Composition for forming silicon-containing underlayer film

Abstract

This composition for forming a silicon-containing underlayer film is used for forming a silicon-containing underlayer film on which a surface-modified layer having a film thickness of 5 nm or less is formed. Said composition contains an [A] component that is a polysiloxane including a Q unit in the amount of 30 mol% or more relative to all units, and a [B] component that is water, but said composition does not contain a [C] component that is a curing catalyst.

Description

Silicon-containing underlayer film forming composition

[0001] The present invention relates to a composition for forming a silicon-containing underlayer film.

[0002] Conventionally, microfabrication using lithography with photoresist has been performed in the manufacture of semiconductor devices. Microfabrication is a processing method in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and then the photoresist is irradiated with actinic rays such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developed, and the substrate is etched using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the pattern. In recent years, with the increasing integration density of semiconductor devices, the actinic rays used have tended to be shorter in wavelength, from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). As the wavelength of actinic rays has become shorter, the impact of actinic rays reflecting off semiconductor substrates has become a major problem. As a result, a method of providing a resist underlayer film called an anti-reflective coating (BARC) between the photoresist and the substrate to be processed has become widely used.

[0003] As a cutting-edge microfabrication technology, 10-nm node devices are being mass-produced using double patterning with ArF immersion lithography. As a next-generation technology, preparations are underway for mass production of 7-nm node devices using double patterning with ArF immersion lithography. Extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm is being considered as a candidate for mass production of the next-generation technology, the 5-nm node.

[0004] In advanced microfabrication, miniaturization is difficult using only a resist film, and the miniaturization process is becoming impossible without the use of a hard mask formed under the resist film. Under these circumstances, one method using a hard mask as a resist underlayer is the multilayer resist method. In this method, an underlayer film with etching selectivity different from that of the resist film, such as a silicon-containing resist underlayer film, is interposed between the resist film and the substrate to be processed. After obtaining a resist pattern, the resist pattern is transferred to the silicon-containing resist underlayer film by dry etching using the resist pattern as an etching mask. Furthermore, the silicon-containing resist underlayer film is used as an etching mask to transfer the pattern to the substrate to be processed or a film serving as a core for spacer processing by dry etching.

[0005] As a composition for forming a silicon-containing resist underlayer film applicable to a multilayer resist method, a composition for forming a resist underlayer film containing a silicon-containing compound obtained by hydrolyzing or condensing a specific silicon compound, or both, has been proposed (see, for example, Patent Document 1).

[0006] Japanese Patent Application Laid-Open No. 2014-157242

[0007] As resist patterns become finer in advanced microfabrication, thinner silicon-containing resist underlayer films are required. Silicon-containing resist underlayer films are required to have properties such as adhesion to the resist film and etching resistance, but it is becoming difficult for thin silicon-containing resist underlayer films to satisfy all of these requirements.

[0008] The present invention has been made in view of these circumstances, and aims to provide a technology that enables the miniaturization of resist patterns by combining a surface modification layer with a silicon-containing underlayer film instead of a single-layer silicon-containing resist underlayer film. The present invention aims to provide a silicon-containing underlayer film-forming composition for forming a silicon-containing underlayer film in a technology that enables the miniaturization of resist patterns by combining a surface modification layer with a silicon-containing underlayer film. The present invention aims to provide a semiconductor device manufacturing method and a pattern forming method that enable the miniaturization of resist patterns by combining a surface modification layer with a silicon-containing underlayer film.

[0009] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0010] That is, the present invention includes the following: [1] A composition for forming a silicon-containing underlayer film on which a surface-modified layer of 5 nm or less in thickness is formed, comprising: [A] component: a polysiloxane containing 30 mol % or more of Q units based on all units, and [B] component: water, and not containing [C] component: a curing catalyst. [2] A composition for forming a silicon-containing underlayer film on which a surface-modified layer of 5 nm or less in thickness is formed, the surface-modified layer being formed on a silicon-containing underlayer film that has been subjected to at least one of a dry etching treatment, a baking treatment at 250°C or higher, and a UV irradiation treatment, and comprising: [A] component: a polysiloxane containing 30 mol % or more of Q units based on all units. [3] The composition for forming a silicon-containing underlayer film according to [2], wherein the atmospheric gas used in the dry etching treatment contains at least one of oxygen gas, hydrogen gas, nitrogen gas, and a rare gas, the wavelength used in the UV irradiation treatment is 170 nm to 370 nm, and the atmosphere is either an oxygen-containing atmosphere or a nitrogen atmosphere. [4] The composition for forming a silicon-containing underlayer film according to [1] or [2], wherein the polysiloxane of the component [A] is a hydrolysis condensation product of a hydrolyzable silane (Si-1), and the hydrolyzable silane (Si-1) contains 30 mol % or more of a hydrolyzable silane represented by the following formula (A): (In formula (A), R is a group or atom bonded to a silicon atom, and each R independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.) [5] The composition for forming a silicon-containing underlayer film according to [4], wherein the hydrolyzable silane (Si-1) further contains a hydrolyzable silane represented by the following formula (B): (In formula (B), R １１ are groups bonded to silicon atoms, and each independently represents an organic group having 1 to 45 carbon atoms. １２are groups or atoms bonded to silicon atoms, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 1 to 3.) [6] The composition for forming a silicon-containing underlayer film according to any one of [1] to [5], wherein the surface modification layer is formed using a composition for forming a surface modification layer containing a polysiloxane and a solvent. [7] The composition for forming a silicon-containing underlayer film according to [6], wherein the polysiloxane contained in the composition for forming a surface modification layer is a hydrolysis condensate of a hydrolyzable silane (Si-2), and the hydrolyzable silane (Si-2) contains a hydrolyzable silane represented by the following formula (S1): (In formula (S1), R ２１ are groups bonded to silicon atoms, and each independently represents an organic group having 1 to 45 carbon atoms. ２２are groups or atoms bonded to silicon atoms, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 1 to 3.) [8] The composition for forming a silicon-containing underlayer film according to any one of [1] to [7], wherein the component [A] comprises a polysiloxane modified product in which at least a portion of the silanol groups have been alcohol-modified or acetal-protected. [9] The composition for forming a silicon-containing underlayer film according to any one of [1] to [8], wherein the composition comprises an alcohol-based solvent.

[10] The composition for forming a silicon-containing underlayer film according to [9], wherein the alcohol-based solvent comprises propylene glycol monoalkyl ether.

[11] The composition for forming a silicon-containing underlayer film according to any one of [1] to

[10] , wherein the composition comprises nitric acid.

[12] The composition for forming a silicon-containing underlayer film according to any one of [1] to

[11] , wherein the composition is used for EUV lithography.

[13] A silicon-containing underlayer film that is a cured product of the silicon-containing underlayer film-forming composition according to any one of [1] to

[12] .

[14] A semiconductor processing substrate comprising a semiconductor substrate and the silicon-containing underlayer film according to

[13] .

[15] A method for manufacturing a semiconductor device, comprising: forming an organic underlayer film on a substrate; forming a silicon-containing underlayer film on the organic underlayer film using the silicon-containing underlayer film-forming composition according to any one of [1] to

[12] ; forming a surface modification layer on the silicon-containing underlayer film; and forming a resist film on the surface modification layer.

[16] The method for manufacturing a semiconductor device according to

[15] , wherein the silicon-containing underlayer film-forming step includes at least one of dry etching, baking at 250°C or higher, and UV irradiation.

[17] The method for manufacturing a semiconductor element according to

[16] , wherein the atmospheric gas in the dry etching treatment contains at least one of oxygen gas, hydrogen gas, nitrogen gas, and a rare gas, the wavelength in the UV irradiation treatment is 170 nm to 370 nm, and the atmosphere is either an oxygen-containing atmosphere or a nitrogen atmosphere.

[18] A pattern formation method comprising the steps of: forming an organic underlayer film on a semiconductor substrate; applying the silicon-containing underlayer film-forming composition according to any one of [1] to

[12] onto the organic underlayer film and baking the composition to form a silicon-containing underlayer film; forming a surface modification layer on the silicon-containing underlayer film; forming a resist film on the surface modification layer; exposing and developing the resist film to obtain a resist pattern; etching the surface modification layer and the silicon-containing underlayer film using the resist pattern as a mask; and etching the organic underlayer film using the patterned surface modification layer and the silicon-containing underlayer film as a mask.

[19] The pattern formation method according to

[18] , wherein the step of forming the silicon-containing underlayer film includes at least one of a dry etching treatment, a baking treatment at 250°C or higher, and a UV irradiation treatment.

[20] The pattern formation method according to

[19] , wherein the atmospheric gas in the dry etching treatment contains at least one of oxygen gas, hydrogen gas, nitrogen gas, and a rare gas, the wavelength in the UV irradiation treatment is 170 nm to 370 nm, and the atmosphere is either an oxygen-containing atmosphere or a nitrogen atmosphere.

[21] The pattern formation method according to

[18] , further comprising, after the step of etching the organic underlayer film, a step of removing the resist underlayer film by a wet method using a chemical solution.

[0011] According to the present invention, it is possible to provide a technology that enables the miniaturization of resist patterns by combining a surface modification layer and a silicon-containing underlayer film instead of a single-layer silicon-containing resist underlayer film. According to the present invention, it is possible to provide a silicon-containing underlayer film-forming composition for forming a silicon-containing underlayer film in a technology that enables the miniaturization of resist patterns by combining a surface modification layer and a silicon-containing underlayer film. According to the present invention, it is possible to provide a semiconductor device manufacturing method and a pattern forming method that enable the miniaturization of resist patterns by combining a surface modification layer and a silicon-containing underlayer film.

[0012] (Silicon-Containing Underlayer Film-Forming Composition) The silicon-containing underlayer film-forming composition of the present invention is a composition for forming a silicon-containing underlayer film on which a surface-modified layer having a thickness of 5 nm or less is formed.

[0013] Although it is usually not easy to form a thin layer on a silicon-containing underlayer film, the use of the composition for forming a silicon-containing underlayer film of the present invention makes it possible to form a surface-modified layer with a thickness of 5 nm or less in a good film state. Furthermore, the functions previously performed by a single-layer silicon-containing resist underlayer film are functionally separated into the surface-modified layer and the silicon-containing underlayer film, and the surface-modified layer is endowed with the function of improving resist pattern formation (for example, improving adhesion), while the silicon-containing underlayer film is endowed with the function of etching resistance, thereby making it possible to respond to miniaturization of the resist pattern.

[0014] First Embodiment A first embodiment of the composition for forming a silicon-containing underlayer film of the present invention contains component [A] and component [B], but does not contain component [C]. Component [A] is a polysiloxane containing 30 mol % or more of Q units relative to all units. Component [B] is water. Component [C] is a curing catalyst.

[0015] Second Embodiment A second embodiment of the silicon-containing underlayer film-forming composition of the present invention contains component [A]. Component [A] is a polysiloxane containing 30 mol % or more of Q units relative to all units. In the second embodiment, a surface-modified layer is formed on a silicon-containing underlayer film that has been subjected to at least one of dry etching, baking at 250°C or higher, and UV irradiation. Details of these treatments will be explained in conjunction with the detailed explanation of the semiconductor device manufacturing method of the present invention. In the second embodiment, for example, the silicon-containing underlayer film-forming composition may contain a curing catalyst. The inventors believe that when the silicon-containing underlayer film-forming composition contains a curing catalyst, the silicon-containing underlayer film obtained from the silicon-containing underlayer film-forming composition tends to have fewer Si—OH groups derived from the polysiloxane. In this case, when an attempt is made to form a surface-modified layer on a silicon-containing underlayer film, the film-forming properties of the surface-modified layer are reduced. Therefore, in the second embodiment, at least one of a dry etching process, a baking process at 250° C. or higher, and a UV irradiation process is performed before the formation of the surface modification layer. By performing these processes, the film-forming properties of the surface modification layer on the silicon-containing underlayer film are improved.

[0016] <Component [A]> The polysiloxane of component [A] contains Q units in an amount of 30 mol% or more, preferably 45 mol% or more, and more preferably 60 mol% or more, based on the total units. The upper limit of the proportion of Q units to the total units in the polysiloxane is not particularly limited, and the proportion of Q units may be, for example, 100 mol% or less, 90 mol% or less, or 85 mol% or less.

[0017] The term "total units" refers to the sum of M units, D units, T units, and Q units constituting the polysiloxane. The polysiloxane does not necessarily have all of the M units, D units, T units, and Q units. The term "M units" refers to (R) ３ SiO １／２Here, each R independently represents a hydrogen atom or an organic group. The number (here, 3) after (R) means that three hydrogen atoms or organic groups are bonded to the silicon atom. In other words, the M unit is a siloxy unit consisting of one silicon atom, three hydrogen atoms or organic groups, and one oxygen atom O. ＊ More specifically, the M unit has three hydrogen atoms or organic groups bonded to one silicon atom, and one oxygen atom O bonded to one silicon atom. ＊ The D unit has (R) ２ SiO ２／２ (each R independently represents a hydrogen atom or an organic group). That is, the D unit has one silicon atom, two hydrogen atoms or organic groups bonded to the silicon atom, and an oxygen atom O bonded to another silicon atom. ＊ The T unit is a unit having two RSiO ３／２ (R represents a hydrogen atom or an organic group). That is, the T unit has one silicon atom, one hydrogen atom or an organic group bonded to the silicon atom, and an oxygen atom O bonded to another silicon atom. ＊ The Q unit is a unit having three SiO ２ That is, the Q unit has one silicon atom and an oxygen atom O bonded to another silicon atom. ＊ It is a unit that has four of these.

[0018] The polysiloxane of component [A] preferably contains 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20 mol% or more of T units relative to all units. The upper limit of the proportion of T units relative to all units in the polysiloxane is not particularly limited, and the proportion of T units may be, for example, 70 mol% or less, 55 mol% or less, or 40 mol% or less.

[0019] The polysiloxane of component [A] preferably contains 70 mol % to 100 mol % of Q units and T units in total, more preferably 80 mol % to 100 mol %, and particularly preferably 90 mol % to 100 mol %, of all units.

[0020] The polysiloxane may include a modified polysiloxane in which a portion of the silanol groups has been modified, for example, a polysiloxane modified product in which a portion of the silanol groups has been alcohol-modified or acetal-protected. Furthermore, the polysiloxane may include, for example, a hydrolysis condensation product of a hydrolyzable silane, and may include a modified polysiloxane in which at least a portion of the silanol groups of the hydrolysis condensation product have been alcohol-modified or acetal-protected. The hydrolyzable silane in the hydrolysis condensation product may include one or more hydrolyzable silanes. Commercially available polysiloxanes can be used as the polysiloxane.

[0021] In the present invention, the "hydrolyzed condensate" of hydrolyzable silane, i.e., the product of hydrolysis and condensation, includes not only polyorganosiloxane polymers, which are condensates in which condensation has been completely completed, but also polyorganosiloxane polymers, which are partial hydrolyzed condensates in which condensation has not been completely completed. Such partial hydrolyzed condensates, like condensates in which condensation has been completely completed, are polymers obtained by hydrolysis and condensation of hydrolyzable silanes, but they are partially hydrolyzed and not condensed, and therefore Si-OH groups remain. In addition to the hydrolyzed condensate, the surface modifier may also contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silanes). In this specification, "hydrolyzable silanes" may also be simply referred to as "silane compounds." In addition, in this specification, "polysiloxanes" may also be referred to as "hydrolyzed condensates."

[0022] The polysiloxane is preferably a hydrolysis condensate of a hydrolyzable silane (Si-1). The hydrolyzable silane (Si-1) contains 30 mol % or more of a hydrolyzable silane represented by the following formula (A): (In formula (1), R represents a group or atom bonded to a silicon atom, and each R independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.)

[0023] When the hydrolyzable silane (Si-1) is subjected to hydrolysis and condensation to obtain a polysiloxane, the proportion of the hydrolyzable silane represented by formula (A) in the hydrolyzable silane (Si-1) is 30 mol% or more, preferably 45 mol% or more, and more preferably 60 mol% or more. The upper limit of the proportion of the hydrolyzable silane represented by formula (A) in the hydrolyzable silane (Si-1) when the hydrolyzable silane (Si-1) is subjected to hydrolysis and condensation to obtain a polysiloxane is not particularly limited, and the proportion may be, for example, 100 mol% or less, 90 mol% or less, or 85 mol% or less.

[0024] R in formula (A) is a hydrolyzable group. Examples of the alkoxy group in R in formula (A) include alkoxy groups having 1 to 4 carbon atoms. The aralkyloxy group in R in formula (A) is a monovalent group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol. 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 aralkyloxy groups include, but are not limited to, phenylmethyloxy (benzyloxy), 2-phenylethyleneoxy, 3-phenyl-n-propyloxy, 4-phenyl-n-butyloxy, 5-phenyl-n-pentyloxy, 6-phenyl-n-hexyloxy, 7-phenyl-n-heptyloxy, 8-phenyl-n-octyloxy, 9-phenyl-n-nonyloxy, and 10-phenyl-n-decyloxy. The acyloxy group for R in formula (A) is a monovalent group derived by removing a hydrogen atom from a carboxyl group (—COOH) of a carboxylic acid compound, and typical examples include an alkylcarbonyloxy group, an arylcarbonyloxy group, or an aralkylcarbonyloxy group, which are derived by removing a hydrogen atom from the carboxyl group of an alkylcarboxylic acid, an arylcarboxylic acid, or an aralkylcarboxylic acid, but are not limited to these.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, a 2-methyl-n-pentyl ...methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, a n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group Examples of the alkyl group include a phenylcarbonyloxy group, a 3-methyl-n-pentylcarbonyloxy group, a 4-methyl-n-pentylcarbonyloxy group, a 1,1-dimethyl-n-butylcarbonyloxy group, a 1,2-dimethyl-n-butylcarbonyloxy group, a 1,3-dimethyl-n-butylcarbonyloxy group, a 2,2-dimethyl-n-butylcarbonyloxy group, a 2,3-dimethyl-n-butylcarbonyloxy group, a 3,3-dimethyl-n-butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a 1,2,2-trimethyl-n-propylcarbonyloxy group, a 1-ethyl-1-methyl-n-propylcarbonyloxy group, a 1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group, and a tosylcarbonyloxy group. Examples of the halogen atom for R in formula (A) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, R is preferably an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms.

[0025] Specific examples of the hydrolyzable silane represented by formula (A) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane.

[0026] The hydrolyzable silane (Si-1) preferably further contains a hydrolyzable silane represented by the following formula (B): (In formula (B), R １１ are groups bonded to silicon atoms, and each independently represents an organic group having 1 to 45 carbon atoms. １２ 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; and a represents an integer of 1 to 3.

[0027] a is preferably 1 or 2, and more preferably 1.

[0028] <<R in formula (B) １２ >> R in formula (B) １２ 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. １２ Specific and preferred examples of include the specific and preferred examples given in the description of R in formula (A).

[0029] <<R in formula (B) １１ >> R in formula (B) １１ are groups bonded to silicon atoms, and each independently represents an organic group having 1 to 45 carbon atoms. １１ is not a hydrolyzable group. １１represents, for example, 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, an optionally substituted alkenyl group, or an organic group having a cyclic urea skeleton; or an organic group having an epoxy group which may be ring-opened, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0030] The alkyl group may be linear, branched, or cyclic, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less. Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl ... a 1,2-dimethyl-n-pentyl group, a 2,2-dimethyl- Examples of such alkyl groups include 1-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. In this specification, "i" means "iso", "s" means "sec", and "t" means "tert".

[0031] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 2,5-dimethylcyclobutyl group, a 2,6-dimethylcyclobutyl group, a 2,7-dimethylcyclobutyl group, a 2,8-dimethylcyclobutyl group, a 2,9-dimethylcyclobutyl group, a 2,10-dimethylcyclobutyl group, a 2,11-dimethylcyclobutyl group, a 2,12-dimethylcyclobutyl group, a 2,13-dimethylcyclobutyl group, a 2,14-dimethylcyclobutyl group, a 2,15-dimethylcyclobutyl group, a 2,16-dimethylcyclobutyl group, a 2,17-dimethylcyclobutyl group, a 2,18-dimethylcyclobutyl group, a 2,19-dimethylcyclobutyl group, a 2,20-dimethylcyclobutyl group, a 2,21-dimethylcyclobutyl group, a 2,222-dimethylcyclobutyl group, a 2,23-dimethylcyclobutyl group, a 2,41-dimethylcyclobutyl group, a 2,42-dimethylcyclobutyl group, a 2,19-dimethylcyclobutyl group, a 2,19-dimethylcyclobutyl group, a 2,19 Examples include cycloalkyl groups such as a methyl cyclobutyl group, a 3,3-dimethyl cyclobutyl group, a 1-n-propyl cyclopropyl group, a 2-n-propyl cyclopropyl group, a 1-i-propyl cyclopropyl group, a 2-i-propyl cyclopropyl group, a 1,2,2-trimethyl cyclopropyl group, a 1,2,3-trimethyl cyclopropyl group, a 2,2,3-trimethyl cyclopropyl group, a 1-ethyl-2-methyl cyclopropyl group, a 2-ethyl-1-methyl cyclopropyl group, a 2-ethyl-2-methyl cyclopropyl group, and a 2-ethyl-3-methyl cyclopropyl group; and bridged ring cycloalkyl groups such as a bicyclobutyl group, a bicyclopentyl group, a bicyclohexyl group, a bicycloheptyl group, a bicyclooctyl group, a bicyclononyl group, and a bicyclodecyl group.

[0032] 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 therein 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, such as 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, a 2-pyrenyl group, Examples include, but are not limited to, a pentacenyl group, a benzopyrenyl group, a triphenylenyl group; a biphenyl-2-yl group (o-biphenylyl group), a biphenyl-3-yl group (m-biphenylyl group), a biphenyl-4-yl group (p-biphenylyl group), a para-terphenyl-4-yl group, a meta-terphenyl-4-yl group, an ortho-terphenyl-4-yl group, a 1,1'-binaphthyl-2-yl group, and a 2,2'-binaphthyl-1-yl group.

[0033] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups include those described 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.

[0034] The halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are alkyl groups, aryl groups, and aralkyl groups, respectively, substituted with one or more halogen atoms. Specific examples of such alkyl groups, aryl groups, and aralkyl groups include those mentioned above.

[0035] 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 even more preferably 10 or less. Specific examples of halogenated alkyl groups 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 pentafluoroethyl 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, but are not limited to these.

[0036] 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, a 2-fluoro-1-naphthyl ... Examples of the fluorocarbon include 1-naphthyl, 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, and heptafluoro-2-naphthyl. Examples of the fluorocarbon include, but are not limited to, 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 (iodine group).

[0037] 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 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,5-trifluorobenzyl group, 2,6 ... 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 also 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.

[0038] The alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are, respectively, 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 are the same as those described above.

[0039] Examples of the alkoxy group as a substituent include linear, branched, and cyclic alkoxy groups having at least one alkyl moiety and having 1 to 20 carbon atoms. Examples of the linear or branched alkoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyl ... 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-pentyloxy, 1,1-dimethyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1, Examples include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.Examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy, cyclopentyloxy, 1-methylcyclobutoxy, 2-methylcyclobutoxy, 3-methylcyclobutoxy, 1,2-dimethylcyclopropoxy, 2,3-dimethylcyclopropoxy, 1-ethylcyclopropoxy, 2-ethylcyclopropoxy, cyclohexyloxy, 1-methylcyclopentyloxy, 2-methylcyclopentyloxy, 3-methylcyclopentyloxy, 1-ethylcyclobutoxy, 2-ethylcyclobutoxy, 3-ethylcyclobutoxy, 1,2-dimethylcyclobutoxy, 1,3 dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0040] Specific examples of alkoxyalkyl groups include, but are not limited to, lower (about 5 carbon atoms or less) alkyloxy-lower (about 5 carbon atoms or less) alkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl groups. Specific examples of alkoxyaryl groups include, but are not limited to, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphthalen-1-yl, 3-methoxynaphthalen-1-yl, 4-methoxynaphthalen-1-yl, 5-methoxynaphthalen-1-yl, 6-methoxynaphthalen-1-yl, and 7-methoxynaphthalen-1-yl groups. Specific examples of the alkoxyaralkyl group include, but are not limited to, a 3-(methoxyphenyl)benzyl group and a 4-(methoxyphenyl)benzyl group.

[0041] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less. Specific examples of the alkenyl group include 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 group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group , 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl- 2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3, 3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl 1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentenyl group, Examples include a cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group, and also include bridged cyclic alkenyl groups such as a bicycloheptenyl group (norbornyl group).

[0042] Furthermore, examples of the substituents 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 group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, alkoxy group, and aralkyloxy group. Specific examples and their preferred carbon numbers are the same as those described above or below. Furthermore, the aryloxy group exemplified as a substituent is a group in which an aryl group is bonded via an oxygen atom (—O—). Specific examples of such aryl groups include the same as those described 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. Specific examples include, but are not limited to, a phenoxy group and a naphthalene-2-yloxy group. Furthermore, when two or more substituents are present, the substituents may be bonded to each other to form a ring.

[0043] Examples of organic groups having an epoxy group, which may be ring-opened, include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, an epoxycyclohexyl group, or groups obtained by ring-opening such epoxy groups. Examples of organic groups having an acryloyl group include an acryloyloxymethyl group, an acryloyloxyethyl group, and an acryloyloxypropyl group. Examples of organic groups having a methacryloyl group include a methacryloyloxymethyl group, a methacryloyloxyethyl group, and a methacryloyloxypropyl group. Examples of organic groups having a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and a mercaptophenyl group. Examples of organic groups having 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. Organic groups having an amino group will be described in more detail below. Examples of organic groups having an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group. However, groups in which an alkoxy group is directly bonded to a silicon atom are excluded. Examples of organic groups having a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group. Examples of organic groups having a cyano group include, but are not limited to, a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, a thiocyanate group, etc.

[0044] The organic group having an amino group can be an organic group having at least one of a primary amino group, a secondary amino group, and a tertiary amino group.Preferably, a hydrolysis condensate obtained by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid to form a counter cation having a tertiary ammonium group can be used.In addition, the organic group can contain heteroatoms such as oxygen atoms and sulfur atoms in addition to the nitrogen atoms constituting the amino group.

[0045] A preferred example of the organic group having an amino group is a group represented by the following formula (A1).

[0046] In formula (A1), R １０１ and R １０２ are each independently a hydrogen atom or a hydrocarbon group, and L are each independently an alkylene group which may be substituted. * represents a bond. Examples of hydrocarbon groups include, but are not limited to, alkyl groups, alkenyl groups, and aryl groups. Specific examples of these alkyl groups, alkenyl groups, and aryl groups include R １ Examples of the alkylene group include the same groups as those described above in the above. The alkylene group may be either linear or branched, and the number of carbon atoms is usually 1 to 10, preferably 1 to 5. Examples include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene. Examples of organic groups having an amino group include, but are not limited to, amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl groups.

[0047] Examples of the organic group having a cyclic urea skeleton include an organic group represented by the following formula (4-2). In formula (4-2), R ４０４ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an organic group having an epoxy group, or an organic group having a sulfonyl group; R ４０５ are each independently an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-). * represents a bond. ４０４ Specific examples of the organic group having an optionally substituted alkyl group, an optionally substituted alkenyl group, and an epoxy group, and suitable carbon numbers thereof, etc. are given in R １２ The same factors as those mentioned above can be mentioned.

[0048] Also, R ４０５The alkylene group may have one or more bonds selected from a sulfide bond, an ether bond and an ester bond at its terminal or in the middle, preferably in the middle. Specific examples of the alkylene group include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as methylethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkylene groups such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; and -CH ２ OCH ２ -, -CH ２ CH ２ OCH ２ -, -CH ２ CH ２ OCH ２ CH ２ -, -CH ２ CH ２ CH ２ OCH ２ CH ２ -, -CH ２ CH ２ OCH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ OCH ２ CH ２ CH ２ -, -CH ２ SCH ２ -, -CH ２ CH ２ SCH ２ -, -CH ２ CH ２ SCH ２ CH ２ -, -CH ２ CH ２ CH２ SCH ２ CH ２ -, -CH ２ CH ２ SCH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ SCH ２ CH ２ CH ２ -, -CH ２ OCH ２ CH ２ SCH ２ Examples of alkylene groups include, but are not limited to, alkylene groups containing ether groups such as -.

[0049] The hydroxyalkylene group is an alkylene group in which at least one hydrogen atom has been replaced with a hydroxy group. Specific examples thereof include, but are not limited to, a hydroxymethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, a 1,2-dihydroxyethylene group, a 1-hydroxytrimethylene group, a 2-hydroxytrimethylene group, a 3-hydroxytrimethylene group, a 1-hydroxytetramethylene group, a 2-hydroxytetramethylene group, a 3-hydroxytetramethylene group, a 4-hydroxytetramethylene group, a 1,2-dihydroxytetramethylene group, a 1,3-dihydroxytetramethylene group, a 1,4-dihydroxytetramethylene group, a 2,3-dihydroxytetramethylene group, a 2,4-dihydroxytetramethylene group, and a 4,4-dihydroxytetramethylene group.

[0050] In formula (4-2), X ４０１ each independently represents any one of the groups represented by the following formulas (4-3) to (4-5), and the carbon atom of the ketone group in the following formulas (4-4) and (4-5) is R ４０５ It bonds to the nitrogen atom to which it is bonded.

[0051] In formulas (4-3) to (4-5), R ４０６ ~R ４１０are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group having an epoxy group or a sulfonyl group. Specific examples of the optionally substituted alkyl group, the optionally substituted alkenyl group, and the organic group having an epoxy group or a sulfonyl group, as well as suitable carbon numbers, etc., are given in R １２ Specific examples of the organic group having a sulfonyl group and the suitable number of carbon atoms are given in R ４０４ The same as those mentioned above can be mentioned for the above. * represents a bond.

[0052] The hydrolyzable silane having an organic group with a cyclic urea skeleton may be a commercially available product, or may be synthesized by a known method described in, for example, WO 2011 / 102470.

[0053] Specific examples of hydrolyzable silanes having an organic group with a cyclic urea skeleton include, but are not limited to, silanes represented by the following formulas (4-1-1) to (4-1-29).

[0054] When the hydrolyzable silane (Si-1) is subjected to hydrolysis and condensation to obtain a polysiloxane, the proportion of the hydrolyzable silane represented by formula (B) in the hydrolyzable silane (Si-1) is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20 mol% or more. The upper limit of the proportion of the hydrolyzable silane represented by formula (B) in the hydrolyzable silane (Si-1) when the hydrolyzable silane (Si-1) is subjected to hydrolysis and condensation to obtain a polysiloxane is not particularly limited, and the proportion may be, for example, 70 mol% or less, 55 mol% or less, or 40 mol% or less.

[0055] When the hydrolyzable silane (Si-1) is subjected to hydrolysis and condensation to obtain a polysiloxane, the total proportion of the hydrolyzable silane represented by formula (A) and the hydrolyzable silane represented by formula (B) in the hydrolyzable silane (Si-1) is not particularly limited, but is preferably 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %, and particularly preferably 90 mol % to 100 mol %.

[0056] The polysiloxane of component [A] may be a hydrolysis condensation product of a hydrolyzable silane (Si-1) containing a silane compound other than those exemplified above, or a modified product thereof, as long as the effects of the present invention are not impaired.

[0057] As described above, the polysiloxane of component [A] can be a modified product in which at least a portion of the silanol groups of the hydrolysis condensation product have been modified. For example, a modified product in which some of the silanol groups have been alcohol-modified or acetal-protected can be used. Examples of the modified polysiloxane include a reaction product obtained by reacting at least a portion of the silanol groups of the hydrolysis condensation product of the hydrolyzable silane with hydroxy groups of an alcohol, a dehydration reaction product of the condensation product with an alcohol, and a modified product in which at least a portion of the silanol groups of the condensation product have been protected with acetal groups.

[0058] The alcohol may be a monohydric alcohol, such as 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, or 1-hexanol. Examples of suitable alcohols include 2-methyl-1-pentanol, 2-hexanol, 3-hexanol, 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, 4-methyl-3-pentanol, and cyclohexanol. Further, for example, alkoxy group-containing alcohols such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

[0059] The reaction between the silanol groups of the hydrolysis condensate and the hydroxyl groups of the alcohol can be carried out by contacting the hydrolysis condensate 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, 60° C., to obtain a modified product in which the silanol groups are capped. In this case, the alcohol capping agent can be used as a solvent in the composition containing the polysiloxane.

[0060] Furthermore, a dehydration reaction product of a hydrolysis condensate of a hydrolyzable silane with an alcohol can be produced by reacting the hydrolysis condensate with an alcohol in the presence of an acid catalyst, capping the silanol groups with the alcohol, and removing the water produced by dehydration from the reaction system. The acid can be 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, and acetic acid, among others. Furthermore, the acid can have a boiling point of 70 to 160°C, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. Thus, the acid preferably has an acid dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160°C. In other words, either a weak acidity or a strong acidity but a low boiling point can be used. The acid can have any properties, depending on the acid dissociation constant and boiling point.

[0061] Acetal protection of the silanol groups in the hydrolysis condensate can be achieved using a vinyl ether, for example, a vinyl ether represented by the following formula (5). By this reaction, a partial structure represented by the following formula (6) can be introduced into the polysiloxane.

[0062] In formula (5), R １ａ , R ２ａ , and R ３ａ each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ４ａ represents an alkyl group having 1 to 10 carbon atoms, and R ２ａ and R ４ａ may be bonded to each other to form a ring. Examples of the alkyl group include those mentioned above. In formula (6), R １ ', R ２ ', and R ３ Each of R ′ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, ４ ' represents an alkyl group having 1 to 10 carbon atoms, and R ２ ' and R ４In formula (6), * indicates a bond to an adjacent atom. The adjacent atom may be, for example, an oxygen atom of a siloxane bond, an oxygen atom of a silanol group, or R in formula (1). １ Examples of the alkyl group include the carbon atoms derived from the following.

[0063] Examples of the vinyl ether represented by formula (5) include 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 3,4-dihydro-2H-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 are preferably used.

[0064] Acetal protection of the silanol groups can be carried out using the hydrolysis condensate, a 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 pyridium paratoluenesulfonate, trifluoromethanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0065] 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.

[0066] The hydrolysis condensate of hydrolyzable silane can be obtained by hydrolyzing and condensing the aforementioned silane compound (hydrolyzable silane). The aforementioned silane compound (hydrolyzable silane) contains an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, i.e., an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or halogenated silyl group (hereinafter referred to as a hydrolyzable group). To hydrolyze these hydrolyzable groups, typically 0.1 to 100 moles, for example, 0.5 to 100 moles, and preferably 1 to 10 moles, of water are used per mole of hydrolyzable group. During the hydrolysis and condensation, a hydrolysis catalyst may be used, or the hydrolysis and condensation may be carried out without the use of a hydrolysis catalyst, for example, to promote the reaction. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of hydrolyzable group. The reaction temperature during hydrolysis and condensation is usually in the range of room temperature or higher and the reflux temperature at normal pressure of the organic solvent that can be used for hydrolysis, and can be, for example, 20 to 110°C, or, for example, 20 to 80°C. The hydrolysis may be complete, i.e., all hydrolyzable groups are converted to silanol groups, or partial, i.e., unreacted hydrolyzable groups may remain. Examples of hydrolysis catalysts that can be used during hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0067] Examples of metal chelate compounds as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di -i-propoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium, di-sec-butoxy bis(acetylacetonate)titanium, di-t-butoxy bis(acetylacetonate)titanium, monoethoxy tris(acetylacetonate)titanium, mono-n-propoxy tris(acetylacetonate)titanium, mono-i-propoxy tris(acetylacetonate)titanium, mono-n-butoxy tris(acetylacetonate)titanium, mono-sec-butoxy tris(acetylacetonate) titanium acetate), mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethoxy di-n-propoxy bis(ethylacetoacetate) titanium, di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate) titanium,Titanium chelate compounds such as mono-n-butoxy tris(ethylacetoacetate)titanium, mono-sec-butoxy tris(ethylacetoacetate)titanium, mono-t-butoxy tris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonate)tris(ethylacetoacetate)titanium, bis(acetylacetonate)bis(ethylacetoacetate)titanium, and tris(acetylacetonate)mono(ethylacetoacetate)titanium; triethoxy mono(acetylacetonate) tri-n-propoxy mono(acetylacetonate) zirconium, tri-i-propoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-t-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, di-i-propoxy bis(acetylacetonate) zirconium cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxy tris(acetylacetonate)zirconium, mono-t-butoxy tris(acetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxy mono(ethylacetoacetate)zirconium, tri-n-propoxy mono(ethylacetoacetate)zirconium, tri-i-propoxy mono(ethylacetoacetate)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-butoxy Examples of the chelate compounds include, but are not limited to, zirconium chelate compounds such as tris(ethylacetoacetate)zirconium, mono-sec-butoxy tris(ethylacetoacetate)zirconium, mono-t-butoxy tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato)tris(ethylacetoacetate)zirconium, bis(acetylacetonato)bis(ethylacetoacetate)zirconium, and tris(acetylacetonato)mono(ethylacetoacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum.

[0068] Examples of organic acids that can be used 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, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0069] Examples of inorganic acids that can be used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0070] 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.

[0071] 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.

[0072] Of 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.

[0073] Among these, in the present invention, nitric acid can be preferably used as the hydrolysis catalyst. The use of nitric acid can improve the storage stability of the reaction solution after hydrolysis and condensation, and in particular, can suppress changes in the molecular weight of the hydrolysis condensate or its modified product. It has been found that the stability of the hydrolysis condensate or its modified product in the solution depends on the pH of the solution. As a result of extensive investigation, it has been found that the pH of the solution falls within a stable range when an appropriate amount of nitric acid is used. Furthermore, as described above, nitric acid can also be used when obtaining a modified product of the hydrolysis condensate, for example, when capping silanol groups with alcohol, and is therefore preferred from the viewpoint of being able to contribute to both the hydrolysis and condensation of hydrolyzable silanes and the alcohol capping of the hydrolysis condensate.

[0074] When carrying out the hydrolysis and condensation, an organic solvent may be used as the solvent, and specific examples thereof include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-propylbenzene, and the like. Aromatic hydrocarbon solvents such as 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, sec-hexanol, and 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, Monoalcohol-based solvents such as phenylmethylcarbinol, diacetone alcohol, and cresol; and polyhydric alcohol-based solvents such as 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, 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, and ethylene glycol dibutyl ether-based solvents such as ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (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, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol acetate Examples of solvents include, but are not limited to, ester-based solvents such as methyl ether, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglyceride, ethylene glycol diacetate, triethylene glycol methyl ether 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-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. ;

[0075] 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 a base, used in the hydrolysis and condensation. Before or after such treatment, by-product alcohol and water, the hydrolysis catalyst, etc., can be removed from the reaction solution by vacuum distillation or the like.

[0076] The hydrolysis condensate or modified product thereof (hereinafter also referred to as polysiloxane) obtained in this manner is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, which can be used directly in the preparation of a silicon-containing underlayer film-forming composition. That is, the reaction solution can be used as is (or diluted) in the preparation of a silicon-containing underlayer film-forming composition. At this time, the hydrolysis catalyst used in the hydrolysis and condensation, by-products, etc., may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst or the nitric acid used in alcohol-capping silanol groups may remain in the polymer varnish solution at approximately 100 ppm to 5,000 ppm. The obtained polysiloxane varnish may be subjected to solvent substitution or diluted with an appropriate solvent. If the storage stability of the obtained polysiloxane varnish is not poor, the organic solvent can be distilled off to achieve a film-forming component concentration of 100%. The film-forming component refers to the components of the composition excluding the solvent component. The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reaction of the hydrolyzable silane. This dilution solvent is not particularly limited, and one or more solvents may be selected and used as desired.

[0077] The weight average molecular weight of the polysiloxane can be, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation of the polysiloxane in the composition, the weight average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coatability, the weight average molecular weight is preferably 700 or more, more preferably 1,000 or more. The weight average molecular weight is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC analysis can be performed using, for example, a GPC apparatus (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 rate) of 1.0 mL / min, and polystyrene (Shodex (registered trademark) manufactured by Showa Denko K.K.) as a standard sample.

[0078] <Component [B]: Water> In the first embodiment, the composition for forming a silicon-containing underlayer film contains water. In the second embodiment, the composition for forming a silicon-containing underlayer film may contain water or may not contain water. As the water, pure water, ultrapure water, ion-exchanged water, etc. can be used.

[0079] The water content in the silicon-containing underlayer film-forming composition can be, for example, 30 mass % or less, preferably 20 mass % or less, and even more preferably 15 mass % or less, relative to the total mass of the solvents contained in the composition.

[0080] <Component [C]: Curing Catalyst> In the first embodiment, the composition for forming a silicon-containing underlayer film does not contain a curing catalyst. In the second embodiment, the composition for forming a silicon-containing underlayer film may or may not contain a curing catalyst.

[0081] Here, "not containing a curing catalyst" in the present invention refers to a case where no curing catalyst is added to the composition for forming a silicon-containing underlayer film. However, a case where no curing catalyst is detected when the composition for forming a silicon-containing underlayer film is subjected to a composition analysis (e.g., mass spectrometry, IR analysis, gas chromatography analysis, etc.) also falls under the category of "not containing a curing catalyst" in the present invention.

[0082] As the curing catalyst, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc. The salts described below as examples of the curing catalyst may be added in the form of a salt, or may form a salt in the composition (a compound that is added as a separate compound and forms a salt in the system).

[0083] The ammonium salt includes those represented by formula (D-1): (In the formula, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3, R ２１ represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0084] Formula (D-2): (In the formula, R ２２ , R ２３ , R ２４ and R ２５ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion, and R ２２ , R ２３ , R ２４ , and R ２５ are each bonded to a nitrogen atom.)

[0085] Formula (D-3): (In the formula, R ２６ and R ２７ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0086] Formula (D-4): (In the formula, R ２８ represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0087] Formula (D-5): (In the formula, R ２９ and R ３０ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion;

[0088] Formula (D-6): (In the formula, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3, and Y － represents an anion.

[0089] Furthermore, the phosphonium salt includes a compound of the formula (D-7): (In the formula, R ３１ , R ３２ , R ３３ , and R ３４ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion, and R ３１ , R ３２ , R ３３ , and R ３４ are bonded to a phosphorus atom.

[0090] Furthermore, the sulfonium salt includes a compound represented by formula (D-8): (In the formula, R ３５ , R ３６ , and R ３７ each independently represents an alkyl group, an aryl group, or an aralkyl group; Y － represents an anion, and R ３５ , R ３６ , and R ３７are each bonded to a sulfur atom.

[0091] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3. R of this quaternary ammonium salt ２１ represents, for example, an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include linear alkyl groups such as ethyl, propyl, and butyl groups, as well as benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and the like.

[0092] The compound of 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, for example, an alkyl group having 1 to 18 carbon atoms such as an ethyl group, a propyl group, a butyl group, a cyclohexyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group. － ) is a chloride ion (Cl － ), bromine 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.

[0093] The compound of formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and R ２６ and R ２７ The number of carbon atoms in R is, for example, 1 to 18. ２６ and R ２７ The total number of carbon atoms in R is preferably 7 or more. ２６ can be exemplified by alkyl groups such as methyl, ethyl, and propyl, aryl groups such as phenyl, and aralkyl groups such as benzyl, and R ２７ Examples of the anion (Y) include aralkyl groups such as benzyl, and alkyl groups such as octyl and octadecyl. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － Although this compound is commercially available, it can also be produced by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an aralkyl halide, alkyl halide, or aryl halide such as benzyl bromide, methyl bromide, or benzene bromide.

[0094] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ２８is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include a butyl group, an octyl group, a benzyl group, and a lauryl group. － ) is a chloride ion (Cl － ), bromine 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 also be produced by reacting pyridine with an alkyl halide or aryl halide, such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0095] The compound of formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine, such as picoline, and R ２９ is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples of R include a methyl group, an octyl group, a lauryl group, and a benzyl group. ３０ is, for example, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. For example, when the compound represented by formula (D-5) is a quaternary ammonium derived from picoline, R ３０ is a methyl group. － ) is a chloride ion (Cl － ), bromine 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 also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0096] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents 2 or 3. Also, an anion (Y － ) is a chloride ion (Cl － ), bromine 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, an 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 － )

[0097] The compound of 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 ３４is, for example, an alkyl group having 1 to 18 carbon atoms such as an ethyl group, a propyl group, a butyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group, and preferably R ３１ ~R ３４ Three of the four substituents are unsubstituted phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O －) and other acid groups. 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 halides, tetraphenylphosphonium halides, tritolylmonoarylphosphonium halides, and tritolylmonoalkylphosphonium halides (all of which the halogen atom is a chlorine atom or a bromine atom). In particular, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritolylmonoarylphosphonium halides such as tritolylmonophenylphosphonium halide, and tritolylmonoalkylphosphonium halides (the halogen atom is a chlorine atom or a bromine atom) are preferred.

[0098] 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.

[0099] The compound of 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 ３７is, for example, an alkyl group having 1 to 18 carbon atoms such as an ethyl group, a propyl group, a butyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group, and preferably R ３５ ~R ３７ Two of the three substituents are unsubstituted phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － Examples of suitable acid groups 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 (all of which 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. Furthermore, triphenylsulfonium halides and triphenylsulfonium carboxylates are preferably used.

[0100] The content of the curing catalyst (C) in the silicon-containing underlayer film-forming composition of the second embodiment is not particularly limited, and may be, for example, 0.1 to 30 parts by mass, 0.5 to 25 parts by mass, or 1 to 20 parts by mass relative to 100 parts by mass of the polysiloxane (A).

[0101] <Component [D]: Organic Solvent> The composition for forming a silicon-containing underlayer film may contain an organic solvent.

[0102] The organic solvent [D] is preferably an alcohol-based solvent, more preferably an alkylene glycol monoalkyl ether that is an alcohol-based solvent, and even more preferably a propylene glycol monoalkyl ether. These organic solvents also serve as capping agents for the silanol groups in the hydrolysis condensate, so that the silicon-containing underlayer film-forming composition can be prepared from the solution obtained by preparing the polysiloxane [A] without the need for solvent substitution or the like. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether.

[0103] Specific examples of other organic solvents [D] include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, 2-hydroxy- Ethyl 2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amino formate methyl acrylate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate,Examples of organic solvents include methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more.

[0104] <Component [E]: Nitric Acid> The silicon-containing underlayer film-forming composition preferably contains nitric acid [E]. Nitric acid [E] may be added during the preparation of the silicon-containing underlayer film-forming composition, but it may also be used as a hydrolysis catalyst or during alcohol capping of silanol groups in the production of the polysiloxane described above, and the nitric acid remaining in the polysiloxane varnish may be treated as nitric acid [E].

[0105] The amount of nitric acid (residual nitric acid amount) [E] can be, for example, 0.0001 mass % to 1 mass %, or 0.001 mass % to 0.1 mass %, or 0.005 mass % to 0.05 mass %, based on the total mass of the composition for forming a silicon-containing underlayer film.

[0106] <Other Additives> Various additives can be blended into the silicon-containing underlayer film-forming composition depending on the intended use of the composition. Examples of additives include crosslinkers, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, 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, anti-reflective films, and pattern reversal films. Examples of various additives are listed below, but are not limited to these.

[0107] <<Stabilizer>> A stabilizer can be added for purposes such as stabilizing the hydrolysis condensate of the hydrolyzable silane. Specific examples of stabilizers include organic acids, water, alcohols, and combinations thereof. Examples of organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Among these, oxalic acid and maleic acid are preferred. When an organic acid is added, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolysis condensate of the hydrolyzable silane. These organic acids can also function as pH adjusters. Preferred alcohols are those that are easily evaporated by heating after application, such as methanol, ethanol, propanol, i-propanol, and butanol. When an alcohol is added, the amount added can be 1 to 20 parts by mass per 100 parts by mass of the composition for forming a silicon-containing underlayer film.

[0108] <<Organic Polymer>> By adding an organic polymer to the composition for forming a silicon-containing underlayer film, it is possible to adjust the dry etching rate (the amount of film thickness reduction per unit time) of the film formed from the composition, as well as the attenuation coefficient and refractive index. The organic polymer is not particularly limited and may be appropriately selected from various organic polymers (condensation polymerization polymers and addition polymerization polymers) depending on the purpose of addition. Specific examples include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing moieties can also be suitably used when such a function is required. Specific examples of such organic polymers include, but are not limited to, addition polymerization polymers containing, as structural units, addition-polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide, and condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0109] When an addition polymerization polymer is used as the organic polymer, the polymer may be either a homopolymer or a copolymer. An addition polymerizable monomer is used to produce the addition polymerization polymer, and specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0110] Specific examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, glycidyl acrylate, and the like, but are not limited to these.

[0111] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, and the like, but are not limited to these.

[0112] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0113] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0114] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0115] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0116] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0117] When a condensation polymerization polymer is used as the organic polymer, examples of such a polymer include a condensation polymerization polymer of a glycol compound and a dicarboxylic acid compound. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, butylene glycol, etc. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc. Examples of polyesters, polyamides, and polyimides such as polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, but are not limited to these. When the organic polymer contains a hydroxy group, this hydroxy group may undergo a crosslinking reaction with a hydrolysis condensate or the like.

[0118] The weight-average molecular weight of the organic polymer can usually be 1,000 to 1,000,000. When an organic polymer is incorporated, from the viewpoint of suppressing precipitation in the composition while fully obtaining the functional effects of the polymer, the weight-average molecular weight can be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000. Such organic polymers may be used alone or in combination of two or more.

[0119] When the composition for forming a silicon-containing underlayer film contains an organic polymer, the content of the organic polymer cannot be generally defined because it is determined appropriately in consideration of the function of the organic polymer, etc., but can usually be in the range of 1 to 200% by mass relative to the mass of the polysiloxane (A). From the viewpoint of suppressing precipitation in the composition, etc., the content can be, for example, 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less; from the viewpoint of fully obtaining the effect, etc., the content can be, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0120] <<Acid Generator>> Examples of acid generators include thermal acid generators and photoacid generators, and photoacid generators are preferably used. Examples of photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, and the like. Note that photoacid generators, for example, carboxylates such as nitrates and maleates of onium salt compounds described below, and hydrochlorides, depending on the type, can also function as a curing catalyst. Examples of thermal acid generators include, but are not limited to, tetramethylammonium nitrate.

[0121] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride. However, the present invention is not limited to these.

[0122] Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited to these.

[0123] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0124] When the composition for forming a silicon-containing underlayer film contains an acid generator, its content cannot be generally defined because it is determined appropriately taking into account the type of acid generator, etc., but is usually in the range of 0.01 to 5 mass % relative to the mass of the polysiloxane (A), and from the viewpoint of suppressing precipitation of the acid generator in the composition, it is preferably 3 mass % or less, more preferably 1 mass % or less, and from the viewpoint of fully obtaining its effects, it is preferably 0.1 mass % or more, more preferably 0.5 mass % or more. The acid generators can be used alone or in combination of two or more, and a photoacid generator and a thermal acid generator may be used in combination.

[0125] <<Surfactant>> A surfactant is effective in suppressing the occurrence of pinholes, striations, etc. when the silicon-containing underlayer film-forming composition is applied to a substrate. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, and UV-curable surfactants. 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 trioleate; Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as oleate and polyoxyethylene sorbitan tristearate, trade names of EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade names of 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 and FC431 (manufactured by 3M Japan Ltd.), Asahiguard (registered trademark) AG710 (manufactured by AGC Corporation), and 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.). These surfactants can be used singly or in combination of two or more.

[0126] When the composition for forming a silicon-containing underlayer film contains a surfactant, the content thereof is 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 polysiloxane (A).

[0127] <<Rheology Modifiers>> Rheology modifiers are added primarily to improve the fluidity of the silicon-containing underlayer film-forming composition, particularly in the baking step, to improve the film thickness uniformity of the formed film and to enhance the filling of the composition into holes. 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 octyldecyl 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 n-butyl stearate and glyceryl stearate. When these rheology modifiers are used, the amount added is typically less than 30% by mass of all the film-forming components of the silicon-containing underlayer film-forming composition.

[0128] <<Adhesion Aid>> An adhesion aid is added mainly for the purpose of improving adhesion to the substrate or an adjacent layer (for example, a surface-modified layer). Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; γ-chloropropyltrimethoxysilane; Examples of such adhesion promoters include other silanes such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. When such adhesion promoters are used, the amount added is usually less than 5% by mass, and preferably less than 2% by mass, of the film-forming components of the silicon-containing underlayer film-forming composition.

[0129] <<pH Adjuster>> Examples of the pH adjuster include acids having one or more carboxylic acid groups, such as the organic acids listed above as stabilizers. When a pH adjuster is used, the amount added may be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass per 100 parts by mass of the polysiloxane (A).

[0130] <<Metal Oxide>> Examples of metal oxides that can be added to the silicon-containing underlayer film-forming composition include, but are not limited to, oxides of one or a combination of two or more of metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0131] The concentration of the film-forming component in the silicon-containing underlayer film-forming composition can 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%, relative to the total mass of the composition. The content of the polysiloxane [A] in the film-forming component is usually 20 mass% to 100 mass%, but from the viewpoint of reproducibly obtaining the effects of the present invention, the lower limit is preferably 50 mass%, more preferably 60 mass%, even more preferably 70 mass%, and even more preferably 80 mass%, and the upper limit is preferably 99 mass%, with the remainder being the additive described below. The silicon-containing underlayer film-forming composition also preferably has a pH of 2 to 5, more preferably 3 to 4.

[0132] In the present invention, the composition for forming a silicon-containing underlayer film may be filtered using a submicrometer-order filter or the like during the production process or after all components have been mixed. The type of material for the filter used here is not important, and examples that can be used include nylon filters and fluororesin filters.

[0133] The composition for forming a silicon-containing underlayer film of the present invention can be suitably used as a composition for forming an underlayer film used in a lithography process.

[0134] The composition for forming a silicon-containing underlayer film of the present invention is preferably used in EUV lithography.

[0135] <Surface modified layer and composition for forming a surface modified layer> The silicon-containing underlayer film-forming composition of the present invention is a composition for forming a silicon-containing underlayer film on which a surface modified layer having a thickness of 5 nm or less is formed. The surface modified layer is formed, for example, using the composition for forming a surface modified layer. The surface modified layer and the composition for forming a surface modified layer are described below.

[0136] The surface modification layer is not particularly limited, but is preferably a silicon-containing layer. The surface modification layer is preferably a layer containing polysiloxane. The polysiloxane in the surface modification layer may or may not be crosslinked.

[0137] <<Surface Modification Layer Forming Composition (S1)>> The surface modification layer is preferably formed using a surface modification layer forming composition containing a polysiloxane and a solvent. Hereinafter, the surface modification layer forming composition containing a polysiloxane and a solvent may be referred to as the surface modification layer forming composition (S1).

[0138] The polysiloxane contained in the surface modification layer forming composition (S1) may be a modified polysiloxane in which some of the silanol groups have been modified, for example, a polysiloxane modified product in which some of the silanol groups have been alcohol-modified or acetal-protected. Furthermore, the polysiloxane may, for example, include a hydrolysis condensation product of a hydrolyzable silane, and may include a modified polysiloxane in which at least some of the silanol groups of the hydrolysis condensation product have been alcohol-modified or acetal-protected. The hydrolyzable silane in the hydrolysis condensation product may contain one or more hydrolyzable silanes. Commercially available polysiloxanes can be used as the polysiloxane. Hereinafter, the polysiloxane contained in the surface modification layer forming composition (S1) may be referred to as "polysiloxane (S)."

[0139] The polysiloxane (S) preferably contains 50 mol% or more, more preferably 65 mol% or more, and particularly preferably 80 mol% or more of T units relative to all units. The upper limit of the proportion of T units relative to all units in the polysiloxane (S) is not particularly limited, and the proportion of T units may be, for example, 100 mol% or less.

[0140] The polysiloxane (S) may or may not contain Q units. The ratio of Q units to all units in the polysiloxane (S) is not particularly limited and may be, for example, 0 mol % to 50 mol %, 0 mol % to 35 mol %, or 0 mol % to 20 mol %.

[0141] The polysiloxane (S) preferably contains 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %, and particularly preferably 90 mol % to 100 mol %, of the total of Q units and T units relative to all units.

[0142] The polysiloxane (S) is preferably a hydrolysis condensate of a hydrolyzable silane (Si-2). The hydrolyzable silane (Si-2) preferably contains a hydrolyzable silane represented by the following formula (S1): (In formula (S1), R ２１ are groups bonded to silicon atoms, and each independently represents an organic group having 1 to 45 carbon atoms. ２２ 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; and a represents an integer of 1 to 3.

[0143] <<<<R in formula (S1) ２１ >>> R in formula (S1) ２１ are groups bonded to silicon atoms, and each independently represents an organic group having 1 to 45 carbon atoms. ２１ is not a hydrolyzable group. ２１R represents, for example, 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, an optionally substituted alkenyl group, or an organic group having a cyclic urea skeleton, or an organic group having an epoxy group which may be ring-opened, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof. ２１ Specific and preferred examples of R in formula (B) include １１ Specific examples and preferred examples are given in the explanation of 1.

[0144] <<<<R in formula (S1) ２２ >>> R in formula (S1) ２２ 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. ２２ Specific and preferred examples of include the specific and preferred examples given in the description of R in formula (A).

[0145] The hydrolyzable silane (Si-1) may contain a hydrolyzable silane represented by the following formula (S2): (In formula (S2), R represents a group or atom bonded to a silicon atom, and each R independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.)

[0146] R in formula (S2) is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. Specific and preferred examples of R in formula (S2) include the specific and preferred examples given in the description of R in formula (A).

[0147] When the hydrolyzable silane (Si-2) is subjected to hydrolysis and condensation to obtain the polysiloxane (S), the proportion of the hydrolyzable silane represented by formula (S1) in the hydrolyzable silane (Si-2) is preferably 50 mol% or more, more preferably 65 mol% or more, and particularly preferably 80 mol% or more. When the hydrolyzable silane (Si-2) is subjected to hydrolysis and condensation to obtain the polysiloxane, the upper limit of the proportion of the hydrolyzable silane represented by formula (S1) in the hydrolyzable silane (Si-2) is not particularly limited, and the proportion may be, for example, 100 mol% or less.

[0148] When the hydrolyzable silane (Si-2) is subjected to hydrolysis and condensation to obtain the polysiloxane (S), the proportion of the hydrolyzable silane represented by formula (S2) in the hydrolyzable silane (Si-2) is not particularly limited, and may be, for example, 0 mol % to 50 mol %, 0 mol % to 35 mol %, or 0 mol % to 20 mol %.

[0149] When the hydrolyzable silane (Si-2) is subjected to hydrolysis and condensation to obtain a polysiloxane, the total ratio of the hydrolyzable silane represented by the formula (S1) and the hydrolyzable silane represented by the formula (S2) in the hydrolyzable silane (Si-2) is not particularly limited, but is preferably 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %, and particularly preferably 90 mol % to 100 mol %.

[0150] The polysiloxane (S) may be a hydrolysis condensate of a hydrolyzable silane (Si-2) containing a silane compound other than those exemplified above, or a modified product thereof, within the range that does not impair the effects of the present invention.

[0151] As described above, the polysiloxane (S) can be a modified product in which at least a portion of the silanol groups of the hydrolysis condensate are modified. For example, a modified product in which some of the silanol groups are alcohol-modified or acetal-protected can be used. Examples of the modified polysiloxane include the reaction product obtained by reacting at least a portion of the silanol groups of the hydrolysis condensate of the hydrolyzable silane with the hydroxyl groups of an alcohol, the dehydration reaction product of the condensate with an alcohol, and a modified product in which at least a portion of the silanol groups of the condensate are protected with an acetal group. Specific examples of alcohols used for alcohol modification include the alcohols listed in the description of the alcohol-modification of the polysiloxane (component [A]). Specific examples of vinyl ethers used for acetal protection include the vinyl ethers listed in the description of the acetal protection of the polysiloxane (component [A]).

[0152] The method for producing the polysiloxane (S) can be, for example, the method for producing the polysiloxane that is the component [A] described above.

[0153] The weight-average molecular weight of the polysiloxane (S) can be, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation of the polysiloxane (S) in the composition, the weight-average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less, and from the viewpoint of achieving both storage stability and coatability, the weight-average molecular weight is preferably 700 or more, more preferably 1,000 or more.

[0154] Examples of the solvent contained in the composition (S1) for forming a surface modification layer include the organic solvent (component [D]) mentioned in the description of the composition for forming a silicon-containing underlayer film.

[0155] The surface modification layer-forming composition (S1) may contain other components. Examples of the other components include the components described in the description of the silicon-containing underlayer film-forming composition. Examples of the components described in the description of the silicon-containing underlayer film-forming composition include a curing catalyst (component [C]), nitric acid (component [E]), water (component [B]), and other additives. More preferably, the composition has a pH of 3 to 4.

[0156] The concentration of the film-forming component in the surface-modifying layer-forming composition (S1) can be, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, or 0.5 to 20.0% by mass, relative to the total mass of the composition. The content of polysiloxane (S) in the film-forming component is usually 20% by mass to 100% by mass, but from the viewpoint of reproducibly obtaining the 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 even more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the additive described below. The surface-modifying layer-forming composition (S1) preferably has a pH of 2 to 5, more preferably 3 to 4.

[0157] In the present invention, the composition for forming a surface modification layer (S1) may be filtered using a submicrometer-order filter or the like during the production process or after all components have been mixed. The material of the filter used here is not limited, and examples thereof include nylon filters and fluororesin filters.

[0158] <<Surface Modification Layer Forming Composition (S2)>> As the surface modification layer forming composition, a composition other than the surface modification layer forming composition (S1) can be used. Examples of such a surface modification layer forming composition (S2) include the following compositions. A substrate processing composition for lithography, comprising a first monomer, a second monomer, and an acid, wherein the first monomer is represented by Chemical Formula 1 shown below, and the second monomer is represented by Chemical Formula 7 shown below, and wherein the molecular weight of the solid content including the first monomer, the second monomer, and the acid is 1,000 g / mol to 50,000 g / mol. X-Si(R1) ２ (R2) ... Chemical Formula 1 (wherein each of R1 and R2 is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and X is i) a cyclic amine or an organic group containing the same, or ii) an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with an amino group, a phenyl group in which at least one hydrogen atom is substituted with an amino group or a hydroxy group, an ester bond, or a combination thereof.) Y-Si(R3) ３ ...Chemical Formula 7 (wherein R3 is an alkoxy group having 1 to 20 carbon atoms, and Y is either i) a cyclic amine or an organic group containing the same, or ii) an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with an amino group, a sulfide bond, an ether bond, or an alkyl group having 1 to 20 carbon atoms bonded to a sulfonyl group, or a combination thereof.)

[0159] Examples of the surface modification layer-forming composition (S2) include the lithography substrate treatment composition described in JP 2019-185008 A. The contents of this publication are incorporated herein by reference in their entirety to the same extent as if set forth herein.

[0160] <<Surface Modification Layer Forming Composition (S3)>> As the surface modification layer forming composition, compositions other than the surface modification layer forming composition (S1) can be used. Examples of such surface modification layer forming compositions (S3) include the following surface modifiers. A surface modifier for a resist pattern is applied to a substrate before forming a resist pattern of 0.10 μm or less on the substrate to enhance adhesion between the substrate and the resist pattern, and includes at least one of a compound represented by the following average composition formula (1): a hydrolyzate of a compound represented by the following average composition formula (1): or a hydrolyzed condensate of a compound represented by the following average composition formula (1): (In the formula, R １ is represented by the general formula: -(CH ２ ) ｎ is a monovalent organic group represented by Y, wherein Y is a hydrogen atom, an acetoxy group, a γ-butyrolactone group, a C1 to C6 carbinol group optionally substituted with a halogen atom, a norbornene group, a toluyl group, a C1 to C3 alkoxyphenyl group, a C6 to C30 aryl group optionally substituted with a halogen atom or a C1 to C3 alkoxysilyl group, a C1 to C4 alkyl group optionally interrupted by an oxygen atom, a phenylsulfonamido group, a monovalent group derived from a cyclic amide optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a monovalent group derived from a cyclic imide optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a C3 to C6 cyclic alkenyl group optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a phenylsulfone group, a p-tolylsulfonyl group, a p-toluenesulfonyl group, or a monovalent group represented by the following formula (1-1) or (1-2) (* represents a bond), n is an integer from 0 to 4, and R ２ is a C1 to C4 monovalent hydrocarbon group, X is a hydrogen atom or a C1 to C4 monovalent hydrocarbon group, a is 1 to 2, b is 0 to 1, c is a number of 0 to 2, and a + b + c ≦ 4.

[0161] Examples of the surface modification layer-forming composition (S3) include the surface modifier for resist patterns described in International Publication No. 2019 / 198700. The contents of this publication are incorporated herein by reference to the same extent as if set forth in their entirety.

[0162] The method for forming the surface modification layer is not particularly limited, and examples thereof include applying a composition for forming a surface modification layer onto a silicon-containing underlayer film. Examples of application methods include appropriate application methods such as using a spinner or a coater. After application, heating (baking) may be performed as necessary. Heating can be performed using a heating means such as a hot plate.

[0163] The method for forming the surface modification layer may also be the following: A surface modification layer-forming composition is applied to a silicon-containing underlayer film to form a surface modification layer precursor, and the surface modification layer precursor is then brought into contact with a thinning liquid to thin the surface modification layer precursor, thereby obtaining a surface modification layer with a thickness of 5 nm or less. In this way, the surface modification layer precursor becomes thinner by the amount of components in the surface modification layer precursor that have migrated to the thinning liquid, resulting in a surface modification layer with a thickness of 5 nm or less.

[0164] The method for contacting the surface-modified layer precursor with the thinning liquid is not particularly limited, but spin coating is preferred because it allows uniform thinning and makes it easy to control the degree of thinning with high precision. That is, it is preferable to thin the surface-modified layer precursor by spin-coating the thinning liquid onto the surface-modified layer precursor to obtain a surface-modified layer with a film thickness of 5 nm or less.

[0165] The thinning liquid is not particularly limited as long as it is a liquid that can thin the surface modification layer precursor by contacting the surface modification layer precursor with the thinning liquid, and examples thereof include organic solvents, water, acidic solutions, alkaline aqueous solutions, etc. In addition, thinners used in the RRC (reducing resist compression) process or the EBR (edge ​​bead removing) process can be used. These can be used alone or in combination of two or more.

[0166] Examples of the organic solvent include alcohols, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic acid esters.

[0167] Examples of alcohols include monoalcohol solvents, polyhydric alcohol solvents, etc. Specific examples of these include the monoalcohol solvents and polyhydric alcohol solvents described above as solvents for hydrolysis and condensation.

[0168] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.

[0169] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include alkylene glycol monoalkyl ether acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0170] Specific examples of other organic solvents include toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate. butyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, iso butyrate Propyl, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxyisobutyrate, methyl 3-hydroxyisobutyrate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, γ-butyrolactone, and the like.

[0171] Examples of acidic solutions include inorganic acid aqueous solutions, organic acid aqueous solutions, and organic acid solutions. Examples of inorganic acid aqueous solutions include hydrochloric acid aqueous solutions, nitric acid aqueous solutions, phosphoric acid aqueous solutions, sulfuric acid aqueous solutions, and perchloric acid aqueous solutions. Examples of organic acid aqueous solutions include acetic acid aqueous solutions, trifluoroacetic acid aqueous solutions, camphorsulfonic acid aqueous solutions, p-toluenesulfonic acid aqueous solutions, and trifluoromethanesulfonic acid aqueous solutions. Examples of organic acid solutions include those in which the water in the above organic acid aqueous solutions has been replaced with an organic solvent. Examples of organic solvents include alkylene glycol alkyl ethers and alkylene glycol monoalkyl ether carboxylic acid esters.

[0172] Examples of alkaline aqueous solutions include developers used in lithography processes. Examples of alkaline aqueous solutions include inorganic alkaline aqueous solutions and organic alkaline aqueous solutions. Examples of inorganic alkaline aqueous solutions include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, sodium phosphate aqueous solution, and potassium phosphate aqueous solution. Examples of organic alkaline aqueous solutions include tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution, monoethanolamine aqueous solution, diethanolamine aqueous solution, and triethanolamine aqueous solution. The concentration of alkali in the alkaline aqueous solution is not particularly limited.

[0173] The RRC (reducing resist consumption) process is a process for reducing the amount of photoresist used, in which a small amount of photoresist is uniformly applied over the entire surface of the substrate by treating the substrate surface with a thinner before applying the photoresist. The EBR (edge ​​bead removing) process is a process for removing unnecessary photoresist residue and other contaminants applied to the edge or rear surface of the substrate during the application process. Examples of thinners used in the RRC and EBR processes include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, ethyl 3-ethoxypropionate, methyl hydroxyisobutyrate, and mixtures thereof.

[0174] The film thickness of the surface modification layer is not particularly limited as long as it is 5 nm or less, and may be, for example, 0.1 nm to 5 nm, 0.1 nm to 4.5 nm, 0.2 nm to 4.5 nm, 0.2 nm to 4 nm, 0.5 nm to 4 nm, 0.5 nm to 3.5 nm, or 0.5 nm to 3 nm.

[0175] The film thickness can be measured, for example, under the following conditions: Measurement device name: Ellipso film thickness measurement device RE-3100 (SCREEN Corporation) SWE (single wavelength ellipsometer) mode Arithmetic mean of 8 points (for example, 8 points measured at 1 cm intervals in the X direction of the wafer)

[0176] (Silicon-containing underlayer film, semiconductor processing substrate, pattern formation method, and semiconductor element manufacturing method) Hereinafter, as one aspect of the present invention, a silicon-containing underlayer film, a semiconductor processing substrate, a pattern formation method, and a semiconductor element manufacturing method using the silicon-containing underlayer film-forming composition of the present invention will be described.

[0177] The silicon-containing underlayer film of the present invention is a cured product of the silicon-containing underlayer film-forming composition of the present invention. The semiconductor processing substrate of the present invention comprises the silicon-containing underlayer film of the present invention.

[0178] The method for manufacturing a semiconductor device of the present invention includes the steps of: forming an organic underlayer film on a substrate; forming a silicon-containing underlayer film on the organic underlayer film using the silicon-containing underlayer film-forming composition of the present invention; forming a surface modification layer on the silicon-containing underlayer film; and forming a resist film on the surface modification layer.

[0179] The pattern formation method of the present invention includes the steps of: forming an organic underlayer film on a semiconductor substrate; applying the silicon-containing underlayer film-forming composition of the present invention onto the organic underlayer film and baking the composition to form a silicon-containing underlayer film; forming a surface modification layer on the silicon-containing underlayer film; forming a resist film on the surface modification layer; exposing and developing the resist film to obtain a resist pattern; etching the surface modification layer and the silicon-containing underlayer film using the resist pattern as a mask; and etching the organic underlayer film using the patterned surface modification layer and the silicon-containing underlayer film as a mask.

[0180] First, the silicon-containing underlayer film-forming composition of the present invention is applied to a substrate used in the manufacture of precision integrated circuit devices (e.g., a semiconductor substrate such as a silicon wafer coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (including alkali-free glass, low-alkali glass, and crystallized glass), a glass substrate formed with an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film, a plastic (polyimide, PET, etc.) substrate, a low-dielectric constant material (low-k material)-coated substrate, a flexible substrate, etc.) by a suitable application method such as a spinner or coater, and then baked using a heating means such as a hot plate to harden the composition and form a silicon-containing underlayer film. Hereinafter, in this specification, the silicon-containing underlayer film refers to a film formed from the silicon-containing underlayer film-forming composition of the present invention. Baking conditions are appropriately selected from a baking temperature of 40°C to 400°C or 80°C to 250°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 150°C to 250°C, and the baking time is 0.5 to 2 minutes. The film thickness of the silicon-containing underlayer film formed here is, for example, 5 nm to 100 nm, or 10 nm to 50 nm, or 10 nm to 30 nm, or 10 nm to 25 nm, or 10 to 20 nm. A silicon-containing underlayer film-forming composition that has been filtered through a nylon filter can be used as the silicon-containing underlayer film-forming composition. Here, the "silicon-containing underlayer film-forming composition that has been filtered through a nylon filter" refers to a composition that has been filtered through a nylon filter during the production of the silicon-containing underlayer film-forming composition or after all of the components have been mixed.

[0181] In the present invention, an organic underlayer film is formed on a substrate, followed by a silicon-containing underlayer film, and then a surface modification layer is formed thereon. However, in some cases, an organic underlayer film may not be provided. The organic underlayer film used here is not particularly limited, and any of those conventionally used in lithography processes can be selected and used. By providing an organic underlayer film, a silicon-containing underlayer film thereon, a surface modification layer thereon, and a resist film (described below) on the substrate, the pattern width of the resist film is narrowed. Even if a thin resist film is applied to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas (described below). For example, the surface modification layer and the silicon-containing underlayer film can be processed using a fluorine-based gas having a sufficiently fast etching rate for the surface modification layer and the silicon-containing underlayer film as an etching gas, and the resist pattern as an etching mask. In addition, the organic underlayer film can be processed by using an oxygen-based gas having a sufficiently high etching rate for the organic underlayer film as an etching gas, and using the patterned surface modification layer and silicon-containing underlayer film as an etching mask.Furthermore, the substrate can be processed by using a fluorine-based gas having a sufficiently high etching rate for the substrate as an etching gas, and using the patterned organic underlayer film as an etching mask.The substrate and coating method that can be used in this case are the same as those described above.

[0182] The step of forming a silicon-containing underlayer film may include at least one of dry etching, baking at 250°C or higher, and UV irradiation. These treatments are performed on the cured product, for example, after applying the silicon-containing underlayer film-forming composition to a substrate and baking it to obtain a cured product. These treatments are particularly effective in improving the film-forming properties of the surface modification layer when the silicon-containing underlayer film-forming composition contains a curing catalyst.

[0183] The conditions for the dry etching process are not particularly limited. The atmospheric gas used in the dry etching process is not particularly limited, and examples thereof include atmospheric gases containing at least one of oxygen gas, hydrogen gas, nitrogen gas, and rare gases. Of these, oxygen gas is preferred. The flow rate of the atmospheric gas used in the dry etching process is not particularly limited, and examples thereof include 10 sccm to 300 sccm. In the dry etching process, gas is converted into plasma, so the dry etching process is usually performed under reduced pressure. The pressure used in this process is not particularly limited, and examples thereof include 0.1 Pa to 10 Pa.

[0184] The baking treatment is usually carried out at a temperature higher than the firing temperature when the silicon-containing underlayer film is formed. In this respect, the baking treatment is usually carried out at 250°C or higher. The atmosphere for the baking treatment is not particularly limited, and examples thereof include an air atmosphere and an inert atmosphere. An example of an inert atmosphere is a nitrogen gas atmosphere. The baking temperature may be 250°C to 500°C, or 300°C to 450°C. The baking time may be, for example, 30 seconds to 10 minutes.

[0185] The conditions for the UV irradiation treatment are not particularly limited. The wavelength (irradiation wavelength) in the UV irradiation treatment is not particularly limited, and examples thereof include 170 nm to 370 nm. The atmosphere for the UV irradiation treatment is not particularly limited, and may be an air atmosphere or an inert atmosphere, but an oxygen-containing atmosphere or a nitrogen atmosphere is preferred. From the viewpoint of generating ozone, the atmosphere for the UV irradiation treatment is preferably an oxygen-containing atmosphere, and more preferably an air atmosphere (air atmosphere). The radiation source (light source) for the UV irradiation treatment is not particularly limited, and examples thereof include a UV lamp, an excimer UV lamp, an excimer laser, a radiation tube, and an electron gun. Among these, from the viewpoint of high ease of handling and high treatment efficiency, an excimer UV lamp (e.g., a xenon excimer lamp: emission center wavelength 172 nm) is preferred. The UV irradiation dose is not particularly limited, and examples thereof include 100 mJ / cm. ２ ~10,000mJ / cm ２Examples include:

[0186] For example, a layer of a resist material (resist film) is formed on the surface modification layer. The resist film can be formed by a well-known method, i.e., by applying a coating-type resist material (resist film-forming composition) on the surface modification layer and baking it. The film 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.

[0187] The photoresist material used in the resist film 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. Examples include a positive photoresist material composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist material composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator, a chemically amplified photoresist material composed of a low molecular weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator, and a chemically amplified photoresist material composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate, a low molecular weight compound that decomposes in the presence of an 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. Other examples include fluorine-containing polymer photoresist materials such as 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).

[0188] Furthermore, instead of a photoresist 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 as the resist film. That is, the silicon-containing underlayer film-forming composition of the present invention can be used for forming an underlayer film for electron beam lithography or an underlayer film for EUV lithography. It is particularly suitable as a composition for forming an underlayer film for EUV lithography. As the electron beam resist material for forming the electron beam resist film, either a negative material or a positive material can be used. Specific examples include a chemically amplified resist material comprising an acid generator and a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate, a chemically amplified resist material comprising an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material, a chemically amplified resist material comprising an acid generator, a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material, a non-chemically amplified resist material comprising a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate, and a non-chemically amplified resist material comprising a binder having a moiety 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.

[0189] Furthermore, as an EUV resist material for forming an EUV resist film, a methacrylate resin-based resist material or a metal-containing resist can be used. Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist. Examples of metal oxide resist materials include a coating composition containing a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal carboxylate bonds, as described in JP-A-2019-113855. One example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described, for example, in paragraph

[0011] of JP-A-2019-532489. Examples of such patent documents include U.S. Pat. No. 9,176,377 B2, U.S. Patent Application Publication No. 2013 / 0224652 A1, U.S. Pat. No. 9,310,684 B2, U.S. Patent Application Publication No. 2016 / 0116839 A1, and U.S. Patent Application Publication No. 15 / 291738.

[0190] Further examples of metal-containing resists include: Coatings containing metal oxo-hydroxo networks with organic ligands via metal carbon and / or metal carboxylate bonds.

[0191] Inorganic oxo / hydroxo-based compositions.

[0192] a coating solution comprising an organic solvent; a first organometallic composition having the formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (where 0<z≦2 and 0<(z+x)≦4), formula R′ ｎ SnX ４－ｎ wherein n=1 or 2, or mixtures thereof, where R and R′ are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn, or a combination thereof; and a hydrolyzable metal compound having the formula MX′ｖ wherein M is a metal selected from groups 2 to 16 of the periodic table of the elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof.

[0193] an organic solvent and a solution of the formula RSnO （３／２－ｘ／２） (OH) ｘ and a first organometallic compound of the formula: wherein 0<x<3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having from 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.

[0194] An aqueous inorganic patterning precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.

[0195] Other examples of metal-containing resists include those described in JP 2011-253185 A, WO 2015 / 026482, WO 2016 / 065120, WO 2017 / 066319, WO 2017 / 156388, WO 2018 / 031896, JP 2020-122959 A, JP 2020-122960 A, WO 2019 / 099981, WO 2019 / 199467, WO 2019 / 195522, WO 2019 / 195522, WO 2020 / 210660, WO 2021 / 011367, and WO 2021 / 016229. The contents of these are incorporated herein in their entirety to the same extent as if set forth in full.

[0196] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method in which a coating-type resist material (a composition for forming a metal-containing resist film) that is a metal-containing resist is coated and baked.

[0197] The metal-containing resist film may also be formed by vapor deposition. Examples of methods for forming a metal-containing resist film by vapor deposition include the method described in JP 2017-116923 A. The contents of JP 2017-116923 A are incorporated herein by reference to the same extent as if fully set forth herein. In JP 2017-116923 A, the metal-containing resist film of the present invention is referred to as a metal oxide-containing film.

[0198] Next, the resist film is exposed to light through a predetermined mask (reticle). For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or an F ２ Excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), electron beam, etc. can be used. After exposure, post-exposure baking can be performed as needed. The post-exposure baking is performed 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.

[0199] Next, development is carried out using a developer (e.g., an alkaline developer). As a result, when a positive photoresist film is used, for example, the exposed portions of the photoresist film are removed, forming a photoresist film pattern. Examples of the developer (alkaline developer) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0200] In the present invention, an organic solvent can be used as a developer, and development is carried out with the developer (solvent) after exposure. As a result, when a negative resist film (e.g., a metal-containing resist film) is used, the unexposed portions of the resist film are removed, and a resist film pattern is formed. Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 4-methyl ... Butyl 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 acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate,Examples of the developer include isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Furthermore, surfactants and the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5°C to 50°C and a development time of 10 to 600 seconds.

[0201] The surface modification layer and the silicon-containing underlayer film (middle layer) are removed using the pattern of the resist film (upper layer) thus formed as a protective film, and then the organic underlayer film (lower layer) is removed using the patterned surface modification layer and the silicon-containing underlayer film (middle layer) as protective films. Finally, the substrate is processed using the patterned organic underlayer film (lower layer) as a protective film. Note that when removing the organic underlayer film (lower layer), a portion of the resist pattern may remain on the patterned surface modification layer and the silicon-containing underlayer film. Furthermore, when processing the substrate, a portion of the patterned silicon-containing underlayer film may remain on the patterned organic underlayer film.

[0202] The removal (patterning) of the surface modification layer and the silicon-containing lower layer (middle layer) is performed by dry etching using the pattern of the resist film (upper layer) as a protective film. ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８Gases such as fluorine, trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. It is preferable to use a halogen-based gas for dry etching of the surface-modified layer and the silicon-containing underlayer film. Resist films (photoresist films) made of organic substances are generally difficult to remove with dry etching using a halogen-based gas. In contrast, for example, surface-modified layers and silicon-containing underlayer films containing a large amount of silicon atoms are quickly removed with a halogen-based gas. Therefore, the reduction in the thickness of the resist film due to dry etching of the surface-modified layer and the silicon-containing underlayer film can be suppressed. As a result, it becomes possible to use a thin resist film. Therefore, it is preferable to use a fluorine-based gas for dry etching of the silicon-containing underlayer film. Examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ ) and the like, but are not limited to these.

[0203] When an organic underlayer film is present between the substrate and the silicon-containing underlayer film, the removal (patterning) of the organic underlayer film (underlayer) is preferably carried out by dry etching using an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.) with the patterned resist film (upper layer) (and the patterned resist film (upper layer) if any remains), the patterned surface modification layer, and the silicon-containing underlayer film (middle layer) as protective films. This is because the silicon-containing underlayer film of the present invention, which contains a large amount of silicon atoms, is difficult to remove by dry etching using an oxygen-based gas. In addition, by using a surface modification layer and a silicon-containing underlayer film instead of the conventional single-layer silicon-containing resist underlayer film, the silicon-containing underlayer film can be made into a composition specialized for providing etching resistance, and therefore the thickness of the silicon-containing underlayer film can be made thinner.

[0204] Thereafter, the (semiconductor) substrate is processed (patterned) using the patterned surface modification layer, the silicon-containing underlayer film (intermediate layer), and, if desired, the patterned organic underlayer film (underlayer) as protective films, preferably by dry etching using a fluorine-based gas. Examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, and difluoromethane (CH ２ F ２ ) etc.

[0205] After removing (patterning) the organic underlayer film or processing (patterning) the substrate, the surface modification layer and the silicon-containing underlayer film can be removed. The surface modification layer and the silicon-containing underlayer film can be removed by dry etching or wet etching (wet method). Dry etching of the surface modification layer and the silicon-containing underlayer film is preferably performed with a fluorine-based gas, as mentioned in the patterning, such as tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ Examples of chemicals used for wet etching of the surface modification layer and the silicon-containing underlayer film include, but are not limited to, dilute hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (HF and NH ４Examples of suitable alkaline solutions include an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution). Examples of alkaline solutions include the aforementioned ammonia hydrogen peroxide solution (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide, and water, as well as aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These chemical solutions can also be used in combination.

[0206] Furthermore, the substrate to which the silicon-containing underlayer film-forming composition is applied may have an organic or inorganic anti-reflective coating formed on its surface by a CVD method or the like, and the silicon-containing underlayer film may be formed thereon. Even when an organic underlayer film is formed on a substrate and then the silicon-containing underlayer film of the present invention is formed thereon, the substrate used may have an organic or inorganic anti-reflective coating formed on its surface by a CVD method or the like.

[0207] The silicon-containing underlayer film formed from the silicon-containing underlayer film-forming composition may also absorb light depending on the wavelength of the light used in the lithography process, and in such cases, can function as an anti-reflection film that has the effect of preventing light from being reflected from the substrate.

[0208] The silicon-containing underlayer film can be applied to a substrate having via holes formed therein for use in a dual damascene process, and can be used as a hole-filling material (embedding material) capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the surface of an uneven semiconductor substrate. Furthermore, the silicon-containing underlayer film of the present invention can be used as an underlayer film for an EUV resist film, not only functioning as a hard mask, but also preventing reflection from the substrate or interface of undesirable exposure light, such as UV (ultraviolet) light or DUV (deep ultraviolet) light (ArF light, KrF light), during EUV exposure (wavelength 13.5 nm), without intermixing with the EUV resist film. Therefore, the silicon-containing underlayer film-forming composition of the present invention can be suitably used to form an underlayer anti-reflective coating for an EUV resist film. That is, it can efficiently prevent reflection as an underlayer for an EUV resist film. When used as an EUV underlayer film, the process can be carried out in the same manner as for an underlayer film for a photoresist.

[0209] The semiconductor processing substrate comprising the silicon-containing underlayer film of the present invention and the semiconductor substrate described above can be used to suitably process the semiconductor substrate. Furthermore, the semiconductor element manufacturing method of the present invention as described above can achieve highly accurate processing of the semiconductor substrate with good reproducibility, and therefore stable manufacturing of semiconductor elements can be expected.

[0210] The present invention will be explained in more detail below by way of synthesis examples and examples, but the present invention is not limited to the following examples.

[0211] In the examples, the apparatus and conditions used for analyzing the physical properties of samples 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 were a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC columns (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as the standard sample. (2) １ H-NMR JEOL nuclear magnetic resonance apparatus １ Evaluation was performed using H-NMR (400 MHz) and d6-acetone as the solvent. (3) Residual amount of nitric acid The amount of nitric acid remaining in the system was measured by ion chromatography evaluation. (4) AFM (atomic force microscope) The film surface roughness was measured using a medium-sized probe microscope system manufactured by Hitachi High-Tech. (5) Film thickness measurement The film thickness was measured under the following conditions. - Name of measuring device: Ellipso film thickness measuring device RE-3100 (SCREEN Co., Ltd.) - SWE (single wavelength ellipsometer) mode - Arithmetic average of 8 points (for example, 8 points measured at 1 cm intervals in the X direction of the wafer)

[0212] [1] Synthesis of Polymer (Hydrolyzed Condensate) (Synthesis Example 1-1) 23.26 g of tetraethoxysilane, 7.11 g of methyltriethoxysilane, 1.58 g of phenyltrimethoxysilane, and 47.93 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 20.12 g of 0.1 M aqueous nitric acid solution was added dropwise while the mixed solution was stirred with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60 ° C. and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol, methanol, and water, were distilled off under reduced pressure, and the solution was concentrated to obtain a hydrolyzed condensate (polymer) solution. Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 140 ° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane having a structure represented by the following formula, and its weight average molecular weight was 3,000 as calculated as polystyrene by GPC. １ H-NMR revealed that the amount of capping with propylene glycol monoethyl ether was 3 mol% relative to the Si atoms. The residual nitric acid content in the polymer solution was 1,200 ppm. The ratio of tetraethoxysilane to the total amount of hydrolyzable silanes added was 70 mol%.

[0213]

[0214] Synthesis Example 1-2: 23.0 g of tetraethoxysilane, 7.0 g of methyltriethoxysilane, 2.02 g of bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane, and 48.1 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.9 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise while the mixed solution was stirred with a magnetic stirrer. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol and water, were distilled off under reduced pressure, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane having a structure represented by the following formula, and its weight average molecular weight was Mw 2,800 as calculated in terms of polystyrene by GPC. １ H-NMR revealed that the amount of capping with propylene glycol monoethyl ether was 3 mol% relative to the Si atoms. The residual nitric acid content in the polymer solution was 1,200 ppm. The ratio of tetraethoxysilane to the total amount of hydrolyzable silanes added was 70 mol%.

[0215]

[0216] (Synthesis Example 1-3) 22.3 g of tetraethoxysilane, 6.82 g of methyltriethoxysilane, 3.16 g of diallyl isocyanurate propyltriethoxysilane, and 48.4 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.3 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise while the mixed solution was stirred with a magnetic stirrer. After the dropwise addition, the flask was transferred to an oil bath adjusted to 60 ° C. and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol and water, were distilled off under reduced pressure, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the solution, and the concentration was adjusted to 20 mass percent in terms of solid residue at 140 ° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered with a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane having a structure represented by the following formula, and its weight average molecular weight was Mw 2,300 as calculated on a polystyrene basis by GPC. １ H-NMR revealed that the amount of capping with propylene glycol monoethyl ether was 2 mol% relative to the Si atoms. The residual nitric acid content in the polymer solution was 1,200 ppm. The ratio of tetraethoxysilane to the total amount of hydrolyzable silanes added was 70 mol%.

[0217]

[0218] Synthesis Example 1-4: 26.4 g of tetraethoxysilane, 5.64 g of methyltriethoxysilane, and 48.0 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 20.0 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. The reaction by-products, ethanol and water, were then distilled off under reduced pressure, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the solution, and the concentration was adjusted to 20 mass percent in terms of solid residue at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered with a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane having a structure represented by the following formula, and its weight average molecular weight, as measured by GPC in terms of polystyrene, was Mw 2,900. Also, １ H-NMR revealed that the amount of capping with propylene glycol monoethyl ether was 3 mol% relative to the Si atoms. The residual nitric acid content in the polymer solution was 1,300 ppm. The ratio of tetraethoxysilane to the total amount of hydrolyzable silanes added was 80 mol%.

[0219]

[0220] Synthesis Example 1-5 32.2 g of tetraethoxysilane and 48.3 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.5 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. The reaction by-products, ethanol and water, were then distilled off under reduced pressure, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the solution, and the concentration was adjusted to 20 mass percent in terms of solid residue at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered with a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane having a structure represented by the following formula, and its weight-average molecular weight, measured as polystyrene equivalent by GPC, was Mw 4,300. Furthermore, １ H-NMR revealed that the amount of capping with propylene glycol monoethyl ether was 3 mol% relative to the Si atoms. The residual nitric acid content in the polymer solution was 1,200 ppm. The ratio of tetraethoxysilane to the total amount of hydrolyzable silanes added was 100 mol%.

[0221]

[0222] [2] Preparation of Compositions for Forming Silicon-Containing Underlayer Films The polysiloxanes (polymers), acid (additive 1), photoacid generators (additive 2), and solvents obtained in Synthesis Examples 1-1 to 1-5 above were mixed in the proportions shown in Table 1, and filtered through a 0.1 μm fluororesin filter to prepare Compositions 1 to 6 for forming silicon-containing underlayer films, respectively. The amounts of each additive in Table 1 are shown in parts by mass. Note that, although the hydrolysis condensate (polymer) was prepared as a solution containing the condensate obtained in the Synthesis Examples, the proportion of polymer added in Table 1 indicates the amount of polymer itself added, not the amount of polymer solution added.

[0223] The abbreviations in Tables 1 and 2 mean the following: MA: Maleic acid TPSNO3: Triphenylsulfonium nitrate PGEE: Propylene glycol monoethyl ether PGME: Propylene glycol monomethyl ether DIW: Ultrapure water

[0224] Compositions 1 to 6 for forming silicon-containing underlayer films further contain the nitric acid contained in the polymer solutions prepared in Synthesis Examples 1 to 5.

[0225] [3] Preparation of Organic Resist Underlayer Film Forming Composition Under nitrogen, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and paratoluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 ml four-neck flask, and 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred. The mixture was heated to 100°C to dissolve the components and initiate polymerization. After 24 hours, the mixture was allowed to cool to 60°C. The cooled reaction mixture was diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to cause precipitation. The resulting precipitate was collected by filtration, and the collected solid was dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL). １ The results of H-NMR measurement were as follows: １ H-NMR (400MHz, DMSO-d ６ ): δ 7.03-7.55 (br, 12H), δ 7.61-8.10 (br, 4H), δ 11.18 (br, 1H) The weight average molecular weight Mw of PCzFL was 2,800 as calculated in terms of polystyrene by GPC, and the polydispersity Mw / Mn was 1.77.

[0226]

[0227] 20 g of PCzFL, 3.0 g of tetramethoxymethylglycoluril (trade name Powder Link 1174, manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.)) as a crosslinking agent, 0.30 g of pyridinium paratoluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (trade name, manufactured by DIC Corporation) as a surfactant were mixed, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 0.10 μm, and further filtered using a polyethylene microfilter with a pore size of 0.05 μm, to prepare a composition for forming an organic resist underlayer film to be used in a multilayer film lithography process.

[0228] [4] Synthesis of Polymer (Hydrolyzed Condensation Product) (Synthesis Example 2-1) 33.42 g of bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane and 50.13 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 16.44 g of a 1 M aqueous nitric acid solution was added dropwise while stirring the resulting mixed solution with a magnetic stirrer. After the dropwise addition, the flask was transferred to an oil bath adjusted to 120°C, and the reaction was allowed to proceed for 20 hours. The reaction by-products, ethanol and water, were then distilled off under reduced pressure, and the resulting solution was concentrated to obtain a hydrolyzed condensation product (polymer) solution. Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted to 20 mass percent, calculated as a solid residue at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (pore size: 0.1 μm). The obtained polymer contained a polysiloxane having a structure represented by the following formula, and its weight average molecular weight was 1,200 as calculated using polystyrene standards by GPC. １ H-NMR revealed that the amount of capping with propylene glycol monoethyl ether was 5 mol % relative to the Si atoms, and the amount of residual nitric acid in the polymer solution was 0.8%.

[0229]

[0230] Synthesis Example 2-2: 35.65 g of diallyl isocyanurate propyltriethoxysilane and 53.48 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 10.87 g of 0.1 M aqueous nitric acid solution was added dropwise to the resulting mixed solution while stirring with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 120°C, and the reaction was allowed to proceed for 20 hours. The reaction by-products, ethanol and water, were then distilled off under reduced pressure, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the resulting solution, and the concentration was adjusted to 20 mass percent, calculated as a solid residue at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered through a nylon filter (pore size 0.1 μm). The resulting polymer contained a polysiloxane having a structure represented by the following formula, and its weight-average molecular weight, calculated as polystyrene by GPC, was 2,300. Furthermore, １ H-NMR revealed that the amount of capping with propylene glycol monoethyl ether was 6 mol % relative to the Si atoms, and the amount of residual nitric acid in the polymer solution was 0.07%.

[0231]

[0232] [5] Preparation of Composition for Forming Surface Modification Layer The polysiloxane (polymer), acid (additive 1), and solvent obtained in Synthesis Examples 2-1 to 2-2 above were mixed in the proportions shown in Table 2, and filtered through a 0.1 μm fluororesin filter to prepare Compositions 1 and 2 for forming surface modification layers, respectively. The amounts of each additive in Table 2 are shown in parts by mass. Note that the hydrolysis condensate (polymer) was prepared as a solution containing the condensate obtained in the synthesis example, but the proportion of polymer added in Table 2 indicates the amount of polymer itself added, not the amount of polymer solution added.

[0233]

[0234] [6] Film-forming property test of compositions for forming surface-modifying layers Compositions 1 to 6 for forming silicon-containing underlayer films were each applied onto a silicon wafer using a spinner. The composition was heated on a hot plate at 215°C for 1 minute to form a Si-containing underlayer film. For Examples 6 to 8, the composition was then subjected to a pre-treatment of O ２ Etching process (oxygen plasma etching process, O ２ : 40 sccm 100 W 8 Pa 60 sec), 400 degree bake (N ２ under ozone-generating conditions, 1000 mJ / cm ２ ) were performed on each of the Si-containing underlayer films. Then, surface-modified layer-forming compositions 1 and 2 were applied to each of the Si-containing underlayer films, which were then heated on a hot plate at 180 degrees for 1 minute. The resulting film was then rinsed with a solution (thinning solution) of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7 / 3 (mass ratio) and thinned to form a surface-modified layer. This resulted in a Si-containing underlayer film having a surface-modified layer (film thickness: 1 nm) thereon. The surface-modified layer was then observed with an AFM, and films with a surface roughness value Sa of 0.3 nm or less were rated "good," while films with a surface roughness value Sa of more than 0.3 nm were rated "poor." The results are shown in Table 3.

[0235]

[0236] [7] Formation of a resist pattern by EUV exposure: positive solvent development (Example 9) The above-mentioned organic resist underlayer film-forming composition was applied to a silicon wafer using a spinner and baked on a hot plate at 215°C for 60 seconds to obtain an organic underlayer film (layer A) with a film thickness of 60 nm. Silicon-containing underlayer film-forming composition 1 was spin-coated thereon and heated at 215°C for 1 minute to form a Si-containing underlayer film (layer B) (20 nm). Then, surface-modifying layer-forming composition 1 was applied to the Si-containing underlayer film, which was then heated on a hot plate at 180°C for 1 minute, and then rinsed with a solution (thinning solution) of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7 / 3 (mass ratio) to thin it, forming a surface-modifying layer. As a result, a Si-containing underlayer film having a surface-modifying layer (thickness: 1 nm) thereon was obtained. Further, an EUV resist solution (methacrylate resin-based resist) was spin-coated thereon and heated at 110°C for 1 minute to form an EUV resist film (C layer), which was then exposed using an ASML EUV exposure system (NXE3400) under conditions of NA = 0.33, σ = 0.60 / 0.82, and quadropole. After exposure, post-exposure baking (PEB, 105°C for 1 minute) was performed, and the film was cooled to room temperature on a cooling plate. It was then developed for 30 seconds using a 2.38% TMAH developer and rinsed to form a resist pattern.

[0237] Example 10 A resist pattern was formed in the same manner as in Example 9, except that composition 5 for forming a silicon-containing underlayer film was used.

[0238] Example 11 Composition 1 for forming a silicon-containing underlayer film was spin-coated onto an organic underlayer film, and the resulting mixture was heated at 215°C for 1 minute. ２ Etching process (oxygen plasma etching process, O ２ The resist pattern was formed in the same manner as in Example 9.

[0239] Example 12 Composition 1 for forming a silicon-containing underlayer film was spin-coated onto an organic underlayer film, heated at 215°C for 1 minute, and then baked at 400°C (N ２ Otherwise, a resist pattern was formed in the same manner as in Example 9.

[0240] For each pattern obtained in Examples 9 to 12, the possibility of forming a 28 nm pitch, 14 nm line and space pattern was evaluated by observing the pattern cross section. In observing the pattern shape, a state in which the shape was between footing and undercut and there was no significant residue in the space portion was evaluated as "good," and an unfavorable state in which the lower portions of the resist pattern were in contact with each other was evaluated as "bridge." The results are shown in Table 4.

[0241]

[0242] [8] Formation of a metal oxide resist pattern by EUV exposure: negative solvent development (Example 13) The above-mentioned organic resist underlayer film-forming composition was applied to a silicon wafer using a spinner and baked on a hot plate at 215 ° C for 60 seconds to obtain an organic underlayer film (layer A) with a film thickness of 60 nm. Silicon-containing underlayer film-forming composition 1 was spin-coated thereon and heated at 215 ° C for 1 minute to form a Si-containing underlayer film (layer B) (20 nm). Then, surface-modifying layer-forming composition 1 was applied to the Si-containing underlayer film, which was then heated on a hot plate at 180 ° C for 1 minute, and then rinsed with a solution (thinning solution) of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7 / 3 (mass ratio) to thin it, forming a surface-modifying layer. As a result, a Si-containing underlayer film having a surface-modifying layer (thickness: 1 nm) thereon was obtained. An EUV resist solution (Sn-containing metal oxide resist) was spin-coated thereon and heated at 100°C for 1 minute to form an EUV resist film (C layer), which was then exposed using an ASML EUV exposure system (NXE3400) under conditions of NA = 0.33, σ = 0.60 / 0.82, and quadropole. After exposure, post-exposure baking (PEB, 180°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate. Development was performed using propylene glycol monomethyl ether acetate for 30 seconds, and post-development baking (250°C for 1 minute) was performed to form a resist pattern.

[0243] Example 14 A resist pattern was formed in the same manner as in Example 13, except that composition 5 for forming a silicon-containing underlayer film was used.

[0244] Example 15 Composition 1 for forming a silicon-containing underlayer film was spin-coated onto an organic underlayer film, and the resulting mixture was heated at 215°C for 1 minute. ２ Etching process (oxygen plasma etching process, O ２ The resist pattern was formed in the same manner as in Example 13.

[0245] Example 16 Composition 1 for forming a silicon-containing underlayer film was spin-coated onto an organic underlayer film, heated at 215°C for 1 minute, and then baked at 400°C (N ２ Otherwise, a resist pattern was formed in the same manner as in Example 13.

[0246] For each pattern obtained in Examples 13 to 16, the possibility of forming a 28 nm pitch, 14 nm line and space pattern was evaluated by observing the pattern cross section. In observing the pattern shape, a state in which the shape was between footing and undercut and there was no significant residue in the space portion was evaluated as "good," and an unfavorable state in which the lower portions of the resist pattern were in contact with each other was evaluated as "bridge." The results are shown in Table 5.

[0247]

Claims

1. A composition for forming a silicon-containing lower layer film on which a surface modification layer with a film thickness of 5 nm or less is formed, comprising: [A] component: a polysiloxane containing 30 mol% or more of Q units based on all units, and [B] component: water, and not containing [C] component: a curing catalyst, the composition for forming a silicon-containing lower layer film.

2. A composition for forming a silicon-containing lower layer film on which a surface modification layer with a film thickness of 5 nm or less is formed, wherein the surface modification layer is formed on the silicon-containing lower layer film that has been subjected to at least one of a dry etching treatment, a baking treatment at 250 °C or higher, and a UV irradiation treatment, and [A] component: a polysiloxane containing 30 mol% or more of Q units based on all units, the composition for forming a silicon-containing lower layer film.

3. The composition for forming a silicon-containing lower layer film according to claim 2, wherein the atmosphere gas in the dry etching treatment contains at least one of oxygen gas, hydrogen gas, nitrogen gas, and rare gas, the wavelength in the UV irradiation treatment is 170 nm to 370 nm, and the atmosphere is either an atmosphere containing oxygen or a nitrogen atmosphere.

4. The polysiloxane as the [A] component is a hydrolytic condensate of a hydrolyzable silane (Si-1), and the hydrolyzable silane (Si-1) contains 30 mol% or more of a hydrolyzable silane represented by the following formula (A). The composition for forming a silicon-containing lower layer film according to claim 1 or 2. (In formula (A), R is a group or atom bonded to a silicon atom, and independently of each other, represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.) 5. The hydrolyzable silane (Si-1) further contains a hydrolyzable silane represented by the following formula (B), and the composition for forming a silicon-containing lower layer film according to claim 4. (In formula (B), R １１ is a group bonded to a silicon atom, and independently of each other, represents an organic group having 1 to 45 carbon atoms. R １２ is a group or atom bonded to a silicon atom, and independently of each other, represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 1 to 3.) 6. The composition for forming a silicon-containing lower layer film according to claim 1 or 2, wherein the surface modification layer is formed using a composition for forming a surface modification layer containing polysiloxane and a solvent.

7. The polysiloxane contained in the composition for forming the surface modification layer is a hydrolysis condensate of a hydrolyzable silane (Si-2), and the hydrolyzable silane (Si-2) contains a hydrolyzable silane represented by the following formula (S1). The composition for forming a silicon-containing lower layer film according to claim 6. (In formula (S1), R ２１ is a group bonded to a silicon atom and independently represents an organic group having 1 to 45 carbon atoms. R ２２ is a group or atom bonded to a silicon atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 1 to 3.) 8. The composition for forming a silicon-containing lower layer film according to claim 1 or 2, wherein the [A] component includes a polysiloxane modified product in which at least a part of the silanol groups is alcohol-modified or acetal-protected.

9. The composition for forming a silicon-containing lower layer film according to claim 1 or 2, containing an alcohol-based solvent.

10. The composition for forming a silicon-containing lower layer film according to claim 9, wherein the alcohol-based solvent includes propylene glycol monoalkyl ether.

11. The composition for forming a silicon-containing lower layer film according to claim 1 or 2, containing nitric acid.

12. The composition for forming a silicon-containing lower layer film according to claim 1 or 2, used for EUV lithography.

13. A silicon-containing lower layer film which is a cured product of the composition for forming a silicon-containing lower layer film according to claim 1 or 2.

14. A semiconductor processing substrate comprising a semiconductor substrate and the silicon-containing lower layer film according to claim 13.

15. A method for manufacturing a semiconductor device, comprising: a step of forming an organic underlayer film on a substrate; a step of forming a silicon-containing underlayer film on the organic underlayer film using the composition for forming a silicon-containing underlayer film according to claim 1 or 2; a step of forming a surface modification layer on the silicon-containing underlayer film; and a step of forming a resist film on the surface modification layer.

16. The method for manufacturing a semiconductor device according to claim 15, wherein the step of forming the silicon-containing underlayer film includes at least one of dry etching treatment, baking treatment at 250 °C or higher, and UV irradiation treatment.

17. The method for manufacturing a semiconductor device according to claim 16, wherein the atmosphere gas in the dry etching treatment includes at least one of oxygen gas, hydrogen gas, nitrogen gas, and noble gas, the wavelength in the UV irradiation treatment is 170 nm to 370 nm, and the atmosphere is either an oxygen-containing atmosphere or a nitrogen atmosphere.

18. A patterning method, comprising: a step of forming an organic underlayer film on a semiconductor substrate; a step of applying the composition for forming a silicon-containing underlayer film according to claim 1 or 2 on the organic underlayer film and baking to form a silicon-containing underlayer film; a step of forming a surface modification layer on the silicon-containing underlayer film; a step of forming a resist film on the surface modification layer; a step of exposing and developing the resist film to obtain a resist pattern; a step of etching the surface modification layer and the silicon-containing underlayer film using the resist pattern as a mask; and a step of etching the organic underlayer film using the patterned surface modification layer and the silicon-containing underlayer film as a mask.

19. The patterning method according to claim 18, wherein the step of forming the silicon-containing underlayer film includes at least one of dry etching treatment, baking treatment at 250 °C or higher, and UV irradiation treatment.

20. The patterning method according to claim 19, wherein the atmosphere gas in the dry etching treatment includes at least one of oxygen gas, hydrogen gas, nitrogen gas, and noble gas, the wavelength in the UV irradiation treatment is 170 nm to 370 nm, and the atmosphere is either an oxygen-containing atmosphere or a nitrogen atmosphere.

21. The method for forming a pattern according to claim 18, further comprising a step of removing the resist underlayer film by a wet method using a chemical solution after the step of etching the organic underlayer film.

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