capped silanol groups) relative to all silicon atoms can be, for example, 20 mol % to 40 mol %.

[0015] In this specification, planarization means that when applied to a resist pattern, there is little difference in film thickness of the applied coating present on the upper portion between the portion where the resist pattern exists (line portion) and the portion where the pattern does not exist (space portion). In the present invention, for example, a degree of unevenness (%) [= (h2 / h1) × 100] defined as the ratio of the film thickness difference (height difference) h2 between the line portion and the space portion to the groove depth (step) h1 of the line portion is less than 50%, for example, less than 40%, can be evaluated as having good planarization.

[0016] One example of the modified polysiloxane is a modified polysiloxane in which at least a portion of the silanol groups of the hydrolysis condensate are alcohol-modified or acetal-protected. Examples of the modified polysiloxane include a reaction product obtained by reacting at least a portion of the silanol groups in the hydrolysis condensate of the hydrolyzable silane with hydroxyl groups of an alcohol, a dehydration reaction product of the condensate with an alcohol, and a modified product in which at least a portion of the silanol groups in the condensate are protected with an acetal group.

[0017] The alcohol may be a monohydric alcohol, for example a monohydric alcohol having 3 to 10 carbon atoms, and a branched alcohol may be used more preferably than a linear alcohol. Examples of the alcohol include methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, Sanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol (methyl isobutyl carbinol), 4-methyl-3-pentanol and cyclohexanol. Further, for example, alkoxy group-containing alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used. Among these, preferred ones include 2-propanol, 4-methyl-2-pentanol (methyl isobutyl carbinol), and the like.

[0018] The reaction between the silanol groups of the condensate and the hydroxyl groups of the alcohol can be carried out by contacting the polysiloxane with the alcohol and reacting for 0.1 to 48 hours, for example 24 hours, at a temperature of 40 to 160° C., for example 120° C., to obtain a modified polysiloxane with capped silanol groups. At this time, the alcohol of the capping agent can be used as a solvent in the pattern reversal coating agent containing (A) the modified polysiloxane.

[0019] Furthermore, the dehydration reaction product of the polysiloxane consisting of the hydrolysis condensate of the hydrolyzable silane and an alcohol can be produced by reacting the polysiloxane with an alcohol in the presence of an acid catalyst, capping the silanol groups with the alcohol, and removing the water generated by the dehydration from the reaction system. The acid that can be used is an organic acid having an acid dissociation constant (pka) of −1 to 5, preferably 4 to 5. Examples of the acid include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., and among these, benzoic acid, isobutyric acid, acetic acid, etc. can be mentioned. The acid to be used may have a boiling point of 70 to 160° C., and examples thereof include trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. As described above, the acid preferably has either an acid dissociation constant (pka) of 4 to 5 or a boiling point of 70 to 160° C. In other words, it is possible to use an acid that has a weak acidity or a strong acidity but a low boiling point. As the acid, it is possible to use either one of the properties, ie, the acid dissociation constant and the boiling point. For example, acetic acid, which has both properties, can be preferably used.

[0020] The acetal protection of the silanol group can be achieved using vinyl ethers, for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, and cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 2,3-dihydro-4H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, and 2,3-dihydrofuran can be preferably used. The acetal protection of the silanol group can be carried out using a polysiloxane consisting of a hydrolysis condensate of the hydrolyzable silane, the vinyl ether, and an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, or 1,4-dioxane, and using a catalyst such as pyridinium paratoluenesulfonate, trifluoromethanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0021] The capping of the silanol groups with an alcohol or the acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane described below.

[0022] As the polysiloxane consisting of the hydrolysis condensation product of the hydrolyzable silane, i.e., the polysiloxane before modification, for example, a hydrolysis condensation product of a hydrolyzable silane containing at least one hydrolyzable silane represented by the formula (1) described later can be used. The hydrolyzable silane in the hydrolysis condensate may contain one or more hydrolyzable silanes. In the present invention, the "hydrolysis condensate" of the hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only polyorganosiloxane polymers that are condensates in which condensation is completely completed, but also polyorganosiloxane polymers that are partial hydrolysis condensates in which condensation is not completely completed. Such partial hydrolysis condensates are polymers obtained by hydrolysis and condensation of hydrolyzable silane compounds, like condensates in which condensation is completely completed, but they are partially hydrolyzed and not condensed, and therefore Si-OH groups remain. In addition to the hydrolysis condensate, the pattern reversal coating agent of the present invention may also contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silane compounds). In this specification, the "hydrolyzable silane" may also be simply referred to as a "silane compound."

[0023] [ka] In formula (1), R 1 are groups bonded to silicon atoms, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof; R 2 are groups or atoms bonded to a silicon atom and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom; a represents an integer of 0 to 3.

[0024] The above (before modification) polysiloxane can be a hydrolysis condensation product of hydrolysis silane (ii) in which a in the above formula (1) is 1, or a co-hydrolysis condensation product of hydrolysis silane (i) in which a in formula (1) is 0 and hydrolysis silane (ii) in which a in formula (1) is 1. The above (before modification) polysiloxane can be used in such a range that the molar ratio of hydrolyzable silane (i):hydrolyzable silane (ii) is 0:100 to 50:50, or 10:90 to 50:50, for example, 20:80 to 40:60.

[0025] In the above formula (1), examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-butyl group, a 2-methyl-n-butyl group, a 2-methyl-n-butyl group, a 2-methyl-n-butyl group, a 2-methyl-n-propyl group, a 2-methyl-n-propyl group, a 2-methyl-n-propyl group, a 2-methyl-n-propyl group, a 2-methyl-n-propyl group, a 2-methyl-n-propyl group, a 2-methyl-n-propyl group, a 2-methyl-n-butyl ... Examples of such groups include ethyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group.

[0026] Cyclic alkyl groups can also be used. Examples of cyclic alkyl groups having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl ...butyl, 2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 2,5-dimethylcyclobutyl, 2,6-dimethylcyclobutyl, 2,7-dimethylcyclobutyl, 2,8-dimethylcyclobutyl, 2,9-dimethylcyclobutyl, 3,10-dimethylcyclobutyl, 2,11-dimethylcyclobutyl, 2,12-dimethylcyclobutyl, 2,13-dimethylcyclobutyl, 2,14-dimethylcyclobutyl, 2,15-dimethylcyclobutyl, 2,16-dimethylcyclobutyl, 2,17-dimethylcyclobutyl, 2,18-dimethylcyclobutyl, 2,19-dimethylcyclobutyl, 2,20-dimethylcyclobutyl, 2,21-dimethylcyclobutyl, 2,22-dimethylcyclobutyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, Examples of cycloalkyl groups include dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bridged ring cycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0027] The aryl group may be any of a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. For example, the aryl group may be an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-naphthacenyl group, a 2-naphthacenyl group, a 5-naphthacenyl group, a 2-chrysenyl group, a 1-pyrenyl group, and a 2-pyrenyl group. , pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), para-terphenyl-4-yl group, meta-terphenyl-4-yl group, ortho-terphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group and the like, but are not limited to these.

[0028] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those mentioned above. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyl groups include, but are not limited to, a phenylmethyl group (benzyl group), a 2-phenylethylene group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, a 6-phenyl-n-hexyl group, a 7-phenyl-n-heptyl group, an 8-phenyl-n-octyl group, a 9-phenyl-n-nonyl group, and a 10-phenyl-n-decyl group.

[0029] The above-mentioned halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms, and specific examples of such alkyl groups, aryl groups, and aralkyl groups include the same as those mentioned above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0030] The number of carbon atoms in the halogenated alkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of the halogenated alkyl group include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentyl group, Examples of the fluoroalkyl group include, but are not limited to, a perfluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group.

[0031] The number of carbon atoms in the halogenated aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of the halogenated aryl group include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group, a 2,3,4,6-tetrafluorophenyl group, a 2,3,5,6-tetrafluorophenyl group, a pentafluorophenyl group, a 2-fluoro-1-naphthyl group, a 3-fluorophenyl group, b-1-naphthyl group, 4-fluoro-1-naphthyl group, 6-fluoro-1-naphthyl group, 7-fluoro-1-naphthyl group, 8-fluoro-1-naphthyl group, 4,5-difluoro-1-naphthyl group, 5,7-difluoro-1-naphthyl group, 5,8-difluoro-1-naphthyl group, 5,6,7,8-tetrafluoro-1-naphthyl group, heptafluoro-1-naphthyl group, 1-fluoro-2-naphthyl group, Examples of such groups include fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, and heptafluoro-2-naphthyl groups, and also include groups in which the fluorine atom (fluoro group) is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group), but are not limited to these.

[0032] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of the halogenated aralkyl group include a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2,3-difluorobenzyl group, a 2,4-difluorobenzyl group, a 2,5-difluorobenzyl group, a 2,6-difluorobenzyl group, a 3,4-difluorobenzyl group, a 3,5-difluorobenzyl group, a 2,3,4-trifluorobenzyl group, a 2,3,5-trifluorobenzyl group, a 2,3,6-trifluorobenzyl group, a 2,4,5-trifluorobenzyl group, a 2,5-trifluorobenzyl group, a 2,6-trifluorobenzyl group, a 2,5-trifluorobenzyl group, a 2,6-trifluorobenzyl group, a 2,7 ... Examples of the fluorobenzyl group include a 2,4,6-trifluorobenzyl group, a 2,3,4,5-tetrafluorobenzyl group, a 2,3,4,6-tetrafluorobenzyl group, a 2,3,5,6-tetrafluorobenzyl group, and a 2,3,4,5,6-pentafluorobenzyl group, and further include groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group), but are not limited to these.

[0033] The above-mentioned alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are alkyl groups, aryl groups, and aralkyl groups substituted with one or more alkoxy groups, and specific examples of such alkyl groups, aryl groups, and aralkyl groups include the same as those mentioned above.

[0034] The alkoxy group includes an alkoxy group having a straight-chain, branched or cyclic alkyl portion having 1 to 20 carbon atoms. Examples of the straight-chain or branched alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 2 ... Methyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl Examples of such groups include a-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.Examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3 -dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group, and 2-ethyl-3-methyl-cyclopropoxy group.

[0035] Specific examples of the alkoxyalkyl group include lower (having about 5 carbon atoms or less) alkyloxy-lower (having about 5 carbon atoms or less) alkyl groups such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group, but are not limited to these. Specific examples of the alkoxyaryl group include, but are not limited to, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-(1-ethoxy)phenyl group, a 3-(1-ethoxy)phenyl group, a 4-(1-ethoxy)phenyl group, a 2-(2-ethoxy)phenyl group, a 3-(2-ethoxy)phenyl group, a 4-(2-ethoxy)phenyl group, a 2-methoxynaphthalen-1-yl group, a 3-methoxynaphthalen-1-yl group, a 4-methoxynaphthalen-1-yl group, a 5-methoxynaphthalen-1-yl group, a 6-methoxynaphthalen-1-yl group, and a 7-methoxynaphthalen-1-yl group. Specific examples of the alkoxyaralkyl group include, but are not limited to, a 3-(methoxyphenyl)benzyl group, a 4-(methoxyphenyl)benzyl group, and the like.

[0036] The alkenyl group includes alkenyl groups having 2 to 10 carbon atoms, such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3 -butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylethenyl, 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 group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2 -dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, Examples of alkenyl groups include 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 groups, and also include bridged ring alkenyl groups such as bicycloheptenyl (norbornyl) groups.

[0037]

[0113] Furthermore, examples of the substituent in the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group include alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, aryloxy groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, alkoxy groups, and aralkyloxy groups. Specific examples of these and suitable numbers of carbon atoms for these groups are the same as those described above or below. The aryloxy group mentioned in the above substituents is a group in which an aryl group is bonded via an oxygen atom (-O-), and specific examples of such an aryl group include the same as those mentioned above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less, and specific examples thereof include, but are not limited to, a phenoxy group, a naphthalene-2-yloxy group, etc. When two or more substituents are present, the substituents may be bonded to each other to form a ring.

[0038] 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. Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group. Examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group. Examples of the organic group having a mercapto group include an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, an octyl mercapto group, and a mercaptophenyl group. Examples of the organic group containing an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group. Examples of the organic group containing an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group, except for groups in which an alkoxy group is directly bonded to a silicon atom. Examples of the organic group containing a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group. Examples of the organic group having a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.

[0039] The aralkyloxy group is a group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol, and specific examples of such aralkyl groups include the same as those mentioned above. The number of carbon atoms in the aralkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less. Specific examples of the aralkyloxy group include a phenylmethyloxy group (benzyloxy group), a 2-phenylethyleneoxy group, a 3-phenyl-n-propyloxy group, a 4-phenyl-n-butyloxy group, a 5-phenyl-n-pentyloxy group, a 6-phenyl-n-hexyloxy group, a 7-phenyl-n-heptyloxy group, an 8-phenyl-n-octyloxy group, a 9-phenyl-n-nonyloxy group, and a 10-phenyl-n-decyloxy group, but are not limited to these.

[0040] The acyloxy group is a group derived by removing a hydrogen atom from the carboxyl group (-COOH) of a carboxylic acid compound, and typically includes, but is not limited to, an alkylcarbonyloxy group, an arylcarbonyloxy group, or an aralkylcarbonyloxy group derived by removing a hydrogen atom from the carboxyl group of an alkylcarboxylic acid, an arylcarboxylic acid, or an aralkylcarboxylic acid. Specific examples of the alkyl group, aryl group, and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid, and aralkylcarboxylic acid are the same as those mentioned above. Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, Examples of such an alkyl group include a methyl-n-butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a 1,2,2-trimethyl-n-propylcarbonyloxy group, a 1-ethyl-1-methyl-n-propylcarbonyloxy group, a 1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group, and a tosylcarbonyloxy group.

[0041] The hydrolyzable silane represented by the above formula (1) preferably includes any one of tetraalkoxysilane in which a in formula (1) is 0, methyltrialkoxysilane, vinyltrialkoxysilane or phenyltrialkoxysilane in which a in formula (1) is 1, and dimethyldialkoxysilane in which a in formula (1) is 2. Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and the like can be preferably used. In the present invention, for example, as the hydrolyzable silane represented by the above formula (1), tetramethoxysilane or tetraethoxysilane and methyltrimethoxysilane or methyltriethoxysilane can be used in a molar ratio range of 20:80 to 40:60.

[0042] The hydrolysis condensate of the hydrolyzed silane can be obtained by hydrolysis and condensation of the above-mentioned silane compound (hydrolyzable silane). The above silane compound (hydrolyzable silane) has an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom directly bonded to a silicon atom, i.e., -Si-R in formula (1). 2 The groups include alkoxysilyl groups, aralkyloxysilyl groups, acyloxysilyl groups, and halogenated silyl groups (hereinafter referred to as hydrolyzable groups). For the hydrolysis of these hydrolyzable groups, usually 0.1 to 100 mol, for example 0.5 to 100 mol, preferably 1 to 10 mol of water is used per mol of the hydrolyzable group. In the hydrolysis and condensation, a hydrolysis catalyst may be used or may not be used for the purpose of promoting the reaction, etc. When a hydrolysis catalyst is used, the amount of the hydrolysis catalyst that can be used is usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, per mol of the hydrolyzable group. The reaction temperature during hydrolysis and condensation is usually in the range of not less than room temperature and not more than the reflux temperature at normal pressure of the organic solvent that can be used for the hydrolysis, and can be, for example, 20 to 110°C, or, for example, 20 to 80°C. The hydrolysis may be complete, ie, all hydrolyzable groups are converted to silanol groups, or it may be partial, ie, some hydrolyzable groups are left unreacted. Examples of hydrolysis catalysts that can be used in the hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0043] Metal chelate compounds as hydrolysis catalysts include, for example, triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di-i-propoxy bis(acetylacetonate)titanium, di-n-butoxy Di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, mono-n-propoxy tris(acetylacetonate) titanium, mono-i-propoxy tris(acetylacetonate) titanium, mono-n-butoxy tris(acetylacetonate) titanium, mono-sec-butoxy tris(acetylacetonate) titanium, mono-t-butoxy tris(acetylacetonate) Titanium, tetrakis(acetylacetonate)titanium, triethoxy mono(ethylacetoacetate)titanium, tri-n-propoxy mono(ethylacetoacetate)titanium, tri-i-propoxy mono(ethylacetoacetate)titanium, tri-n-butoxy mono(ethylacetoacetate)titanium, tri-sec-butoxy mono(ethylacetoacetate)titanium, tri-t-butoxy mono(ethylacetoacetate)titanium, diethoxy bis(ethylacetoacetate)titanium, di-n-propoxy bis(ethylacetoacetate) di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate) titanium, mono-n-butoxy tris(ethylacetoacetate) titanium, mono-sec- Titanium chelate compounds such as titanium chelate, mono-t-butoxy tris(ethylacetoacetate) titanium, mono-t-butoxy tris(ethylacetoacetate) titanium, tetrakis(ethylacetoacetate) titanium, mono(acetylacetonato) tris(ethylacetoacetate) titanium, bis(acetylacetonato) bis(ethylacetoacetate) titanium, tris(acetylacetonato) mono(ethylacetoacetate) titanium; triethoxy mono(acetylacetonato) zirconium, tri-n-propoxy mono(acetylacetonato) zirconium,Tri-i-propoxy mono(acetylacetonate)zirconium, tri-n-butoxy mono(acetylacetonate)zirconium, tri-sec-butoxy mono(acetylacetonate)zirconium, tri-t-butoxy mono(acetylacetonate)zirconium, diethoxy bis(acetylacetonate)zirconium, di-n-propoxy bis(acetylacetonate)zirconium, di-i-propoxy bis(acetylacetonate)zirconium, di-n-butoxy bis(acetylacetonate)zirconium , di-sec-butoxy bis(acetylacetonate)zirconium, di-t-butoxy bis(acetylacetonate)zirconium, monoethoxy tris(acetylacetonate)zirconium, mono-n-propoxy tris(acetylacetonate)zirconium, mono-i-propoxy tris(acetylacetonate)zirconium, mono-n-butoxy tris(acetylacetonate)zirconium, mono-sec-butoxy tris(acetylacetonate)zirconium, mono-t-butoxy tris(acetylacetonate)zirconium Cetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxy mono(ethylacetoacetate)zirconium, tri-n-propoxy mono(ethylacetoacetate)zirconium, tri-i-propoxy mono(ethylacetoacetate)zirconium, tri-n-butoxy mono(ethylacetoacetate)zirconium, tri-sec-butoxy mono(ethylacetoacetate)zirconium, tri-t-butoxy mono(ethylacetoacetate)zirconium, diethoxy bis (ethylacetoacetate)zirconium, di-n-propoxy bis(ethylacetoacetate)zirconium, di-i-propoxy bis(ethylacetoacetate)zirconium, di-n-butoxy bis(ethylacetoacetate)zirconium, di-sec-butoxy bis(ethylacetoacetate)zirconium, di-t-butoxy bis(ethylacetoacetate)zirconium, monoethoxy tris(ethylacetoacetate)zirconium, mono-n-propoxy tris(ethylacetoacetate)zirconium,Mono-i-propoxy tris(ethylacetoacetate)zirconium, mono-n, Examples of the chelate compounds include, but are not limited to, zirconium chelate compounds such as mono-sec-butoxy tris(ethylacetoacetate) zirconium, mono-t-butoxy tris(ethylacetoacetate) zirconium, tetrakis(ethylacetoacetate) zirconium, mono(acetylacetonato) tris(ethylacetoacetate) zirconium, bis(acetylacetonato) bis(ethylacetoacetate) zirconium, and tris(acetylacetonato) mono(ethylacetoacetate) zirconium; and aluminum chelate compounds such as tris(acetylacetonato) aluminum and tris(ethylacetoacetate) aluminum.

[0044] Examples of organic acids as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0045] Examples of inorganic acids as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0046] Examples of organic bases as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0047] Examples of inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

[0048] 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.

[0049] In the present invention, nitric acid can be suitably used as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the change in molecular weight of the hydrolysis condensate can be suppressed. As described above, nitric acid can also be used when obtaining a modified product of the hydrolysis and condensation product, for example, when capping a silanol group with an alcohol. Therefore, nitric acid is preferable from the viewpoint of being able to contribute to both the hydrolysis and condensation of the hydrolyzable silane and the alcohol capping of the hydrolysis and condensation product.

[0050] In carrying out the hydrolysis and condensation, an organic solvent may be used as a solvent. Specific examples of the solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, and cyclohexane. aliphatic hydrocarbon solvents such as hexane and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, and n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, , sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, 4-methyl-2-pentanol (methyl isobutyl carbinol), sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol , sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol and other monoalcohol solvents; ethylene glycol, propylene glycol, 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 Polyhydric alcohol solvents such as ricol, triethylene glycol, tripropylene glycol, and glycerin; ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone;Ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n- ether solvents such as butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;Diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl acetate; Glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, i-acetylacetate Examples of suitable solvents include, but are not limited to, ester solvents such as methyl lactate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more.

[0051] Among these organic solvents, from the viewpoint of contributing as an organic solvent that does not damage the resist film (C) described below, aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, and n-amylnaphthalene; methanol; Examples of the solvent include monoalcohol solvents such as ethanol, n-propanol, i-propanol, n-hexanol, 2-methylpentanol, 4-methyl-2-pentanol (methyl isobutyl carbinol), sec-hexanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol (dimethyl isobutyl carbinol), n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, and sec-heptadecyl alcohol; and ketone solvents such as acetone.

[0052] After completion of the hydrolysis and condensation reactions, the reaction solution can be used as is or after dilution or concentration, neutralized, and treated with an ion exchange resin to remove the hydrolysis catalyst, such as an acid or base, used in the hydrolysis and condensation. Before or after such treatment, by-products such as alcohol and water, and the hydrolysis catalyst used can be removed from the reaction solution by vacuum distillation or the like.

[0053] The hydrolysis condensate is subjected to the above-mentioned capping treatment by modification of the silanol groups with alcohol or acetal protection to obtain a modified polysiloxane. As described above, the capping treatment may be performed simultaneously with the hydrolysis and condensation of the hydrolyzable silane, or after the simultaneous hydrolysis and condensation, a further capping treatment may be performed to adjust the capping ratio (amount of silanol groups).

[0054] The modified polysiloxane thus obtained is in the form of a varnish dissolved in an organic solvent, which can be used as is for the preparation of a coating agent for pattern reversal described below. That is, the reaction solution can be used as is (or diluted) for the preparation of a coating agent for pattern reversal, and at this time, the hydrolysis catalyst used in the hydrolysis and condensation, the alcohol or acid used in the capping treatment, the vinyl ether, by-products, etc. do not impair the effects of the present invention. It may remain in the reaction solution as long as it is not excessively diluted. The obtained varnish may be subjected to solvent substitution or may be diluted with an appropriate solvent. If the obtained varnish has good storage stability, the organic solvent may be distilled off to make the solid concentration 100%. The organic solvent used for the solvent substitution or dilution of the varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane. The dilution solvent is not particularly limited, and one or more kinds may be arbitrarily selected and used.

[0055] (B) Curing catalyst The silicon-containing planarizing pattern reversal coating agent of the present invention contains (B) a curing catalyst. By containing (B) a curing catalyst, the cured film formed from the pattern reversal coating agent has resistance to the organic solvent used to remove the resist pattern described below. In addition, by blending (B) a curing catalyst, the curing is promoted when the pattern reversal coating agent is baked, and it can be cured even under relatively low temperature conditions.

[0056] As the curing catalyst, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc. The following salts described as examples of the curing catalyst may be added in the form of a salt, or may form a salt in the composition (added as a separate compound and forming a salt in the system).

[0057] The ammonium salt may be represented by the formula (D-1): [ka] (In the formula, m a is an integer from 2 to 11, n a is an integer between 2 and 3, R 21 represents an alkyl group or an aryl group; Y - represents an anion. Formula (D-2): [ka] (In the formula, R 22 , R 23 , R 24 and R 25 represents an alkyl or aryl group, N represents a nitrogen atom, Y - represents an anion, and R 22 , R 23 , R 24 , and R 25 are each bonded to a nitrogen atom), Formula (D-3): [ka] (In the formula, R 26 and R 27 represents an alkyl or aryl group, N represents a nitrogen atom, Y - represents an anion), Formula (D-4): [ka] (In the formula, R28 represents an alkyl or aryl group, N represents a nitrogen atom, Y - represents an anion), Formula (D-5): [ka] (In the formula, R 29 and R 30 represents an alkyl or aryl group, N represents a nitrogen atom, Y - represents an anion), Formula (D-6): [ka] (In the formula, m a is an integer from 2 to 11, n a represents an integer of 2 or 3, H represents a hydrogen atom, N represents a nitrogen atom, Y - represents an anion).

[0058] The phosphonium salt may also be a compound represented by the formula (D-7): [ka] (In the formula, R 31 , R 32 , R 33 , and R 34 represents an alkyl or aryl group, P represents a phosphorus atom, Y - represents an anion, and R 31 , R 32 , R 33 , and R 34 are each bonded to a phosphorus atom).

[0059] The sulfonium salt may also be represented by the formula (D-8): [ka] (In the formula, R 35 , R 36, and R 37 represents an alkyl or aryl group, S represents a sulfur atom, Y - represents an anion, and R 35 , R 36 , and R 37 are each bonded to a sulfur atom).

[0060] The compound of the above formula (D-1) is a quaternary ammonium salt derived from an amine, m a represents an integer from 2 to 11; n a represents an integer of 2 or 3. R of this quaternary ammonium salt 21 represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10, or an aryl group having 6 to 18 carbon atoms, and examples thereof include linear alkyl groups such as ethyl, propyl, and butyl groups, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I - ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O - ) and the like acid groups.

[0061] The compound of the above formula (D-2) is R 22 R 23 R 24 R 25 N + Y - The R of this quaternary ammonium salt is 22 , R 23 , R 24 and R 25 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I- ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O - The quaternary ammonium salt is commercially available, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0062] The compound of the above formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and R 26 and R 27 has 1 to 18 carbon atoms; R 26 and R 27 The total number of carbon atoms in R is preferably 7 or more. 26 represents methyl, ethyl, propyl, phenyl, and benzyl groups, and R 27 Examples of the anion (Y - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I - ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O - This compound is commercially available, but can also be produced by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an alkyl halide or aryl halide such as benzyl bromide or methyl bromide.

[0063] The compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine. , R 28is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, such as a butyl group, an octyl group, a benzyl group, or a lauryl group. - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I - ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O - ) and other acid groups. This compound is commercially available, but can be produced, for example, by reacting pyridine with an alkyl halide, such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide, or an aryl halide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0064] The compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine, such as picoline, and R 29 R is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples of such groups include a methyl group, an octyl group, a lauryl group, and a benzyl group. 30 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. For example, in the case of a quaternary ammonium derived from picoline, R 30 is a methyl group. - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I - ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O -) and other acid groups. This compound is commercially available, but can be produced by reacting a substituted pyridine such as picoline with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or an aryl halide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0065] The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, m a represents an integer from 2 to 11; n a represents an integer of 2 or 3. Also, the anion (Y - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I - ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O - The compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, the anion (Y - ) is (HCOO - ) and when acetic acid is used, the anion (Y - ) is (CH 3 COO - ) When phenol is used, the anion (Y - ) is (C 6 H 5 O - ).

[0066] The compound of the above formula (D-7) is R 31 R 32 R 33 R 34 P + Y - It is a quaternary phosphonium salt having the structure: R 31 , R 32, R 33 , and R 34 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably R 31 ~R 34 Of the four substituents, three are phenyl groups or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I - ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O - This compound is commercially available, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, Examples of the halogenated tetraphenylphosphonium include halogenated tritolyl monoaryl phosphonium, and halogenated tritolyl monoalkyl phosphonium (wherein the halogen atom is a chlorine atom or a bromine atom). In particular, halogenated triphenyl monoalkyl phosphonium such as halogenated triphenyl methyl phosphonium and halogenated triphenyl ethyl phosphonium, halogenated triphenyl monoaryl phosphonium such as halogenated triphenyl benzyl phosphonium, halogenated tritolyl monoaryl phosphonium such as halogenated tritolyl monophenyl phosphonium, and halogenated tritolyl monoalkyl phosphonium such as halogenated tritolyl monomethyl phosphonium are preferred (wherein the halogen atom is a chlorine atom or a bromine atom).

[0067] Examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0068] The compound of the above formula (D-8) is R 35 R 36 R 37 S + Y - It is a tertiary sulfonium salt having the structure: R 35 , R 36 , and R 37 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably R 35 ~R 37 Of the three substituents, two are phenyl groups or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. - ) is a chloride ion (Cl - ), bromide ion (Br - ), iodine ion (I - ) and carboxylate ions (-COO - ), sulfonato (-SO 3 - ), alcoholate (-O -), maleic acid anion, nitrate anion, and other acid groups can be mentioned. This compound is available as a commercial product, and examples thereof include trialkylsulfonium halides such as tri-n-butylsulfonium halides and tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halides and diphenylethylsulfonium halides, triphenylsulfonium halides (wherein the halogen atom is a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. In addition, triphenylsulfonium halides and triphenylsulfonium carboxylates can be preferably used.

[0069] In the present invention, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of the nitrogen-containing silane compound include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0070] The (B) curing catalyst is present in an amount of 0.1 to 20 parts by mass, or 0.5 to 10 parts by mass, or 1 to 5 parts by mass, per 100 parts by mass of the (A) modified polysiloxane.

[0071] (C) Organic solvent that does not damage the resist film The (C) organic solvent used in the silicon-containing planarizing pattern reversal coating agent of the present invention is The organic solvent is capable of dissolving and mixing the (A) modified polysiloxane, (B) curing catalyst, and other components described below, and does not damage the resist film. In this specification, the term "organic solvent that does not damage the resist film" refers to an organic solvent that does not dissolve the resist film (is poorly soluble) when the planarizing pattern reversal coating agent of the present invention is applied onto the resist film (resist pattern). By using such an organic solvent in the coating agent for pattern reversal, intermixing with the underlying resist film (resist pattern) does not occur, and prior treatment to increase the solvent resistance of the resist film (resist pattern), such as exposure, is not required.

[0072] For example, the organic solvent (C) may be a hydrophobic alcohol that is poorly soluble in the resist film. As an index of the poor solubility, for example, the reduction (reduction rate) in the film thickness of the resist film when it is contacted with the target resist film for 60 seconds may be used. For example, the hydrophobic alcohol may be a hydrophobic alcohol that, when it is contacted with a resist film made of an ArF resist material for 60 seconds, reduces the film thickness after contact by 10 nm or less compared to the resist film thickness before contact, or reduces the film thickness after contact by 10% or less compared to the resist film thickness before contact. More specifically, for example, aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, and n-amylnaphthalene; methanol, ethanol, n-propanol, Examples of such solvents include monoalcohol solvents such as i-propanol (2-propanol), n-hexanol, 2-methylpentanol, sec-hexanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 4-methyl-2-pentanol (methyl isobutyl carbinol), 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, and sec-heptadecyl alcohol; and ketone solvents such as acetone. Among these, 2-propanol, 4-methyl-2-pentanol (methyl isobutyl carbinol), etc. are preferable from the viewpoint that they can be used as the alcohol used in the capping of the above-mentioned polysiloxane and as the solvent used in the hydrolysis and condensation.

[0073] In addition, the composition may contain other solvents in addition to the organic solvent (C) as long as the effect of the present invention is not impaired. Examples of such other solvents include monoalcohol solvents such as n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, 2-ethylbutanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpropanediol, and the like. Polyhydric alcohol solvents such as 2,4-ethylpentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethylhexanediol, 1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanediol, ketone solvents such as acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono ether solvents such as diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;Diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene acetate Examples of suitable solvents include ester-based solvents such as glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone.

[0074] The silicon-containing planarizing pattern reversal coating agent of the present invention contains the above-mentioned (A) modified polysiloxane, (B) curing catalyst, and (C) organic solvent that does not damage the resist film, and may contain other components described below as desired. The solid content of the planarizing pattern reversal coating agent may be, for example, 0.1 to 50 mass%, 0.1 to 30 mass%, 0.1 to 25 mass%, or 0.5 to 20.0 mass% based on the total mass of the coating agent. The solid content refers to the total components of the coating agent excluding the (C) organic solvent (and other organic solvents). The content of the modified polysiloxane (A) in the solid content is usually 20% by mass or more and less than 100% by mass. From the viewpoint of reproducibly obtaining the above-mentioned effects of the present invention, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and still more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being The additives described below may be used. The coating agent for pattern reversal preferably has a pH of 2-5, and more preferably has a pH of 3-4.

[0075] The above-mentioned pattern reversal coating agent can be produced by mixing the above-mentioned (A) modified polysiloxane, (B) curing catalyst, (C) organic solvent that does not damage the resist film, and other components described below as desired. In this case, a solution containing the (A) modified polysiloxane may be prepared in advance, and this solution may be mixed with the (B) curing catalyst, (C) organic solvent that does not damage the resist film, and other components. In addition, the reaction solution used when preparing the (A) modified polysiloxane may be used as is for preparing the above-mentioned pattern reversal coating agent. The order of mixing is not particularly limited. For example, (A) the solution containing the modified polysiloxane may be mixed with (B) the curing catalyst and (C) the organic solvent that does not damage the resist film, and other components may be added to the mixture, or (A) the solution containing the modified polysiloxane, (B) the curing catalyst, (C) the organic solvent that does not damage the resist film, and other components may be mixed simultaneously. If necessary, (C) an organic solvent that does not damage the resist film may be added at the end, or some components that are relatively soluble in (C) an organic solvent that does not damage the resist film may be left out of the mixture and added at the end, but from the viewpoint of suppressing aggregation or separation of the components and reproducibly preparing a composition with excellent uniformity, it is preferable to prepare a solution in which (A) the modified polysiloxane is well dissolved in advance and use this to prepare the composition. Note that (A) the modified polysiloxane may aggregate or precipitate when mixed with (B) the curing catalyst and (C) the organic solvent that does not damage the resist film, depending on the type and amount of these to be mixed together, and the amount and properties of other components. In addition, when preparing a composition using a solution in which the (A) modified polysiloxane is dissolved, it is necessary to determine the concentration of the (A) modified polysiloxane solution and the amount used so that the final composition contains the desired amount of (A) modified polysiloxane. In preparing the composition, heating may be performed appropriately within a range in which the components are not decomposed or deteriorated.

[0076] In the present invention, the pattern reversal coating agent may be filtered using a sub-micrometer filter or the like during the production process or after all the components are mixed. The material of the filter used in this case is not limited, and for example, a nylon filter, a fluororesin filter, or the like can be used.

[0077] Various additives can be incorporated into the silicon-containing planarizing pattern reversal coating agent of the present invention. Examples of the additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymer compounds, photoacid generators (onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, etc.), surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), rheology adjusters, adhesion aids, and other known additives that are blended into materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, antireflection films, and pattern reversal films. Various additives are exemplified below, but are not limited to these.

[0078] <Surfactant> The surfactant is effective in suppressing the occurrence of pinholes, striations, etc., when the silicon-containing planarizing pattern reversal coating agent is applied onto a resist pattern. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc. More specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl 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, and polyoxyethylene sorbitan tristearate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as oleate and polyoxyethylene sorbitan tristearate, trade names: F-TOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade names: Megafac (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Fluorad F Examples of suitable surfactants include, but are not limited to, fluorine-based surfactants such as C430, FC431 (manufactured by 3M Japan Ltd.), Asahi Guard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The surfactants can be used alone or in combination of two or more. When a surfactant is used, the amount of the surfactant added is, for example, usually 0.0001 to 5 mass %, preferably 0.001 to 4 mass %, and more preferably 0.01 to 3 mass %, relative to the mass of the (A) modified polysiloxane.

[0079] <Rheology modifier> The rheology control agent is mainly added to improve the fluidity of the silicon-containing planarizing pattern reversal coating agent, and especially in the baking process, to improve the uniformity of the film thickness of the film formed and to enhance the filling of the composition into the hole.Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate, adipic acid derivatives such as di-n-butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyl decyl adipate, maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate, and stearic acid derivatives such as normal butyl stearate and glyceryl stearate. When these rheology control agents are used, the amount added is usually less than 30% by mass based on the total solid content of the silicon-containing planarizing pattern reversal coating agent.

[0080] [Method of forming inversion pattern] The present invention is also directed to a method for pattern reversal, i.e., a method for forming a reverse pattern, using the above-described silicon-containing planarizing pattern reversal coating as a reverse material (pattern reversal material). The pattern reversal method generally includes the steps of: (1) forming a resist film on a substrate; (2) forming a resist pattern by irradiation with light or an electron beam and development; (3) applying the silicon-containing planarizing pattern reversal coating agent onto the patterned resist film during or after development, and baking the coating agent to form a cured film; (4) etching back the surface of the cured film by dry etching to expose the resist pattern surface of the patterned resist film; and (5) removing the patterned resist film by wet etching to reverse the pattern. As described above, the silicon-containing planarizing pattern reversal coating agent of the present invention is a coating agent for coating on a resist pattern, more specifically, a coating agent for coating on a line and space resist pattern. The coating agent is coated on a resist pattern having a layout of sparse and dense pattern areas (line parts). Moreover, the resist pattern may be a pattern formed by nanoimprinting.

[0081] <Process (1)> Substrates used in the pattern reversal method of the present invention include substrates used in the manufacture of precision integrated circuit elements (for example, semiconductor substrates such as silicon wafers coated with a silicon oxide film, a silicon nitride film or a silicon oxynitride film, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass and crystallized glass), glass substrates on which an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film is formed, plastic (polyimide, PET, etc.) substrates, substrates coated with low dielectric constant materials (low-k materials), flexible substrates, etc.). A coating type resist material (e.g., a composition for forming a photoresist film) is applied onto the substrate by a suitable coating method such as spin coating, dipping, flow coating, inkjet coating, spraying, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, blade coating, air knife coating, etc., and then baked to form a layer of the photoresist material (resist film). The baking conditions can be, for example, a baking temperature of 70 to 150° C. and a baking time of 0.5 to 5 minutes. The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0082] The photoresist material used in the formation of the resist film in step (1) is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative and positive photoresist materials can be used. For example, there are positive photoresist materials consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresist materials consisting of a binder having a group that decomposes with acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresist materials consisting of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresist materials consisting of a binder having a group that decomposes with acid to increase the alkaline dissolution rate, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist material, and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772JN (trade name) manufactured by JSR Corporation, and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. In addition, examples of fluorine-containing polymer photoresist materials include those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0083] Furthermore, for the resist film, a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film) can be used instead of a photoresist film. The electron beam resist material may be either a negative-type material or a positive-type material. Specific examples thereof include a chemically amplified resist material consisting of an acid generator and a binder having a group that is decomposed by an acid to change the alkali dissolution rate, an alkali-soluble binder and an acid generator, These include chemically amplified resist materials made of low molecular weight compounds that decompose in the presence of acid to change the alkaline dissolution rate of the resist material, chemically amplified resist materials made of an acid generator, a binder having a group that decomposes in the presence of acid to change the alkaline dissolution rate, and a low molecular weight compound that decomposes in the presence of acid to change the alkaline dissolution rate of the resist material, non-chemically amplified resist materials made of a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate, and non-chemically amplified resist materials made of a binder having a site that is cleaved by an electron beam to change the alkaline dissolution rate. When these electron beam resist materials are used, a resist film pattern can be formed in the same way as when a photoresist material is used with an electron beam as the irradiation source. As the EUV resist material, a methacrylate resin-based resist material can be used.

[0084] Among these, chemically amplified photoresist materials comprising a binder having a group that is decomposed by acid to increase the alkali dissolution rate and a photoacid generator, such as acrylic photoresist materials and methacrylic photoresists, and particularly acrylic or methacrylic positive photoresist materials, can be preferably used.

[0085] Incidentally, the step (1) may be a step (1-1) including a step of forming a resist underlayer film on a substrate before forming a resist film on the substrate. Here, the resist underlayer film has anti-reflection and organic hard mask functions. In this case, the resist film is formed after the resist underlayer film is formed on the semiconductor substrate.

[0086] Also, the step (1-1) may include a step of forming a resist underlayer film on a substrate, a step of forming a silicon hard mask on the underlayer film, and a step of forming a resist film on the hard mask.

[0087] The resist underlayer film used in the above step (1-1) is used to prevent diffuse reflection during exposure of the upper resist film and to improve adhesion with the resist film, and can be made of, for example, an acrylic resin or a novolac resin. The resist underlayer film can be formed into a coating having a thickness of 1 to 1,000 nm on the semiconductor substrate.

[0088] The resist underlayer film used in step (1-1) is a hard mask using an organic resin, and is made of a material with a high carbon content and a low hydrogen content. Examples of such materials include polyvinylnaphthalene resins, carbazole novolac resins, phenol novolac resins, and naphthol novolac resins. These resins can be used to form a coating film with a thickness of 5 to 1,000 nm on a semiconductor substrate.

[0089] In addition, the silicon hard mask used in the above step (1-1) can be a polysiloxane obtained by hydrolysis of a hydrolyzable silane. For example, polysiloxanes obtained by hydrolysis of tetraethoxysilane, methyltrimethoxysilane, and phenyltriethoxysilane can be exemplified. These can form a coating with a thickness of 5 to 200 nm on the resist underlayer film.

[0090] <Process (2)> In the next step (2), the resist is exposed (by light or electron beam) through a predetermined mask and developed to form a resist pattern. First, the resist film is exposed through a predetermined mask (reticle). For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), an EUV (wavelength 13.5 nm), an electron beam, etc. can be used. After the exposure, a post exposure bake may be carried out as necessary under conditions appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 minutes to 10 minutes.

[0091] Next, development is carried out with a developer (e.g., an alkaline developer). As a result, when a positive photoresist film is used, the photoresist film in the exposed portion is removed, and a pattern of the photoresist film is formed. Examples of the developer (alkaline developer) include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline, or an aqueous solution of an amine such as ethanolamine, propylamine, or ethylenediamine. Furthermore, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

[0092] <Process (3)> Next, in step (3), the silicon-containing planarizing pattern reversal coating agent is applied onto the resist film on which the pattern is formed during or after development, and then baked to form a hardened film. Through this step, the pattern reversal coating agent is embedded into the formed resist pattern.

[0093] As the coating method, the above-mentioned methods can be used. The baking conditions are a baking temperature of 80°C to 150°C and a baking time of 0.5 to 2 minutes. In order to achieve high uniformity without bias in the distribution of the film thickness and to promote the reaction by the curing catalyst, the temperature may be changed in two or more stages. In the present invention, the curing of the pattern reversal coating agent is promoted during baking by the blending of the above-mentioned (B) curing catalyst, and a cured film can be obtained even under the above-mentioned relatively low baking conditions. If the baking temperature is higher than the above range, the curing of the film is promoted, but there is a risk that the temperature will be higher than the glass transition point of the binder contained in the lower resist film, and in that case, there is a risk of problems such as the resist film melting. The baking method is not particularly limited, and may be, for example, a method in which the solvent is evaporated using a hot plate or an oven in a suitable atmosphere such as air, an inert gas such as nitrogen, or a vacuum. The thickness of the cured film is appropriately adjusted to a thickness that covers the underlying resist pattern, and is, for example, 10 to 1,000 nm, or 20 to 500 nm, or 50 to 300 nm, or 100 to 200 nm, or 10 to 100 nm.

[0094] As the silicon-containing planarizing pattern reversal coating agent used in forming the cured film, a silicon-containing planarizing pattern reversal coating agent filtered through a nylon filter can be used. Here, the term "silicon-containing planarizing pattern reversal coating agent filtered through a nylon filter" refers to a coating agent that is filtered through a nylon filter during the production process of the coating agent or after all the components are mixed. This refers to a coating material that has been subjected to filter filtration.

[0095] <Process (4)> After step (3), the surface of the cured film of the silicon-containing planarizing pattern reversal coating agent of the present invention is etched back to expose the resist pattern surface (the portion (line portion) where the resist pattern exists). This step allows the surface of the resist pattern (the portion where the resist pattern is present (line portion)) to coincide with the surface of the cured film, and the difference in gas etching rate between the resist pattern and the cured film is eliminated. Therefore, only the resist components are removed and the components of the hardened film remain, resulting in pattern inversion. The etch-back is performed by dry etching using a gas capable of removing the cured film, such as tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, difluoromethane (CH 2 F 2 ) is used.

[0096] <Process (5)> In step (5), the resist pattern (patterned resist film) is removed by etching to reverse the pattern. By this step, the original resist pattern is removed, and a reverse pattern is formed by the pattern reversal forming polymer (cured product of modified polysiloxane) contained in the silicon-containing planarizing pattern reversal coating agent.

[0097] The present invention is characterized in that the resist film is removed by wet etching. When the resist film is removed by dry etching, the cured film needs to be resistant to etching gas. As described above, if the silicon content of the reversal material is increased in order to increase the dry etching resistance of the reversal material, there is a risk that the reversal material may lose its ability to be embedded in the resist pattern or its planarization ability. Furthermore, removing the resist film by dry etching can cause defects in the shape of the pattern top (surface) and sidewalls of the inverted pattern, making it difficult to obtain a rectangular inverted pattern. Furthermore, the etching may extend beyond the resist film to the layers below it. In the present invention, wet etching is employed as a means for removing the resist film, so that the resist film, which is an uncured film, can be selectively removed.

[0098] As the chemical solution used for wet etching of the resist pattern, for example, an organic solvent that can be used as a developer when developing the resist pattern can be used. Examples of the chemical solution (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether, 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, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate. , 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl -3-Methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propionate Examples of the chemicals include propyl phosphate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate, which can be used alone or in combination of two or more. Furthermore, surfactants and the like can be added to these chemical solutions.

[0099] The wet etching conditions are appropriately selected from the temperature range of 20° C. to 80° C. and the time range of 10 seconds to 600 seconds.

[0100] In the present invention, a resist pattern is formed on a substrate as described above, and the resist pattern is coated with the silicon-containing planarizing pattern reversal coating agent of the present invention. This fills the gaps between the resist patterns, and then the coating agent is baked to form a hardened film. The upper part of the hardened film is then etched back with a fluorine-based gas to expose the upper part of the resist pattern, and the resist pattern is then removed by wet etching, so that the resist pattern disappears and the silicon-based pattern derived from the silicon-based hardened film remains, thereby reversing the pattern.

[0101] If the surface of the silicon-based cured film is not flattened to a certain level during the above-mentioned etch-back, when the resist pattern surface is exposed by etching back, the top of the line part of the resist pattern and the embedded space part are not horizontal, and a constant horizontal inversion pattern cannot be obtained even after the pattern is inverted. This is undesirable because it leads to non-uniform processing of the lower layer in the subsequent etching of the lower layer. The silicon-containing planarizing pattern reversal coating agent of the present invention uses a modified polysiloxane in which the silanol groups in the polysiloxane are capped, and when a resist pattern formed on a semiconductor substrate is coated with the coating agent, a flat coating surface having good embedding properties is obtained, and good pattern reversal is achieved. Furthermore, the silicon-containing planarizing pattern reversal coating agent of the present invention uses a curing catalyst and an organic solvent that does not damage the resist film, so that adverse effects on the resist pattern shape during coating of the resist pattern can be suppressed, and wet etching can be selected for removing the resist pattern, making it possible to selectively remove the resist film, which is a non-cured film.

[0102] By using the silicon-containing planarizing pattern reversal coating agent of the present invention and the reversal pattern forming method of the present invention described above, a reverse pattern can be obtained, which can be used to suitably process a semiconductor substrate. Therefore, the present invention also covers a method for manufacturing a semiconductor element using the above-mentioned reversal pattern forming method. EXAMPLES

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0104] The apparatus and conditions used for analyzing the physical properties of the samples shown below are as follows. (1) Molecular weight measurement The molecular weight of the polysiloxane used in the present invention is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC measurement conditions are, for example, a GPC apparatus (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow velocity) of 1.0 mL / min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.). (2) 1 H-NMR JEOL nuclear magnetic resonance spectrometer 1 The evaluation was performed by H-NMR (400 MHz) using d6-Acetone as the solvent.

[0105] [Synthesis of polymer (modified polysiloxane)] <Synthesis Example 1> 22.2 g (30 mol%) of tetraethoxysilane, 44.4 g (70 mol%) of methyltriethoxysilane, and 100 g of acetone were placed in a 500 mL flask, and while the mixed solution in the flask was stirred with a magnetic stirrer, 21.2 g of a 0.01 mol / L aqueous nitric acid solution was added dropwise to the mixed solution. After the dropwise addition, the flask was transferred to an oil bath adjusted to 85°C, and the reaction was carried out under heating and reflux for 20 hours. Thereafter, the reaction solution was cooled to room temperature, and 100 g of 4-methyl-2-pentanol was added to the reaction solution. Acetone, water, nitric acid, and ethanol, which is a reaction by-product, were distilled off from the reaction solution under reduced pressure to concentrate the solution, thereby obtaining a 4-methyl-2-pentanol solution of a cohydrolyzed condensate (polymer). 4-methyl-2-pentanol was appropriately added to adjust the solid content concentration to 13% by mass. 20 mg of acetic acid was added to 15 g of the above polymer solution. The flask was transferred to an oil bath adjusted to 120° C., and the reaction was carried out for 48 hours under heating and reflux. The weight average molecular weight Mw measured by GPC was 4,000 in terms of polystyrene. The resulting polysiloxane was a polysiloxane in which some of the silanol groups had been capped with 4-methyl-2-pentanol (modified polysiloxane P1).

[0106] <Synthesis Example 2> 64.7 g (60 mol%) of tetraethoxysilane, 36.9 g (40 mol%) of methyltriethoxysilane, and 100 g of acetone were placed in a 500 mL flask, and while the mixed solution in the flask was stirred with a magnetic stirrer, 32.6 g of a 0.01 mol / L aqueous nitric acid solution was added dropwise to the mixed solution. After the dropwise addition, the flask was transferred to an oil bath adjusted to 85°C and reacted for 20 hours under heating and reflux. Thereafter, the reaction solution was cooled to room temperature, and 100 g of 4-methyl-2-pentanol was added to the reaction solution. Acetone, water, nitric acid, and ethanol, which was a reaction by-product, were distilled off under reduced pressure from the reaction solution to concentrate it, thereby obtaining a 4-methyl-2-pentanol solution of a cohydrolyzed condensate (polymer). The above polymer solution was transferred to an oil bath adjusted to 140°C and reacted for 24 hours under heating and reflux. 4-Methyl-2-pentanol was added appropriately to adjust the solid content concentration to 13% by mass. The weight average molecular weight Mw measured by GPC was 4,000 in terms of polystyrene. The resulting polysiloxane was a polysiloxane in which some of the silanol groups had been capped with 4-methyl-2-pentanol (modified polysiloxane P2).

[0107] [Calculation of silanol group ratio and capping ratio] The silanol group ratio and capping ratio in the polymer are 1 The values ​​were calculated using H NMR. The measurements were performed using a JNM-ECA500 (manufactured by JEOL). First, the integral ratio of the chemical shift value (0.0-0.3 ppm) of the methyl proton of methyltriethoxysilane was taken as the standard. The chemical shift value of the methine proton of 4-methyl-2-pentanol is detected at around 3.8 ppm, but when it forms a bond with a silicon atom through a dehydration condensation reaction with a silanol group, i.e., when a capping reaction of the silanol group with 4-methyl-2-pentanol occurs, the chemical shift value of the methine proton moves to around 4.2 ppm. After the capping reaction, the integral ratio of the methine proton that has moved to around 4.2 ppm is measured, and compared with the integral ratio of the methyl proton of methyltriethoxysilane measured earlier, the silicon in the polymer can be determined. The silanol group ratio (residual rate) per atom and the capping rate of 4-methyl-2-pentanol were calculated.

[0108] The silanol group ratio in the polysiloxane and the capping ratio of 4-methyl-2-pentanol were calculated using the modified polysiloxanes P1 and CP1 prepared in Synthesis Example 1 and Comparative Synthesis Example 1. The results are shown in Table 1. In Table 1, 4-methyl-2-pentanol is abbreviated as MIBC.

[0109] [Table 1]

[0110] [Preparation of coating solution] The modified polysiloxanes (P1, P2) obtained in the above synthesis examples, a curing catalyst (benzyltrimethylammonium chloride), and a solvent were mixed in the ratios shown in Table 2 to obtain silicon-containing planarizing pattern reversal coating agents (coating solutions) of Examples 1 and 2. The amounts of each additive in Table 2 are shown in parts by mass. The modified polysiloxane (polymer) was used as a solution containing the modified polysiloxane obtained in the above synthesis example, and a curing catalyst was added thereto, and a solvent was further added to prepare a coating solution. The polymer content shown in Table 2 does not indicate the polymer solution, but indicates the solid content obtained by excluding the solvent from the polymer solution. In Table 2, benzyltrimethylammonium chloride is abbreviated as BTEAC and 4-methyl-2-pentanol is abbreviated as MIBC.

[0111] [Table 2]

[0112] [Evaluation of planarization and filling properties] The planarizing property and filling property of each of the silicon-containing planarizing pattern reversal coating agents (coating solutions) of Examples 1 and 2 were evaluated by the following procedures. The silicon-containing planarizing pattern reversal coating agent of Example 1 or Example 2 was applied onto a stepped substrate (a substrate having a continuous pattern consisting of area (a) groove depth 220 nm, groove width 50 nm-area (b) no groove (pattern)-area (c) groove depth 220 nm, groove width 800 nm) using a spin coater at a rotation speed of 1,500 rpm for 60 seconds, and then dried on a hot plate at 140°C for 1 minute to obtain a cured film of Example 3 or Example 4. The cured film The film thickness was set to 120 nm. Next, the cross-sectional shape of the obtained cured film was observed by cross-sectional SEM to evaluate the planarization. The planarization was evaluated by observing the groove pattern of the step substrate, measuring the film thickness at the thinnest part and the thickest part based on the groove bottom, and calculating the film thickness difference from these. The smaller the film thickness difference, the better the planarization can be evaluated. In addition, the presence or absence of voids inside the grooves was confirmed by cross-sectional SEM, and those in which insufficient filling (voids) was confirmed were rated as poor, and those in which no insufficient filling was confirmed were rated as good. The results are shown in Table 3. Cross-sectional SEM photographs (magnification: 100,000 times) of the cured film used for evaluation are shown in Figure 1 (Example 3) and Figure 2 (Example 4), respectively. In each figure, (a), (b), and (c) respectively correspond to the above area (a) groove depth 220 nm, groove width 50 nm, (b) area (b) no groove (pattern) (line portion of stepped substrate), and area (c) groove depth 220 nm, groove width 800 nm.

[0113] [Table 3]

[0114] As shown in Table 3 and FIG. 1, the silicon-containing planarizing pattern reversal coating agent of Example 1 had good groove embedding properties, and the cured film of Example 3, which had better planarization properties than Example 2, was obtained. In the coating material of Example 2, voids (black spots in the grooves in FIG. 2(a)) were observed in the grooves, and the difference in film thickness was larger than that in the coating material of Example 1 (see FIG. 1(c) and FIG. 2(c)).

[0115] [Pattern reversal evaluation] <Photoresist pattern formation> A resist underlayer film material (ARC29A, Nissan Chemical Co., Ltd.) was applied onto a silicon wafer using a spinner. The silicon wafer was placed on a hot plate and heated at 205°C for 1 minute to form a resist underlayer film with a thickness of 80 nm. A commercially available acrylic photoresist solution was applied onto the resist underlayer film using a spinner, and the resulting solution was heated on a hot plate at 110°C for 90 seconds to form a photoresist film (thickness 0.12 μm). Next, ArF exposure was performed through a photomask using a scanner (Nikon Corporation, NSR-S307E). The photomask was selected according to the resist pattern to be formed. After exposure, the resist was post-exposure baked (PEB) at 110°C for 90 seconds on a hot plate, cooled, and then developed using a 2.38% aqueous solution of tetramethylammonium hydroxide as the developer in an industrial standard 60-second single paddle process. Through the above steps, the desired resist pattern (a 1:1 line and space pattern with a line width of 65 nm) was formed.

[0116] <Resist pattern embedding process> The silicon-containing planarizing pattern reversal coating agent (coating liquid) of Example 1 was applied using a spinner onto a resist pattern (1:1 line and space pattern with a line width of 65 nm) formed on a silicon wafer, and baked at 140°C for 1 second to obtain a cured film covering the resist pattern.

[0117] <Resist etch-back and wet resist removal processes> The cured film coated with the resist pattern was then subjected to parallel plate type RIE using RIE-2 The resist was exposed (the resist pattern surface was exposed) using 00NL (manufactured by SUMCO Corporation). CF 4 The etching was performed for 103 seconds by dry etching using a single gas (flow rate 50 sccm), and the upper part of the resist pattern was exposed (cross-sectional SEM photograph (magnification: 100,000 times): Figure 3). Thereafter, the wafer was immersed in OK73 thinner (Tokyo Ohka Kogyo Co., Ltd.) heated to 60° C. for 180 seconds to perform wet removal of the resist (cross-sectional SEM photograph (magnification: 100,000 times): FIG. 4). The results are shown in Table 4.

[0118] [Table 4]

[0119] As shown in Table 4 and FIGS. 3 and 4, the above procedure confirmed that the resist was exposed and then wet removed, and a good reverse pattern was obtained.

Claims

1. A process for forming a resist film on a substrate, A step of forming a resist pattern by irradiation with light or an electron beam and development; A step of applying a silicon-containing planarizing pattern reversal coating agent onto the resist film having the pattern formed thereon during or after development, and baking the coating agent to form a hardened film; a step of etching back the surface of the cured film by dry etching to expose a resist pattern surface of the resist film on which a pattern has been formed; removing the patterned resist film by wet etching to reverse the pattern; A method for forming a reverse pattern, comprising the steps of: The silicon-containing planarizing pattern reversal coating agent is (A) a modified polysiloxane comprising a hydrolysis condensate of a hydrolyzable silane, in which at least a portion of the silanol groups contained therein are capped; (B) a curing catalyst; (C) an organic solvent that does not damage the resist film; and In the step of reversing the pattern, the patterned resist film is removed by wet etching using an organic solvent. A method for forming an inversion pattern.

2. The organic solvent (C) contains a hydrophobic alcohol that is poorly soluble in the resist film. The method for forming a reverse pattern according to claim 1 .

3. 3. The method for forming a reversal pattern according to claim 2, wherein the organic solvent (C) contains a hydrophobic alcohol that, when brought into contact with a resist film made of an ArF resist material for 60 seconds, reduces the thickness of the resist film after contact by 10% or less relative to the thickness of the resist film before contact.

4. The ratio of silanol groups to all silicon atoms in the modified polysiloxane (A) is 50 moles 4. The method for forming a reverse pattern according to claim 1, wherein the surface roughness is 0.01 to 0.1%.

5. The modified polysiloxane (A) a modified product of the hydrolysis-condensation product in which at least a portion of the silanol groups of the hydrolysis-condensation product are modified with alcohol; A modified product of the hydrolysis condensation product in which at least a part of the silanol groups of the hydrolysis condensation product are acetal-protected, and The hydrolysis condensation product and the alcohol dehydration reaction product are included. The method for forming a reverse pattern according to claim 1 .

6. 6. The method for forming a reverse pattern according to claim 5, wherein said alcohol is a monohydric alcohol.

7. 7. The method for forming a reverse pattern according to claim 5, wherein the modified polysiloxane (A) contains a dehydration reaction product of the hydrolysis-condensation product and an alcohol.

8. 8. The method for forming a reverse pattern according to claim 1, wherein the polysiloxane consisting of the hydrolysis condensation product of the hydrolyzable silane is a hydrolysis condensation product of a hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1): 【Chemistry 1】 (In the formula, R １ are groups bonded to silicon atoms, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof; R ２ are groups or atoms bonded to a silicon atom, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom; a represents an integer of 0 to 3.

9. The polysiloxane comprising the hydrolysis condensate of the hydrolyzable silane is A hydrolysis condensate of a hydrolyzable silane (ii) in which a in the above formula (1) is 1, or a co-hydrolyzable silane (i) in which a in the above formula (1) is 0 and a co-hydrolyzable silane (ii) in which a in the above formula (1) is 1; The method for forming a reverse pattern according to claim 8 .

10. The polysiloxane comprising the hydrolysis condensate of the hydrolyzable silane is a co-hydrolyzed condensate having the hydrolyzable silane (i) and the hydrolyzable silane (ii) in a molar ratio of 20:80 to 40:60; The method for forming a reverse pattern according to claim 9 .

11. 11. The method for forming a reversal pattern according to claim 1, wherein the resist film is a film made of an ArF resist material.

12. The method for forming a reversal pattern according to claim 1 , wherein in the step of forming the cured film, a baking temperature is 80° C. to 180° C.

13. A method for manufacturing a semiconductor device, comprising using the method for forming a reverse pattern according to claim 1 .

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