Silicon-containing photoresist underlayer film composition containing additives

Abstract

This invention provides a silicon-containing composition for forming a photoresist underlayer film, which is used to form a photoresist underlayer film that can be peeled off in semiconductor substrate and other processing steps not only by conventional dry etching methods, but also by wet etching methods using solutions such as dilute hydrofluoric acid, buffered hydrofluoric acid, and alkaline solutions, and exhibits particularly excellent solubility in alkaline solutions (basic solutions); and provides a composition for forming a photoresist underlayer film for lithography, which is used to form a photoresist underlayer film with excellent preservation stability and low residue in dry etching steps. The composition for forming a silicon-containing photoresist underlayer film of the present invention is a hydrolyzed condensate containing a mixture of hydrolyzed silanes, wherein the hydrolyzed silane mixture contains hydrolyzed silanes represented by formula (1) or hydrolyzed silanes represented by formula (2); it is used to form a silicon-containing photoresist underlayer film soluble in a basic pharmaceutical solution; (in formula (1), R1 is a group bonded to silicon atoms, representing an organic group containing a succinic anhydride skeleton.); (in formula (2), R4 is a group bonded to silicon atoms, representing a monovalent group represented by formula (2-1).)

Description

Technical Field

[0001] This invention relates to a composition for forming a photoresist underlayer film, and provides a silicon-containing composition for forming a photoresist underlayer film, which can form a silicon-containing film that can form a low-roughness pattern in micro-patterning, and can be easily peeled off using a stripping solution that will not damage the necessary coating-type organic underlayer film and carbon-based CVD film in the semiconductor substrate and patterning steps. In particular, it exhibits solubility in alkaline solutions (basic solutions) and maintains peelability after dry etching. Prior Technology

[0002] In the manufacturing of semiconductor devices, photoresist lithography has been used for microfabrication. The aforementioned microfabrication is carried out as follows: a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer; an active light such as ultraviolet light is irradiated onto the film through a photomask pattern depicting a semiconductor element, and development is performed; the obtained photoresist pattern is used as a protective film to etch the substrate, thereby forming fine bumps and depressions on the substrate surface corresponding to the aforementioned pattern. In recent years, the increasing density of semiconductor devices has led to a trend towards shorter wavelengths of active light, shifting from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). With the shortening of active light wavelengths, the reflection of active light from the semiconductor substrate has become a major problem. Therefore, a method is now widely used that involves placing a bottom anti-reflective coating (BARC) between the photoresist and the substrate.

[0003] As the lower layer film between the semiconductor substrate and the photoresist, a film containing metallic elements such as silicon or titanium, known as a hard photomask, is currently used. In this case, the photoresist and the hard photomask differ greatly in their composition, so the removal speed by dry etching depends primarily on the type of gas used in the dry etching process. Furthermore, by appropriately selecting the type of gas, the hard photomask can be removed by dry etching without a significant reduction in the thickness of the photoresist film. As mentioned above, in recent semiconductor device manufacturing, to achieve various effects, primarily anti-reflection, a photoresist lower layer film is placed between the semiconductor substrate and the photoresist. While compositions for photoresist underlayers have been studied to date, the diverse range of required properties necessitates the development of novel materials for photoresist underlayers. For example, a composition for forming a coating-type BPSG (borophosphorus glass) film containing a structure based on a specific silicic acid framework has been disclosed, with the aim of forming a wet-etchable film (Patent Document 1); and a composition for forming a silicon-containing photoresist underlayer containing a carbonyl structure has been disclosed, with the aim of removing photomask residues after photolithography using a chemical solution (Patent Document 2). [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2016-74774 [Patent Document 2] International Publication No. 2018 / 181989 Summary of the Invention

[0005] [The technical problem that the invention aims to solve]

[0006] In the most advanced semiconductor devices, as the implanted layers become smaller, multilayer processes are often used. Typically, in multilayer processes, the aforementioned dry etching is used to transfer the lower layer, and finally, dry etching or ashing is used to process the substrate or remove the residue of the photomask after substrate processing, such as the removal of the lower layer film containing photoresist film or photoresist lower layer film.

[0007] The present invention is made in view of the above-mentioned circumstances, and its object is to provide a silicon-containing composition for forming a photoresist underlayer film, which is used to form a photoresist underlayer film that can be peeled off in semiconductor substrate and other processing steps not only by conventional dry etching methods, but also by wet etching methods using solutions such as dilute hydrofluoric acid, buffered hydrofluoric acid, and alkaline solutions (basic solutions), and in particular exhibits excellent solubility in alkaline solutions (basic solutions); and to provide a silicon-containing composition for forming a photoresist underlayer film that is used to form a photoresist underlayer film with excellent preservation stability and low residue in dry etching steps. [Technical means]

[0008] After repeated and in-depth research to solve the above-mentioned problems, the inventors discovered that: a film obtained from a composition containing a specific hydrolytic condensate (polysiloxane) derived from a hydrolyzable silane having a succinic acid liver skeleton or a hydrolyzable silane having a group derived from phosphonic acid exhibits excellent solubility in alkaline solutions (basic pharmaceutical solutions); furthermore, a film obtained from a composition containing a hydrolyzable condensate (polysiloxane) derived from a hydrolyzable silane exhibits excellent solubility in alkaline solutions (basic pharmaceutical solutions), wherein the hydrolyzable silane contains a specific additive (compound A) having a chemical structure containing a cation AX+ and an anion AZ-; thus, the present invention is completed.

[0009] That is, the present invention includes the following states. [1] A composition for forming a silicon-containing photoresist underlayer film, comprising a hydrolysis condensate containing a mixture of hydrolyzable silanes, wherein the hydrolyzable silane mixture contains at least one of a hydrolyzable silane represented by formula (1) and a hydrolyzable silane represented by formula (2); It is used to form a silicon-containing photoresist lower layer film that is soluble in basic pharmaceutical solutions; [Chemistry 1] (in formula (1),) R1 is a group bonded to silicon atoms, representing an organic group containing a succinic anhydride skeleton; R2 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organic group containing an epoxy group, acrylonitrile, methacrylonitrile, mercapto, amino group, acetamino group, alkoxy group, sulfonylurea group, or cyano group, or a combination thereof; R 3 represents a group or atom bonded to a silicon atom, which can independently represent an alkoxy, arylalkoxy, acetoxy, or halogen atom; a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. [Chemistry 2] (in formula (2),) R4 is a group bonded to silicon atoms, represented by the following formula (2-1) as a monovalent group. [Chemistry 3] (In equation (2-1),) R 201~R 202 independently represent hydrogen atoms and organogroups containing substituted alkyl groups; R 203 represents substituted alkyl groups; * represents bonds bonded to silicon atoms. R5 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organic group containing an epoxy group, acrylonitrile, methacrylonitrile, mercapto, amino group, acetamino group, alkoxy group, sulfonylurea group, or cyano group, or a combination thereof; R 6 represents a group or atom bonded to a silicon atom, which can independently represent an alkoxy, arylalkoxy, acetoxy, or halogen atom; a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. [2] The silicon-containing photoresist underlayer film forming composition as described in item [1], wherein the silicon-containing photoresist underlayer film forming composition further contains: a compound A having a chemical structure comprising a cation AX+ and an anion AZ- and the aforementioned anion having a molecular weight of 65 or more. [3] The composition for forming a silicon-containing photoresist underlayer film as described in item [2], wherein the aforementioned anion AZ- is an anion selected from at least one of the groups of anions represented by (A) to (E) below; [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] (In formulas (A) to (E), R 301 represents a substituted alkyl group, a substituted aryl group, a substituted haloalkyl group, a substituted aralkyl group, or an organogroup containing an ester bond (-C(=O)-O- or -OC(=O)-), or a combination thereof; Z represents an aromatic ring, a cyclic alkane, or a non-aromatic cyclic alkene; R 501 indicates an alkyl group that may be partially or wholly substituted with fluorine atoms; R 302 and R 303 independently represent alkyl groups; R 304 and R 305 represent alkyl groups independently. [4] The silicon-containing composition for forming a photoresist underlayer film as described in any of items [1] to [3], wherein the aforementioned hydrolyzable silane mixture further contains a hydrolyzable silane represented by the following formula (3); [Chemistry 10] (in formula (3),) R 7 is a group bonded to silicon atoms, representing an organogroup containing an alkenyl group; R8 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organic group containing an epoxy group, acrylonitrile, methacrylonitrile, mercapto, amino group, acetamino group, alkoxy group, sulfonylurea group, or cyano group, or a combination thereof; R 9 represents a group or atom bonded to a silicon atom, which can independently represent an alkoxy, arylalkoxy, acetoxy, or halogen atom; a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. [5] The composition for forming a silicon-containing photoresist underlayer film as described in item [4], wherein the aforementioned hydrolyzable silane mixture further contains a hydrolyzable silane represented by the following formula (4); [Chemistry 11] (in equation (4),) R 10 represents a group or atom bonded to a silicon atom, which can be independently represented as an alkoxy, arylalkoxy, acetoxy, or halogen atom. [6] A composition for forming a silicon-containing photoresist underlayer film, which is used to form a silicon-containing photoresist underlayer film soluble in a basic pharmaceutical solution. The composition for forming the silicon-containing photoresist lower layer film contains: compound A having a chemical structure comprising a cation AX+ and an anion AZ-, wherein the molecular weight of the aforementioned anion is 65 or more. [7] The composition for forming a silicon-containing photoresist underlayer film as described in item [6], wherein the aforementioned anion AZ- is an anion selected from at least one of the groups of anions represented by (A) to (E) below; [Chemistry 12] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] [Chemistry 17] (In formulas (A) to (E), R 301 represents a substituted alkyl group, a substituted aryl group, a substituted haloalkyl group, a substituted aralkyl group, or an organogroup containing an ester bond (-C(=O)-O- or -OC(=O)-), or a combination thereof; Z represents an aromatic ring, a cyclic alkane, or a non-aromatic cyclic alkene; R 501 indicates an alkyl group that may be partially or wholly substituted with fluorine atoms; R 302 and R 303 independently represent alkyl groups; R 304 and R 305 represent alkyl groups independently. [8] A silicon-containing photoresist underlayer film, which is a silicon-containing photoresist underlayer film formed using a composition for forming a photoresist underlayer film as described in any one of items [1] to [7]. [9] A pattern forming method, comprising: The step of forming an organic lower layer film on a semiconductor substrate; The step of coating the aforementioned organic lower layer film with the composition for forming a photoresist lower layer film as described in any one of items [1] to [7], and firing it to form a silicon-containing photoresist lower layer film; The step of coating a composition for forming a photoresist film onto the aforementioned silicon-containing photoresist lower layer film to form a photoresist film; The steps of exposing and developing the aforementioned photoresist film to obtain a photoresist pattern; The steps of applying the aforementioned photoresist pattern to a photomask and etching the aforementioned silicon-containing photoresist underlayer film; and The process involves using the patterned silicon-containing photoresist underlayer as a photomask and etching the aforementioned organic underlayer.

[10] The pattern forming method as described in item [9] further includes, after the aforementioned step of etching the organic underlayer film, a step of removing the silicon-containing photoresist underlayer film by a wet method using a chemical solution.

[11] The pattern forming method as described in item

[10] , wherein the aforementioned liquid is an alkaline liquid. [Effects of the Invention]

[0010] In this invention, by using a silane compound with a specific structure containing a succinic acid liver skeleton or a group derived from phosphonic acid as a component of the hydrolyzed condensate obtained from hydrolyzed silane as a component of the composition for forming the lower layer of photoresist, the film formed by this composition, even if it is a silicon-based film, can exhibit excellent solubility for basic drug solutions and can improve the removal performance by wet methods. Furthermore, in this invention, by using a specific additive (compound A) having a chemical structure containing cations AX+ and anions AZ- as a component of a composition for forming a photoresist lower layer film containing a hydrolytic condensate obtained using a silane compound, the film formed by this composition, even if it is a silicon-based film, can exhibit excellent solubility for basic pharmaceutical solutions and improve the removal performance by wet methods. Therefore, when using the composition for forming a photoresist underlayer film of the present invention to process patterns such as photoresist films or semiconductor substrates, in the case of removing residues from the photomask after processing, such as in the case of removing a lower layer film containing a photoresist film or a photoresist underlayer film, it is possible to easily remove the residues with a solution, and to manufacture semiconductor devices with minimal damage to the substrate. Furthermore, according to the present invention, when a film formed from a composition containing the above-mentioned hydrolytic condensate is subjected to dry etching, the removability of residues by etching can be improved. Implementation

[0011] The present invention will now be described in detail. Furthermore, the following description of the constituent elements is for illustrative purposes only and the present invention is not limited thereto.

[0012] [Composition for forming silicon-containing photoresist underlayer film] The present invention relates to a composition for forming a silicon-containing photoresist underlayer film that can be peeled off by a wet method, and particularly exhibits excellent solubility for basic pharmaceutical solutions. The composition for forming the photoresist lower layer film of the present invention is a hydrolytic condensate containing a mixture of hydrolyzable silanes. One characteristic of the composition for forming a photoresist underlayer film of the present invention is that it contains a product (hydrolysis condensate) obtained by hydrolyzing and condensing a mixture of hydrolyzable silanes containing a specific structure. This will be described in detail below in the section on (the silicon-containing composition for forming a photoresist underlayer film of the first state). Furthermore, one of the characteristics of the composition for forming the photoresist underlayer film of the present invention is that it contains a hydrolyzed condensate of a hydrolyzable silane mixture and a specific additive (compound A) having a chemical structure comprising a cation AX+ and an anion AZ-. This will be described in detail below in the section on (the silicon-containing composition for forming the photoresist underlayer film of the second state). The composition for forming the photoresist lower layer film of the present invention may contain, in addition to a hydrolyzed condensate of a hydrolyzable silane mixture and a specific additive (compound A), a solvent or other components described later.

[0013] In this invention, the hydrolysis condensate includes not only fully condensed organosiloxane polymers but also partially hydrolyzed organosiloxane polymers that have not fully condensed. These partially hydrolyzed condensates are similar to fully condensed condensates, both being polymers obtained through the hydrolysis and condensation of hydrolyzable silane compounds. However, some of them stop hydrolysis without further condensation, thus retaining Si-OH groups. Furthermore, the composition for forming the photoresist lower layer film of this invention, in addition to the hydrolysis condensate, may also contain uncondensed hydrolysates (fully hydrolyzed, partially hydrolyzed), and monomers (hydrolyzable silane compounds). Furthermore, in this specification, "hydrolyzable silane" is sometimes abbreviated as "silane compound".

[0014] (Composition for forming the silicon-containing photoresist underlayer film of the first state sample) The composition for forming the photoresist lower layer film of the present invention is a hydrolysis condensate containing a mixture of hydrolyzable silanes with a specific structure.

[0015] <Hydrolysis condensate of hydrolyzable silane mixtures> The hydrolyzable silane mixture contains hydrolyzable silane represented by formula (1) or hydrolyzable silane represented by formula (2), and may also contain hydrolyzable silane represented by formula (3), hydrolyzable silane represented by tetraalkoxysilane represented by formula (4), hydrolyzable silane represented by formula (5), and other hydrolyzable silanes as required.

[0016] <<Silane compounds represented by formula (1) (hydrolyzable silanes)>> The hydrolytic condensate used in the composition for forming the photoresist lower layer film of the present invention may be a product of the hydrolytic condensation of a mixture of hydrolyzable silanes containing a silane compound represented by the following formula (1).

[0017] [Chemistry 18]

[0018] R1 is a group bonded to silicon atoms, representing an organic group containing a succinic anhydride skeleton.

[0019] The organic group of R 1 mentioned above is not particularly limited as long as it contains the above-mentioned skeleton.

[0020] For example, an organic group containing a succinic anhydride skeleton includes not only the skeleton itself, but also organic groups in which one or more hydrogen atoms in an alkyl group are replaced by a succinic anhydride skeleton.

[0021] The alkyl groups substituted with the hydrogen atoms via the succinic anhydride skeleton are not particularly limited and can be any of the following: straight-chain, branched, or cyclic. The number of carbon atoms is usually 40 or less, for example, 30 or less, more for example, 20 or less, or 10 or less. Specific examples of the aforementioned straight-chain or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4- Methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these. Specific examples of the aforementioned cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl- Cycloalkyl groups such as cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc.; bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl, etc., but not limited to these.

[0022] The organic group of R1 mentioned above can be represented by, for example, a monovalent group represented by the following formula (1-1).

[0023] [Chemistry 19]

[0024] R 401 indicates, for example, an alkyl group derived from a linear, branched, or cyclic alkyl group by removing a hydrogen atom. * indicates a bond with a silicon atom.

[0025] In formula (1), R2 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted halogenated alkyl group, or a substituted alkoxyalkyl group, or an organic group containing an epoxy group, acrylonitrile, methacrylamide, mercapto, amino group, acetamino group, alkoxy group, sulfonylurea group, or cyano group, or a combination thereof.

[0026] In formula (1), R2 is an alkyl group, for example, an alkyl group having 1 to 10 carbon atoms in a straight or branched chain, such as: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl 3-Methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc. Alternatively, cyclic alkyl groups, such as those with 3 to 10 carbon atoms, can also be used, including: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl 1,3-Dimethyl-cyclobutyl, 2,2-Dimethyl-cyclobutyl, 2,3-Dimethyl-cyclobutyl, 2,4-Dimethyl-cyclobutyl, 3,3-Dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0027] In formula (1), R2 is a alkyl halide that has been substituted with a halogen atom. The halogen atoms mentioned above can include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. In addition, specific examples of alkyl groups can be given as the same examples as above. While there is no particular limitation on the number of carbon atoms in alkyl halides, it is ideally less than 40, more ideally less than 30, even more ideally less than 20, and even more ideally less than 10. Specific examples of alkyl halides include: monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropyl-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, etc., but are not limited to these.

[0028] In formula (1), R2 is an alkoxyalkyl group, which refers to an alkyl group that has been substituted with an alkoxy group. Specific examples of alkyl groups can be given as the examples above. Specific examples of alkoxy groups include alkoxy groups with straight-chain, branched, or cyclic alkyl moieties having 1 to 20 carbon atoms. Examples of straight-chain or branched alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, tertiary butoxy, n-pentoxy, 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-hexoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3- ...methyl-n-propoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-pentoxy, 1-methyl-n-propoxy, 1-methyl-n-pentoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-pentoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-pentoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-pentoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1-methyl-n-propoxy, 1 Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc. In addition, cyclic alkoxy groups include, for example: cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentoxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentoxy, 2-methyl-cyclopentoxy, 3-methyl-cyclopentoxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3-di... Methyl-cyclobutoxy, 2,2-dimethyl-cyclobutoxy, 2,3-dimethyl-cyclobutoxy, 2,4-dimethyl-cyclobutoxy, 3,3-dimethyl-cyclobutoxy, 1-n-propyl-cyclopropoxy, 2-n-propyl-cyclopropoxy, 1-isopropyl-cyclopropoxy, 2-isopropyl-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 1,2,3-trimethyl-cyclopropoxy, 2,2,3-trimethyl-cyclopropoxy, 1-ethyl-2-methyl-cyclopropoxy, 2-ethyl-1-methyl-cyclopropoxy, 2-ethyl-2-methyl-cyclopropoxy, and 2-ethyl-3-methyl-cyclopropoxy, etc. While there is no particular limitation on the number of carbon atoms in alkoxyalkyl groups, the ideal number is 40 or less, more ideally 30 or less, even more ideally 20 or less, and even more ideally 10 or less. Specific examples of alkoxyalkyl groups include, but are not limited to, methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, ethoxymethyl, and other lower alkoxyalkyl groups.

[0029] Examples of substituents in the aforementioned alkyl, halogenated alkyl, or alkoxyalkyl groups include: alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxy, arylalkoxy, etc. Specific examples of alkyl, halogenated alkyl, alkoxyalkyl, and alkoxy groups, and their ideal carbon number, can be given as examples as described above.

[0030] The aryl groups listed in the above substituents may include, for example: phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-mercaptophenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, and 9-phenanthyl, etc., but are not limited to these.

[0031] The aralkyl groups listed in the above substituents may include, for example, phenylmethyl (benzyl), 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, 10-phenyl-n-decyl, etc., but are not limited to these.

[0032] The halogenated aryl groups listed above are aryl groups substituted with halogen atoms. Specific examples of such aryl groups can be given as described above. Halogen atoms can include fluorine, chlorine, bromine, iodine, etc. While there is no particular limitation on the number of carbon atoms in aryl halogenated compounds, the ideal number is below 40, more ideally below 30, and even more ideally below 20. Specific examples of halogenated aryl groups include: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl. Fluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-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, heptafluoro-2-naphthyl, etc., but not limited to these.

[0033] The aralkyl halides listed above are aralkyl halides substituted with halogen atoms. Specific examples of such aralkyl halides and halogen atoms can be given as above. While there is no particular limitation on the number of carbon atoms in aralkyl halides, it is ideally less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of aralkyl halides include: 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, etc., but are not limited to these.

[0034] The aryloxy groups listed in the above substituents are groups in which the aryl group is bonded via an oxygen atom (-O-). Specific examples of such aryl groups can be given as the examples described above. Although there is no particular limitation on the number of carbon atoms in the above aryloxy groups, it is ideally 40 or less, more ideally 30 or less, and even more ideally 20 or less; specific examples include phenoxy, naphth-2-yloxy, etc., but are not limited to these. Furthermore, when there are two or more substituents, the substituents can bond together to form a ring.

[0035] The alkoxyaryl groups listed above are aryl groups substituted with alkoxy groups. Specific examples of such alkoxy and aryl groups can be given in the same manner as those described above. While there is no particular limitation on the number of carbon atoms in an alkoxyaryl group, it is ideally below 40, more ideally below 30, and even more ideally below 20. Specific examples of alkoxyaryl groups include: 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-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, 7-methoxynaphth-1-yl, etc., but are not limited to these.

[0036] The alkoxyaryl groups listed above are aryl groups substituted with alkoxy groups. Specific examples of such alkoxy groups and aryl groups can be given as above. While there is no particular limitation on the number of carbon atoms in alkoxyaryl groups, it is ideally less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of alkoxyaryl groups include 3-(methoxyphenyl)benzyl, 4-(methoxyphenyl)benzyl, etc., but are not limited to these.

[0037] The alkenyl groups listed above as substituents can include substituted alkenyl groups, such as those with 2 to 10 carbon atoms. More specifically, examples include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-secondary butylvinyl, 1,3- Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Tributylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2-Methyl-3-cyclopentenyl Alkenes include 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl; cross-linked cyclic alkenyl groups such as dicycloheptenyl (norcamphenyl) can also be listed.

[0038] The arylalkoxy groups listed above are derived from the hydroxyl groups of aryl alkyl alcohols by removing a hydrogen atom. Specific examples of such aryl alkyl groups can be given as above. While there is no particular limitation on the number of carbon atoms in arylalkoxy groups, it is ideally less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of arylalkoxy groups include: benzyloxy, 2-phenylethyloxy, 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, 10-phenyl-n-decyloxy, etc., but are not limited to these.

[0039] The organic groups containing epoxy groups in R2 in the above formula (1) can be listed as: epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxypropoxybutyl, epoxycyclohexyl, etc., but are not limited to these. The organic groups containing acrylamide in R2 in the above formula (1) can be listed as: acrylamide methyl, acrylamide ethyl, acrylamide propyl, etc., but are not limited to these. The organic group containing methacrylic acid in R2 in the above formula (1) can be listed as: methacrylic acid methyl, methacrylic acid ethyl, methacrylic acid propyl, etc., but not limited to these. The organic groups containing thiol groups in R2 in the above formula (1) can be listed as: ethyl thiol, butyl thiol, hexyl thiol, octyl thiol, etc., but are not limited to these. The organic groups containing an amino group in formula (1) above can be listed as: amino group, aminomethyl group, aminoethyl group, dimethylaminoethyl group, dimethylaminopropyl group, etc., but not limited to these. In formula (1) above, R2 contains an alkoxy group, such as methoxymethyl and methoxyethyl, but is not limited to these. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded. The organic groups containing sulfonyl groups in R2 of the above formula (1) can be listed as sulfonylalkyl groups and sulfonylaryl groups, but are not limited to these. The organic groups containing cyano groups in R2 in the above formula (1) can be listed as cyanoethyl, cyanopropyl, etc., but are not limited to these.

[0040] In formula (1), R3 is a group or atom bonded to a silicon atom, and each group independently represents an alkoxy, arylalkoxy, acetoxy, or halogen atom. Examples of the above-mentioned alkoxy and halogen atoms can be given as above.

[0041] Arylalkoxy groups are derived from aryl alkyl alcohols by removing a hydrogen atom from the hydroxyl group. Specific examples of such aryl alkyl groups can be given as the examples above. While there is no particular limitation on the number of carbon atoms in arylalkoxy groups, it is ideally less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of arylalkoxy groups include: benzyloxy, 2-phenylethyloxy, 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, 10-phenyl-n-decyloxy, etc., but are not limited to these.

[0042] A hydroxyl group is a group derived by removing a hydrogen atom from the carboxylic acid group of a carboxylic acid compound. Typical examples include alkyl carbonyloxy, aryl carbonyloxy, or aralkyl carbonyloxy derived by removing a hydrogen atom from the carboxylic acid group of an alkyl carboxylic acid, aryl carboxylic acid, or aralkyl carboxylic acid, but not limited to these. Specific examples of alkyl, aryl, and aralkyl groups in such alkyl carboxylic acids, aryl carboxylic acids, and aralkyl carboxylic acids can be given by examples similar to those described above. Specific examples of aceoxy groups include those with 2 to 20 carbon atoms. Examples include: methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, secondary butyl carbonyloxy, tertiary butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl-n-butyl carbonyloxy, 2-methyl-n-butyl carbonyloxy, 3-methyl-n-butyl carbonyloxy, 1,1-dimethyl-n-propyl carbonyloxy, 1,2-dimethyl-n-propyl carbonyloxy, 2,2-dimethyl-n-propyl carbonyloxy, 1-ethyl-n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-pentyl carbonyloxy, 4-methyl-n-... Pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and toluenesulfonylcarbonyloxy, etc., but not limited to these.

[0043] In the above formula (1), a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. b ideally represents 0 or 1, and even more ideally 0.

[0044] Specific examples of compounds represented by the above formula (1) include, for example, silane compounds containing a succinic acid skeleton such as [(3-trimethoxysilyl)propyl]succinic anhydride, [(3-triethoxysilyl)propyl]succinic anhydride, [(3-trimethoxysilyl)ethyl]succinic anhydride, and [(3-trimethoxysilyl)butyl]succinic anhydride.

[0045] <<Silane compounds represented by formula (2) (hydrolyzable silanes)>> The hydrolytic condensate used in the composition for forming the photoresist lower layer film of the present invention may be a product of the hydrolytic condensation of a mixture of hydrolyzable silanes containing a silane compound represented by the following formula (2).

[0046] [Chemistry 20]

[0047] R4 is a group bonded to silicon atoms, represented by the following formula (2-1) as a monovalent group.

[0048] [Chemistry 21]

[0049] In formula (2-1), R 201~R 202 independently represent hydrogen atoms and organic groups containing substituted alkyl groups, R 203 represents substituted alkyl groups, and * represents bonds bonded to silicon atoms.

[0050] In formula (2), the substituted alkyl group in the monovalent group represented by formula (2-1) of R 4 is the same as the substituted alkyl group described by R 2 in formula (1) above. Organic groups containing substituted alkyl groups, such as substituted alkyl groups, can be listed as examples.

[0051] In formula (2), R4, represented by formula (2-1), is a divalent group derived by further removing a hydrogen atom from the aforementioned substituted alkyl group. It can be any of the following: linear, branched, or cyclic. Specific examples of alkyl groups include: linear alkyl groups such as methylene, ethyl alkyl group, trimethylene, methyl ethyl alkyl group, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkyl groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethyl alkyl group, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkyl groups such as 1,2-cyclopropyldiyl, 1,2-cyclobutyldiyl, 1,3-cyclobutyldiyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; and those containing -CH₂OCH₂-. -CH 2CH 2OCH 2-, -CH 2CH 2OCH 2CH 2-, -CH 2CH 2CH 2OCH 2CH 2-, -CH 2CH 2OCH 2CH 2CH 2-, -CH 2CH 2CH 2OCH 2CH 2CH 2-, -CH 2SCH 2-, -CH 2CH 2SCH 2-, -CH 2CH 2SCH 2CH 2-, -CH 2CH 2CH 2SCH 2CH 2-, -CH 2CH 2SCH 2CH 2CH 2-, -CH 2CH 2CH 2SCH 2CH 2CH 2-, -CH 2OCH 2CH 2SCH 2- and other ether groups, etc., but not limited to these.

[0052] In equation (2), R5 is the same as R2 in equation (1) above.

[0053] In equation (2), R6 is the same as R3 in equation (1) above.

[0054] In the above formula (2), a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. b ideally represents 0 or 1, and even more ideally 0.

[0055] Specific examples of compounds represented by the above formula (2) include, for example, diethyl phosphonate [(3-triethoxysilyl)ethyl]phosphonate and other silane compounds containing alkylphosphonic acids.

[0056] <<Silane compounds represented by formula (3) (hydrolyzable silanes)>> The hydrolytic condensate used in the composition for forming the photoresist lower layer film of the present invention may further contain a hydrolytic silane represented by the following formula (3).

[0057] [Chemistry 22]

[0058] R 7 is a group bonded to silicon atoms, representing an organic group containing an alkenyl group.

[0059] The organic group of R 7 mentioned above is not particularly limited as long as it contains the above-mentioned group.

[0060] For example, an alkenyl-containing organic group not only includes the alkenyl itself, but also includes organic groups in which one or more hydrogen atoms in an alkyl group are replaced by an alkenyl group.

[0061] Furthermore, the alkenyl group in R 7 above, as described in R 2 of formula (1) above, can be substituted alkenyl groups, for example, alkenyl groups with 2 to 10 carbon atoms. More specifically, examples include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl Alkenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-secondary butylvinyl, 1,3- Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Tributylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2-Methyl-3-cyclopentenyl Alkenes include 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl; cross-linked cyclic alkenyl groups such as dicycloheptenyl (norcamphenyl) can also be listed. Of the above, R7 ideally contains a vinyl group.

[0062] In equation (3), R 8 is the same as R 2 in equation (1) above.

[0063] In equation (3), R9 is the same as R3 in equation (1) above.

[0064] In the above formula (3), a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. b ideally represents 0 or 1, and even more ideally 0.

[0065] Specific examples of compounds represented by the above formula (3) include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylethoxysilane, dimethylvinylethoxysilane, dimethylvinylethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane Allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiethoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethyl Silane compounds containing alkenyl (vinyl) groups, such as chlorosilane, allyl dimethyl ethoxysilane, diallyl dimethoxysilane, diallyl diethoxysilane, diallyl dichlorosilane, diallyl diethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, and p-styryltrimethoxysilane.

[0066] <<Silane compounds represented by formula (4) (hydrolyzable silanes)>> The hydrolytic condensate used in the composition for forming the photoresist lower layer film of the present invention may further contain a hydrolyzable silane represented by the following formula (4).

[0067] [Chemistry 23]

[0068] R 10 represents a group or atom bonded to a silicon atom, which can be independently represented as an alkoxy, arylalkoxy, acetoxy, or halogen atom. Specific examples of alkoxy, arylalkoxy, and acetoxy groups can be given as examples as those described above.

[0069] Specific examples of hydrolyzable silanes represented by formula (4) include, for example: tetramethoxysilane, tetrachlorosilane, tetraethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane.

[0070] From the viewpoint of increasing the crosslinking density of the film obtained from the composition of the present invention, suppressing the diffusion of the photoresist film components into the obtained film, and maintaining and improving the photoresist properties of the photoresist film, it is ideal to use tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane represented by formula (4).

[0071] <<Silane compounds represented by formula (5) (hydrolyzable silanes)>> The hydrolytic condensate used in the composition for forming the photoresist lower layer film of the present invention may further contain a hydrolyzable silane represented by the following formula (5).

[0072] [Chemistry 24]

[0073] R 11 is a group bonded to a silicon atom, representing an organic group containing at least one of the groups selected from aryl, substituted amino, and groups represented by formula (5-2) described below.

[0074] The organic group of R 11 mentioned above is not particularly limited as long as it contains the above-mentioned group.

[0075] For example, an organogroup containing an aryl group and a group represented by formula (5-2) described below includes not only the group itself, but also organogroups in which one or more hydrogen atoms in an alkyl group are substituted by at least one group selected from the group consisting of an aryl group and a group represented by formula (5-2) described below. Furthermore, among the substituents in the substituted amino groups specified in R 11, alkyl groups are ideally listed. In particular, substitution with alkyl groups having 1 to 4 carbon atoms is ideal.

[0076] The aryl group in R 11 above can be substituted aryl groups, for example, aryl groups with 6 to 20 carbon atoms. More specifically, as described in R 2 of formula (1) above, aryl groups can include: phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-mercaptophenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl and 9-phenanthyl, etc.

[0077] In addition, groups containing the above-mentioned aryl groups can be listed as: substituted aryl groups, substituted halogenated aryl groups, substituted halogenated aryl groups, substituted alkoxyaryl groups, substituted alkoxyaryl groups, etc.

[0078] The above-mentioned aryl groups are alkyl groups that have been substituted with aryl groups. Specific examples of such aryl groups and alkyl groups can be given in the same way as those above. While there is no particular limitation on the number of carbon atoms in aralkyl groups, it is ideally less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of aralkyl groups, as described in the explanation of R2 in formula (1) above, include, for example: phenylmethyl (benzyl), 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, 10-phenyl-n-decyl, etc., but are not limited to these.

[0079] The aforementioned halogenated aryl groups are aryl groups substituted with halogen atoms. Specific examples of such aryl groups can be given in the same manner as those described above. The halogen atoms mentioned above can include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. While there is no particular limitation on the number of carbon atoms in aryl halogenated compounds, the ideal number is below 40, more ideally below 30, and even more ideally below 20. Specific examples of halogenated aryl groups, as described by R2 in formula (1) above, include: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl. The range includes, but is not limited to, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-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, heptafluoro-2-naphthyl, etc.

[0080] The aforementioned aralkyl halide is an aralkyl group substituted with a halogen atom. Specific examples of such aralkyl groups and halogen atoms can be given as the examples above. While there is no particular limitation on the number of carbon atoms in aralkyl halides, it is ideally less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of aralkyl halides, as described by R2 in formula (1) above, include: 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, etc., but are not limited to these.

[0081] The above-mentioned alkoxyaryl groups are aryl groups substituted with alkoxy groups. Specific examples of such aryl groups and alkoxy groups can be given as the examples above.

[0082] While there is no particular limitation on the number of carbon atoms in an alkoxyaryl group, it is ideally below 40, more ideally below 30, and even more ideally below 20. Specific examples of alkoxyaryl groups, as described in the explanation of R2 in formula (1) above, include: 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-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, 7-methoxynaphth-1-yl, etc., but are not limited to these.

[0083] The above-mentioned alkoxyaryl groups are aryl groups substituted with alkoxy groups. Specific examples of such alkoxy groups and aryl groups can be given as the examples above. While there is no particular limitation on the number of carbon atoms in alkoxyaryl groups, it is ideally less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of alkoxyaryl groups include 3-(methoxyphenyl)benzyl, 4-(methoxyphenyl)benzyl, etc., but are not limited to these.

[0084] Furthermore, examples of substituted amino groups in R 11 include, for example, amino groups, or alkylamino groups substituted with alkyl groups having 1 to 4 carbon atoms. More specifically, examples include, but are not limited to, amino groups, aminomethyl groups, aminoethyl groups, dimethylaminoethyl groups, dimethylaminopropyl groups, etc.

[0085] Furthermore, the group represented by the following formula (5-2) in R 11 above,

[0086] [Chemistry 25] Wherein, X 101 independently represents any one of the following formulas (5-3) to (5-5), and the carbon atom of the ketone group in formulas (5-4) and (5-5) is bonded to the nitrogen atom of R 102 in formula (5-2).

[0087] [Chemistry 26] In formulas (5-3) to (5-5), R 103 to R 107 independently represent hydrogen atoms, substituted alkyl groups, substituted alkenyl groups, or organic groups containing epoxy or sulfonyl groups. Specific examples of substituted alkyl groups and substituted alkenyl groups, as well as the ideal number of carbon atoms, can be listed as follows: examples of alkyl groups related to R 1 that are the same as those listed as alkyl groups substituted with hydrogen atoms via succinic anhydride skeletons, and examples of alkenyl groups that are the same as those mentioned above. In addition, organic groups containing epoxy groups include, but are not limited to, glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and glycidoxycyclohexyl. Organic groups containing sulfonyl groups include, but are not limited to, sulfonylalkyl and sulfonylaryl groups.

[0088] In the above formula (5-2), R 101 independently represents a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organic group containing an epoxy group or a sulfonylurea group; R 102 independently represents an alkyl group, a hydroxyalkyl group, a sulfur bond (-S-), an ether bond (-O-), or an ester bond (-C(=O)-O- or -OC(=O)-). Here, specific examples of substituted alkyl groups, substituted alkenyl groups, epoxy groups, or organogroups containing epoxy groups, and the ideal number of carbon atoms, can be given as the same examples as those related to R 103 to R 107. In addition, substituted alkyl groups are ideally alkyl groups in which the terminal hydrogen atom is replaced by a vinyl group, and specific examples include allyl, 2-vinylethyl, 3-vinylpropyl, 4-vinylbutyl, etc.

[0089] The aforementioned alkyl group is a divalent group derived by further removing one hydrogen atom from the aforementioned alkyl group, and can be any one of straight chain, branched chain, or cyclic chain; the number of carbon atoms in the alkyl group is not particularly limited, but ideally it is 40 or less, more ideally it is 30 or less, even more ideally it is 20 or less, and even more ideally it is 10 or less. In addition, the alkyl group of R102 may have one or more of the following at its end or in the middle, ideally in the middle: a sulfur bond, an ether bond, and an ester bond. Specific examples of alkyl groups include: linear alkyl groups such as methylene, ethyl alkyl group, trimethylene, methyl ethyl alkyl group, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkyl groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethyl alkyl group, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkyl groups such as 1,2-cyclopropyldiyl, 1,2-cyclobutyldiyl, 1,3-cyclobutyldiyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; and those containing -CH₂OCH₂-. -CH 2CH 2OCH 2-, -CH 2CH 2OCH 2CH 2-, -CH 2CH 2CH 2OCH 2CH 2-, -CH 2CH 2OCH 2CH 2CH 2-, -CH 2CH 2CH 2OCH 2CH 2CH 2-, -CH 2SCH 2-, -CH 2CH 2SCH 2-, -CH 2CH 2SCH 2CH 2-, -CH 2CH 2CH 2SCH 2CH 2-, -CH 2CH 2SCH 2CH 2CH 2-, -CH 2CH 2CH 2SCH 2CH 2CH 2-, -CH 2OCH 2CH 2SCH 2- and other ether groups, etc., but not limited to these.

[0090] A hydroxyl group is a group in which at least one hydrogen atom of the above-mentioned alkyl group is replaced by a hydroxyl group. Specific examples include: hydroxymethylene, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, 1-hydroxytrimethylene, 2-hydroxytrimethylene, 3-hydroxytrimethylene, 1-hydroxytetramethylene, 2-hydroxytetramethylene, 3-hydroxytetramethylene, 4-hydroxytetramethylene, 1,2-dihydroxytetramethylene, 1,3-dihydroxytetramethylene, 1,4-dihydroxytetramethylene, 2,3-dihydroxytetramethylene, 2,4-dihydroxytetramethylene, 4,4-dihydroxytetramethylene, etc., but not limited to these.

[0091] In the above, R 11 is ideally a group containing at least one group selected from the group consisting of phenyl, diaminopropyl, and isocyanuric acid skeleton (in formula (5-2), X 101 represents a group represented by formula (5-5)).

[0092] In equation (5), R12 is the same as R2 in equation (1) above.

[0093] In equation (5), R13 is the same as R3 in equation (1) above.

[0094] In the above formula (5), a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. b ideally represents 0 or 1, more ideally 0.

[0095] Specific examples of compounds represented by the above formula (5) include: phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane. Silane, Triphenylacetoxysilane, Triphenylchlorosilane, 3-Anilinepropyltrimethoxysilane, 3-Anilinepropyltriethoxysilane, Dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, Benzyltrimethoxysilane, Benzyltriethoxysilane, Benzylmethyldimethoxysilane, Benzylmethyldiethoxysilane, Benzyldimethylmethoxysilane Silanes containing phenyl groups include: benzyl dimethyl ethoxysilane, benzyl dimethyl chlorosilane, phenylethyl trimethoxysilane, phenylethyl triethoxysilane, phenylethyl trichlorosilane, phenylethyl triethoxysilane, phenylethyl methyl dimethoxysilane, phenylethyl methyl diethoxysilane, phenylethyl methyl dichlorosilane, and phenylethyl methyl diethoxysilane.Methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltrichlorosilane, methoxyphenylethyltrimethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltrichlorosilane Alkane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane Silane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltrichlorosilane, tri-butoxyphenyltrimethoxysilane, tri-butoxyphenyltriethoxysilane, tri-butoxyphenyltriethoxysilane, tri-butoxyphenyltrichlorosilane, tri-butoxybenzyltrimethoxysilane, tri-butoxybenzyltriethoxysilane, tri-butoxybenzyl Triacetoxysilane, tributoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, etc., silane compounds containing substituted aryl groups; dimethylaminopropyltrimethoxysilane, etc.

[0096] Furthermore, a specific example of a silane compound represented by the above formula (5) is a silane compound containing an organic group represented by the above formula (5-2). It can be a commercially available product or synthesized using the conventional methods described in International Publication No. 2011 / 102470, etc. Specific examples of silane compounds containing organic groups represented by the above formula (5-2) can be listed below, but are not limited to these.

[0097] [Chemistry 27]

[0098] [Chemistry 28]

[0099] [Chemistry 29]

[0100] Furthermore, silane compounds represented by the above formula (5) can also include aryl-containing silane compounds represented by formulas (A-1) to (A-41).

[0101] [Chemistry 30]

[0102] [Chemistry 31]

[0103] [Chemistry 32]

[0104] <<Other Silane Compounds (Hydrolyzable Silanes)>> In this invention, for the purpose of adjusting membrane properties such as membrane density, the above-mentioned hydrolyzable silane mixture may use silane compounds represented by the above formula (1) or (2), or, as needed, silane compounds represented by the above formula (3), (4) or (5), and other silane compounds represented by the following formula (6) (other hydrolyzable silanes).

[0105] [Chemistry 33] In formula (6), R14 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted halogenated alkyl group, or a substituted alkoxyalkyl group, or an organic group containing an epoxy group, acrylonitrile, methacrylamide, mercapto, acetamino, alkoxy, sulfonylurea, or cyano group, or a combination thereof. In addition, R 15 represents a group or atom bonded to a silicon atom, which can be independently represented as an alkoxy, arylalkoxy, acetoxy, or halogen atom. Furthermore, c represents an integer from 1 to 3.

[0106] Specific examples of each group in R 14 above, and their ideal number of carbon atoms, can be listed in relation to the above groups and number of carbon atoms related to R 2. Specific examples of each group in R 15 above, and their ideal number of carbon atoms, can be listed in relation to the above groups and atoms related to R 3, as well as the number of carbon atoms. Specific examples of hydrolyzable silanes represented by formula (6) include: methyltrimethoxysilane, methyltrichlorosilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltribenzyloxysilane, methyltriphenylethoxysilane, propylene oxide methyltrimethoxysilane, propylene oxide methyltriethoxysilane, α-propylene oxide ethyltrimethoxysilane, α-propylene oxide ethyltriethoxysilane, β-propylene oxide ethyltrimethoxysilane, β-propylene oxide ethyltriethoxysilane, α-propylene oxide propyltrimethoxysilane, α-propylene oxide propyltriethoxysilane, β-propylene oxide propyltrimeth ... γ-Oxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxypropyltriethoxysilane Propyleneoxybutyltrimethoxysilane, γ-epoxypropoxybutyltriethoxysilane, δ-epoxypropoxybutyltrimethoxysilane, δ-epoxypropoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β- (3,4-Epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-Epoxycyclohexyl)ethyltributoxysilane, γ-(3,4-Epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-Epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-Epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-Epoxycyclohexyl)butyltriethoxysilane, epoxypropoxymethylmethyldimethoxysilane, epoxypropoxymethylmethyldiethoxysilane, α-Epoxypropoxyethylmethyldimethoxysilane, α-Epoxypropoxyethylmethyldiethoxysilane, β-Epoxypropoxyethylmethyldimethoxysilane, β-Epoxypropoxyethyldimethoxysilane Ethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, bicyclo(2,2,1)heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonamidopropyltriethoxysilane Dimethyl dimethoxysilane, dimethyl diethoxysilane, γ-chloropropylmethyl dimethoxysilane, γ-chloropropylmethyl diethoxysilane, dimethyl diethoxysilane, γ-methacryloxypropylmethyl dimethoxysilane, γ-methacryloxypropylmethyl diethoxysilane, γ-mercaptopropylmethyl dimethoxysilane, γ-mercaptomethyl diethoxysilane, etc., but not limited to these.

[0107] In addition to the examples above, other silane compounds (hydrolyzable silanes) may also be contained in the hydrolyzable silane mixtures without impairing the effects of the present invention.

[0108] As described above, the composition for forming the photoresist lower layer film of the present invention contains a hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture. In one ideal embodiment of the present invention, the composition for forming the photoresist lower layer film of the present invention contains at least the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture. In one ideal embodiment of the present invention, the hydrolytic condensate containing the composition for forming the photoresist lower layer film of the present invention contains a hydrolytic condensate obtained using the following hydrolytic silanes: hydrolytic silanes other than those represented by formula (1) or formula (2), such as hydrolytic silanes represented by formula (3), hydrolytic silanes represented by formula (4), hydrolytic silanes represented by formula (5), hydrolytic silanes represented by formula (6), or other hydrolytic silanes not represented by these formulas.

[0109] In the case of using a silane compound represented by formula (1) in a hydrolyzable silane mixture, the amount of silane compound represented by formula (1) added is, for example, 0.1 to 30 mol, relative to the amount of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture added at 100 mol%. In the case of using a silane compound represented by formula (2) in a hydrolyzable silane mixture, the amount of silane compound represented by formula (2) added is, for example, 0.1 to 30 mol, relative to the amount of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture added in 100 mol%. In the case of using a silane compound represented by formula (3) in a hydrolyzable silane mixture, the amount of silane compound represented by formula (3) added is, for example, 15 to 50 mol, relative to the amount of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture added. In the case where a silane compound represented by formula (4) is used in a hydrolyzable silane mixture, the amount of silane compound represented by formula (4) added relative to 100 mol% of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture may be, for example, 30 to 70 mol%, or 25 to 45 mol. In the case where a silane compound represented by formula (5) is used in a hydrolyzable silane mixture (for example, when a silane compound in formula (5) is used where R 11 is aryl), the amount of silane compound represented by formula (5) added relative to 100 mol% of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture can be, for example, 0.01 to 5 mol.

[0110] The weight-average molecular weight of the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture can be, for example, 500 to 1,000,000. From the viewpoint of inhibiting the precipitation of hydrolyzed condensates in the composition, the weight-average molecular weight is ideally 500,000 or less, more ideally 250,000 or less, and even more ideally 100,000 or less; from the viewpoint of balancing storage stability and coatability, it is ideally 700 or more, and even more ideally 1,000 or more. Furthermore, the weight-average molecular weight is the molecular weight converted from polystyrene by GPC analysis. GPC analysis can be performed as follows, for example, using 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 Corporation), setting the column temperature to 40°C, using tetrahydrofuran as the dissolution solution, setting the flow rate to 1.0 mL / min, and using polystyrene (manufactured by Showa Denko Corporation) as the standard sample.

[0111] The hydrolysis condensate of the above-mentioned hydrolyzable silane mixture can be obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane). The aforementioned silane compounds (hydrolyzable silanes) contain alkoxy, arylalkoxy, acetoxy, and halogen atoms that are directly bonded to silicon atoms, that is, they contain alkoxysilyl, arylalkoxysilyl, acetoxysilyl, and halogenated silicon groups as hydrolyzing groups. In the hydrolysis of these hydrolyzable groups, the amount of water used per 1 mol of hydrolyzable group is typically 0.5 to 100 mol, ideally 1 to 10 mol. Hydrolysis and condensation can be carried out with or without a hydrolysis catalyst, either to promote the reaction. When a hydrolysis catalyst is used, the amount of hydrolysis catalyst that can be used per 1 mole of hydrolyzable group is typically 0.0001 to 10 moles, ideally 0.001 to 1 mole. The reaction temperature for hydrolysis and condensation is usually above room temperature and below the reflux temperature of the organic solvent that can be used for hydrolysis at normal pressure. For example, it can be 20~110℃, or 20~80℃. Hydrolysis can be complete, meaning all hydrolyzable groups are converted into silanol groups, or it can be partial, meaning unreacted hydrolyzable groups remain. Hydrolysis catalysts that can be used during hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0112] Examples of metal chelating compounds that serve as hydrolysis catalysts include: triethoxymono(acetylene)titanium, tri-n-propoxymono(acetylene)titanium, triisopropoxymono(acetylene)titanium, tri-n-butoxymono(acetylene)titanium, tri-dibutoxymono(acetylene)titanium, tri-tertoxymono(acetylene)titanium, diethoxybis(acetylene)titanium, di-n-propoxybis(acetylene)titanium, diisopropoxybis(acetylene)titanium, and di-n-butoxybis(acetylene)titanium. Di-dibutoxy-bis(acetophenone)titanium, Di-tert-butoxy-bis(acetophenone)titanium, Monoethoxy-tris(acetophenone)titanium, Mono-n-propoxy-tris(acetophenone)titanium, Mono-isopropoxy-tris(acetophenone)titanium, Mono-n-butoxy-tris(acetophenone)titanium, Mono-dibutoxy-tris(acetophenone)titanium, Mono-tert-butoxy-tris(acetophenone)titanium, Tetra(acetophenone)titanium, Triethoxy-mono(acetyl ethyl ester)titanium, Tri-n-propoxy-mono(acetyl ethyl ester)titanium, Triisopropoxy- Mono(ethyl acetate) titanium, tri-n-butoxy-mono(ethyl acetate) titanium, tri-di-butoxy-mono(ethyl acetate) titanium, tri-tertiary-butoxy-mono(ethyl acetate) titanium, diethoxy-bis(ethyl acetate) titanium, di-n-propoxy-bis(ethyl acetate) titanium, diisopropoxy-bis(ethyl acetate) titanium, di-n-butoxy-bis(ethyl acetate) titanium, di-di-di-butoxy-bis(ethyl acetate) titanium, di-di-di-butoxy-bis(ethyl acetate) titanium, di-tertiary-butoxy-bis(ethyl acetate) titanium, monoethoxy Titanium chelate compounds include: · Titanium trioxide (ethyl acetate) , ...Triethoxymono(acetylene)zirconium, Tri-n-propoxymono(acetylene)zirconium, Triisopropoxymono(acetylene)zirconium, Tri-n-butoxymono(acetylene)zirconium, Tri-dibutoxymono(acetylene)zirconium, Tri-tertoxymono(acetylene)zirconium, Diethoxybis(acetylene)zirconium, Di-n-propoxybis(acetylene)zirconium, Diisopropoxybis(acetylene)zirconium, Di-n-butoxybis(acetylene)zirconium, Di-di-dibutoxybis(acetylene)zirconium, Di-tertoxybis(acetylene)zirconium, Di-tertoxybis(acetylene)zirconium Zirconium (acetyl acetone), monoethoxy-tris(acetyl acetone) zirconium, mono-n-propoxy-tris(acetyl acetone) zirconium, monoisopropoxy-tris(acetyl acetone) zirconium, mono-n-butoxy-tris(acetyl acetone) zirconium, mono-dibutoxy-tris(acetyl acetone) zirconium, mono-tertoxy-tris(acetyl acetone) zirconium, zirconium tetra(acetyl acetone) zirconium, triethoxy-mono(acetyl ethyl ester) zirconium, tri-n-propoxy-mono(acetyl ethyl ester) zirconium, triisopropoxy-mono(acetyl ethyl ester) zirconium, tri-n-butoxy-mono(acetyl ethyl ester) zirconium, Tri-dibutoxy-mono(ethyl acetate)zirconium, Tri-tertoxy-mono(ethyl acetate)zirconium, Diethoxy-bis(ethyl acetate)zirconium, Di-n-propoxy-bis(ethyl acetate)zirconium, Diisopropoxy-bis(ethyl acetate)zirconium, Di-n-butoxy-bis(ethyl acetate)zirconium, Di-di-dibutoxy-bis(ethyl acetate)zirconium, Di-tertoxy-bis(ethyl acetate)zirconium, Monoethoxy-tris(ethyl acetate)zirconium, Mono-n-propoxy-tris(ethyl acetate)zirconium, Monoiso ... Zirconium chelates include propoxy-triethyl(ethyl acetate)zirconium, mono-n-butoxy-triethyl(ethyl acetate)zirconium, mono-di-butoxy-triethyl(ethyl acetate)zirconium, mono-tertoxy-triethyl(ethyl acetate)zirconium, tetra(ethyl acetate)zirconium, mono(ethyl acetone)triethyl(ethyl acetate)zirconium, bis(ethyl acetone)bis(ethyl acetate)zirconium, triethyl(ethyl acetone)mono(ethyl acetate)zirconium, etc.; aluminum chelates include triethyl(ethyl acetone)aluminum, triethyl(ethyl acetate)aluminum, etc., but are not limited to these.

[0113] Organic acids that can serve as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric 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, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linolenic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc.

[0114] Inorganic acids that can act as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0115] Organic bases that can serve as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, methylpyridine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, etc. Inorganic bases that can serve as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0116] Ideally, these catalysts are metal chelates, organic acids, or inorganic acids. One of these can be used alone, or two or more can be used in combination.

[0117] In this invention, nitric acid can be appropriately used as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, especially the molecular weight change of the hydrolyzed condensate can be suppressed. It is known that the stability of the hydrolyzed condensate in a liquid depends on the pH of the solution. Further research has shown that by using an appropriate amount of nitric acid, the pH of the solution can be kept within a stable range.

[0118] Organic solvents can also be used as solvents during hydrolysis and condensation. Specific examples include: aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentanenaphthalene; and methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isopentanol, 2-methylbutanol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, and 2-methylpentanol. Monool solvents such as hexanol, 2-ethylbutanol, n-heptanol, heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, 2-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, undecyl alcohol, trimethylnonanol, tetradecyl alcohol, heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, etc.; polyol solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, etc. Alcohol solvents; acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2,4-pentanedione, acetone-based acetone, diacetone alcohol, acetophenone, ketone, etc.; ketone solvents; diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxolane, 4-methyldioxolane, dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, etc. Ether solvents including diethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, 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, 2-methyltetrahydrofuran, etc.Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, butyl acetate 2, n-pentyl acetate, pentyl acetate 2, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate Ester solvents such as acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl 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-methylpropionic acid, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfide, cyclobutanesulfonate, and 1,3-propanesulfonyl lactone, etc., but not limited to these. These solvents may be used alone or in combination of two or more.

[0119] After the hydrolysis and condensation reactions are completed, the reaction solution can be neutralized by directly or by diluting or concentrating it, and then treated with an ion exchange resin to remove the hydrolysis catalysts such as acids or bases used in the hydrolysis and condensation. In addition, byproducts such as alcohols and water, as well as the hydrolysis catalysts used, can be removed from the reaction solution before or after such treatment by means such as vacuum distillation.

[0120] The resulting hydrolytic condensate (hereinafter also referred to as polysiloxane) is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and can be directly used as a component for forming the photoresist lower layer film as described later. The obtained polysiloxane varnish can be solvent-substituted, and can also be diluted with a suitable solvent. Furthermore, the obtained polysiloxane varnish, provided its storage stability is not poor, can also have the organic solvent removed by distillation to achieve a solids concentration of 100%. The organic solvent used for solvent substitution and dilution of the aforementioned polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reactions of hydrolyzable silane mixtures. There are no particular limitations on the diluent; one or more solvents may be used arbitrarily.

[0121] The composition for forming the photoresist lower layer film of the present invention, in addition to the hydrolysis condensate (polysiloxane) of the above-mentioned hydrolyzable silane mixture, may also contain a solvent, a specific additive (compound A) having a chemical structure containing cations AX+ and anions AZ-, and other components.

[0122] Solvent The solvent used in the composition for forming the photoresist underlayer film of the present invention can be used without restriction, as long as it is a solvent that can dissolve the solid components in the composition for forming the photoresist underlayer film. There are no particular limitations on the solvent, as long as it can dissolve the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture, the specific additive (compound A), and other components.

[0123] Specific examples include: methyl cellulose acetate, ethyl cellulose acetate, propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, propylene glycol monobutyl ether, 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, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, 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, pentyl 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, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyethyl, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl, ethyl ethoxyethyl, methyl 3-methoxypropionate, 3- Ethyl 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, γ-butyrolactone, etc.; one solvent may be used alone or two or more solvents may be used in combination.

[0124] Furthermore, the composition for forming the photoresist lower layer film of the present invention may also contain water as a solvent. When water is contained as a solvent, its content relative to the total mass of the solvent contained in the composition may, for example, be 30% by mass or less, ideally 20% by mass or less, and more ideally 15% by mass or less.

[0125] <Specific additive (compound A)> By further containing a specific additive (compound A) having a chemical structure containing cations AX+ and anions AZ- in the composition for forming a photoresist lower layer film containing the hydrolyzed silane mixture (polysiloxane) described above, a photoresist lower layer film exhibiting superior solubility in alkaline solutions (basic pharmaceutical solutions) can be formed.

[0126] The specific additive (compound A) refers to a compound having a chemical structure containing a cation AX+ and an anion AZ-, and the molecular weight of the anion is 65 or more.

[0127] In a specific additive (compound A), "cation" refers to an atom or group of atoms with a positive charge; "anion" refers to an atom or group of atoms with a negative charge.

[0128] By including a specific additive (compound A) in the composition for forming the photoresist lower layer film, the solubility of the photoresist lower layer film in alkaline solutions (basic drug solutions) is increased. The reason is speculated to be as follows: the anions of the specific additive (compound A) exist between the hydrolysis condensates (polymers), thereby inhibiting the cross-linking bonds of the hydrolysis condensates, or the anions themselves bond and cap, so three-dimensional cross-linking does not occur.

[0129] From the viewpoint of inhibiting condensation, the molecular weight of the anionic AZ- is ideally above 65. Furthermore, from the viewpoint of maintaining dry etching resistance, it is ideally below 500.

[0130] <<Anion AZ ->> In compound A, the anion AZ- can exist either outside or inside the cation AX+. "The anion AZ - existing outside the molecule of the cation AX +" refers to the state in which the anion AZ - does not bind to the cation AX + via covalent bonds, but exists as a structural unit independent of the cation AX +. Examples of this state include the form of compound A mentioned above, such as salts. Hereinafter, anions existing outside the molecule of cations will also be referred to as relative anions. Furthermore, in compound A, the anion AZ- can also be covalently bonded to the cation AX+. That is, compound A can also be in the form of an intramolecular salt (also known as a zwitterion).

[0131] There are no particular restrictions on the types of anions AZ-, as long as they meet the above-mentioned condition that the molecular weight of the anion is 65 or above. Examples of anions with chemical structures represented by (A) to (E) below can be listed.

[0132] [Chemistry 34]

[0133] [Chemistry 35]

[0134] [Chemistry 36]

[0135] [Chemistry 37]

[0136] [Chemistry 38]

[0137] [Chemistry 39]

[0138] In formulas (A) to (E), R 301 represents a substituted alkyl group, a substituted aryl group, a substituted haloalkyl group, a substituted aralkyl group, or an organogroup containing an ester bond (-C(=O)-O- or -OC(=O)-), or a combination thereof; Z represents an aromatic ring, a cyclic alkane, or a non-aromatic cyclic alkene; R 501 indicates an alkyl group that may be partially or wholly substituted with fluorine atoms; R 302 and R 303 independently represent alkyl groups; R 304 and R 305 represent alkyl groups independently of each other. Specific examples of the alkyl, aryl, haloalkyl, and aralkyl groups mentioned above can be given as examples as described above. Specific examples of substituents that can replace the aforementioned alkyl groups can also be given as examples as described above.

[0139] Specific additives (compound A) can be exemplified by compounds having sulfonic acid anions represented by the above formula (A). Compounds having a sulfonic acid anion represented by formula (A) above include not only compounds having an anion represented by formula (A) outside the molecule, but also compounds having an anion represented by formula (A) inside the molecule of sulfobetaines such as lauryl sulfobetaine or myristyl sulfobetaine (see compounds (Add-6) and (Add-7) below).

[0140] Specific additives (compound A) may include, for example, compounds having anions containing a triazole skeleton represented by formula (B-1) or formula (B-2) above. In formula (B-2), Z represents an aromatic ring, cyclic alkane, or non-aromatic cyclic alkene with 1 to 6 carbon atoms. Ideally, a particular additive (compound A) is a compound having an anion represented by formula (B-2), where Z in formula (B-2) is ideally an aromatic ring. That is, an ideal embodiment of a particular additive (compound A) can be exemplified by compounds having an anion containing a benzotriazole skeleton represented by (b-1) below.

[0141] [Chemistry 40]

[0142] A specific additive (compound A) can be exemplified by compounds represented by the above formula (C). In formula (C), R 501 represents an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having some or all of the alkyl group substituted with fluorine atoms, or a perfluoroalkyl group. R 501 is ideally CF 3-based or C 4F 9-based. In particular, a specific additive (compound A) is more preferably a compound having, for example, an anion of a bis(trifluoromethanesulfonyl)imine represented as shown in (c-1).

[0143] [Chemistry 41]

[0144] Specific additives (compound A) can be exemplified by compounds having a thiophosphate anion represented by the above formula (D).

[0145] Specific additives (compound A) can be exemplified by compounds having a phosphate anion represented by the above formula (E).

[0146] Specific examples of a particular additive (compound A) may be listed as compounds represented by the following formulas (Add-1) to (Add-11), but are not limited to these.

[0147] [Chemistry 42] ･･･(Add-1)

[0148] [Chemistry 43] ･･･(Add-2)

[0149] [Chemistry 44] ･･･(Add-3)

[0150] [Chemistry 45] ･･･(Add-4)

[0151] [Chemistry 46] ･･･(Add-5)

[0152] [Chemistry 47] ･･･(Add-6)

[0153] [Chemistry 48] ･･･(Add-7)

[0154] [Chemistry 49] ･･･(Add-8)

[0155] [Chem. 50] ･･･(Add-9)

[0156] [Chemistry 51] ･･･(Add-10)

[0157] [Chemistry 52] ･･･(Add-11)

[0158] When the composition for forming the photoresist underlayer film of the present invention contains specific additives, the content of the additives can be 1 to 30 parts by mass relative to 100 parts by mass of the composition for forming the photoresist underlayer film.

[0159] <Other Ingredients (Other Additives)> In the composition for forming the photoresist lower layer film of the present invention, various additives (also referred to as other additives) other than the specific additives mentioned above can be added depending on the purpose of the composition. Other components (additives) that can be used in the composition for forming the photoresist underlayer film include, for example, the following conventional additives used in the materials (compositions) for forming various films that can be used in the manufacture of semiconductor devices, such as photoresist underlayer films, antireflective films, and pattern reversal films: curing catalysts (ammonium salts, phosphine salts, phosphonium salts, sulfur salts, nitrogen-containing silane compounds, etc.), crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymer compounds, acid generating agents, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon surfactants, fluorine surfactants, UV-curing surfactants, etc.), pH adjusters, rheology modifiers, adhesion aids, etc. Furthermore, although various additives are listed below, they are not limited to these.

[0160] Hardening Catalyst The aforementioned hardening catalyst can use ammonium salts, phosphine salts, phosphonium salts, strontium salts, etc. Furthermore, the following salts described as an example of a hardening catalyst can be added in the form of salts, or can be any of the following substances that form salts in the aforementioned components (substances added in the form of another compound and forming salts within the system).

[0161] The above-mentioned ammonium salts can be listed as follows: Quaternary ammonium salts having a structure represented by formula (D-1):

[0162] [Chemistry 53] (In the formula, m represents an integer from 2 to 11, n represents an integer from 2 to 3, R21 represents alkyl or aryl, and Y- represents an anion); Quaternary ammonium salts having a structure represented by formula (D-2):

[0163] [Chemistry 54] (In the formula, R22, R23, R24 and R25 represent alkyl or aryl groups, N represents a nitrogen atom, and Y- represents an anion; and R22, R23, R24 and R25 are bonded to the nitrogen atom via CN bonds, respectively); Quaternary ammonium salts having a structure represented by formula (D-3):

[0164] [Chemistry 55] (In the formula, R26 and R27 represent alkyl or aryl groups, N represents a nitrogen atom, and Y- represents an anion); Quaternary ammonium salts having a structure represented by formula (D-4):

[0165] [Chemistry 56] (In the formula, R28 represents alkyl or aryl, N represents nitrogen atom, and Y- represents anion); Quaternary ammonium salts having a structure represented by formula (D-5):

[0166] [Chemistry 57] (In the formula, R29 and R30 represent alkyl or aryl groups, N represents a nitrogen atom, and Y- represents an anion); Tertiary ammonium salts having a structure represented by formula (D-6):

[0167] [Chem. 58] (In the formula, m represents an integer from 2 to 11, n represents an integer from 2 to 3, H represents a hydrogen atom, N represents a nitrogen atom, and Y- represents an anion).

[0168] Furthermore, the aforementioned phosphonium salts can be categorized into fourth-order phosphonium salts represented by formula (D-7):

[0169] [Chemistry 59] (In the formula, R31, R32, R33, and R34 represent alkyl or aryl groups, P represents a phosphorus atom, and Y- represents an anion; and R31, R32, R33, and R34 are bonded to phosphorus atoms by CP bonds respectively).

[0170] Furthermore, the aforementioned sulfur salts can be categorized into tertiary sulfur salts represented by formula (D-8):

[0171] [Chemistry 60] (In the formula, R35, R36, and R37 represent alkyl or aryl groups, S represents a sulfur atom, and Y- represents an anion; and R35, R36, and R37 are bonded to sulfur atoms via CS bonds, respectively).

[0172] The compound of formula (D-1) above is a quaternary ammonium salt derived from an amine, where m represents an integer from 2 to 11 and n represents an integer from 2 to 3. R21 of this quaternary ammonium salt represents an alkyl group with 1 to 18 carbon atoms, ideally an alkyl group with 2 to 10 carbon atoms, or an aryl group with 6 to 18 carbon atoms. Examples include straight-chain alkyl groups such as ethyl, propyl, and butyl; or benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. Furthermore, the anion (Y-) can include halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), or acid groups such as carboxylate (-COO-), sulfonic acid (-SO3-), and alkoxide (-O-).

[0173] The compound of formula (D-2) above is a quaternary ammonium salt represented by R 22R 23R 24R 25N +Y -. R 22, R 23, R 24, and R 25 of this quaternary ammonium salt are alkyl groups with 1 to 18 carbon atoms, or aryl groups with 6 to 18 carbon atoms. Anions (Y -) can include halide ions such as chloride ions (Cl -), bromide ions (Br -), and iodide ions (I -), or acid groups such as carboxylic acid groups (-COO -), sulfonic acid groups (-SO 3 -), and alkoxide groups (-O -). This quaternary ammonium salt is commercially available and examples include: tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0174] The compound of formula (D-3) above is a quaternary ammonium salt derived from a 1-substituted imidazole. R26 and R27 have 1 to 18 carbon atoms, and the total number of carbon atoms in R26 and R27 is ideally 7 or more. Examples of R26 include methyl, ethyl, propyl, phenyl, and benzyl; examples of R27 include benzyl, octyl, and octadecyl. Anions (Y-) can include halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), or acid groups such as carboxylic acid groups (-COO-), sulfonic acid groups (-SO3-), and alkoxides (-O-). Although this compound is commercially available, it can be prepared by reacting imidazole compounds such as 1-methylimidazolium and 1-benzylimidazolium with alkyl halides such as benzyl bromide and methyl bromide, or aryl halides.

[0175] The compound of formula (D-4) above is a quaternary ammonium salt derived from pyridine. R 28 is an alkyl group with 1 to 18 carbon atoms, ideally an alkyl group with 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, such as butyl, octyl, benzyl, and lauryl. The anion (Y-) can be a halide ion such as chloride (Cl-), bromide (Br-), or iodide (I-), or an acid group such as a carboxylic acid group (-COO-), sulfonic acid group (-SO3-), or alkoxide (-O-). Although this compound can also be obtained commercially, it can be prepared by reacting pyridine with alkyl halides or aryl halides such as lauryl chloride, benzyl chloride, benzyl bromide, methane bromide, and octane bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0176] The compound of formula (D-5) above is a quaternary ammonium salt derived from substituted pyridines, such as methylpyridine. R29 is an alkyl group with 1 to 18 carbon atoms, ideally an alkyl group with 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, such as methyl, octyl, lauryl, benzyl, etc. R30 is an alkyl group with 1 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms. For example, in the case of a quaternary ammonium salt derived from methylpyridine, R30 is methyl. Anions (Y-) can be listed as: halide ions such as chloride ions (Cl-), bromide ions (Br-), iodide ions (I-), or acid groups such as carboxylic acid groups (-COO-), sulfonic acid groups (-SO3-), alkoxides (-O-). While this compound is also available commercially, it can be produced by reacting substituted pyridines, such as methylpyridine, with alkyl halides or aryl halides, such as methane bromide, octane bromide, lauryl chloride, benzyl chloride, and benzyl bromide. Examples of this compound include N-benzylmethylpyridinium chloride, N-benzylmethylpyridinium bromide, and N-laurylmethylpyridinium chloride.

[0177] The compound of formula (D-6) above is a tertiary ammonium salt derived from an amine, where m represents an integer from 2 to 11, and n represents an integer from 2 to 3. Furthermore, the anion (Y-) can be listed as: halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), or acid groups such as carboxylic acid groups (-COO-), sulfonic acid groups (-SO3-), and alkoxides (-O-). This compound can be prepared by reacting an amine with a carboxylic acid or a weak acid such as a phenol. Examples of carboxylic acids include formic acid and acetic acid. When formic acid is used, the anion (Y-) is (HCOO-); when acetic acid is used, the anion (Y-) is (CH3COO-). Furthermore, when a phenol is used, the anion (Y-) is (C6H5O-).

[0178] The compound of formula (D-7) above is a quaternary phosphonium salt having the structure R 31R 32R 33R 34P +Y -. R 31, R 32, R 33, and R 34 are alkyl groups with 1 to 18 carbon atoms or aryl groups with 6 to 18 carbon atoms. Ideally, three of the four substituents in R 31 to R 34 are phenyl or substituted phenyl groups, such as phenyl or tolyl, and the remaining one is an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms. In addition, the anion (Y -) can be listed as: halide ions such as chloride ion (Cl -), bromide ion (Br -), iodide ion (I -), or acid groups such as carboxylic acid group (-COO -), sulfonic acid group (-SO 3 -), alkoxide group (-O -). This compound is available in commercially available forms, such as: tetrabutylphosphonium halide, tetrapropylphosphonium halide, and other tetraalkylphosphonium halide; triethylbenzylphosphonium halide, and other trialkylbenzylphosphonium halide; triphenylmethylphosphonium halide, triphenylethylphosphonium halide, and other triphenylmonoalkylphosphonium halide; triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, trimethylmethylmonoarylphosphonium halide, or trimethylmethylmonoalkylphosphonium halide (where the halogen atom is a chlorine atom or a bromine atom). In particular, ideally triphenylmethylphosphonium halide, triphenylethylphosphonium halide, or triphenylmonoalkylphosphonium halide; triphenylbenzylphosphonium halide, or triphenylmonoarylphosphonium halide; trimethylmethylphosphonium halide, or trimethylmethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).

[0179] In addition, phosphine derivatives include: primary phosphine such as methylphosphine, ethylphosphine, propionylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphine such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, and diphenylphosphine; and tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0180] The compound of formula (D-8) above is a tertiary strontium salt having the structure R 35R 36R 37S +Y -. R 35, R 36, and R 37 are alkyl groups with 1 to 18 carbon atoms or aryl groups with 6 to 18 carbon atoms. Ideally, two of the three substituents in R 35 to R 37 are phenyl or substituted phenyl groups, such as phenyl or tolyl, and the remaining one is an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms. In addition, the anion (Y -) can be listed as: halide ions such as chloride ion (Cl -), bromide ion (Br -), iodide ion (I -), or acid groups such as carboxylic acid group (-COO -), sulfonic acid group (-SO 3 -), alkoxide (-O -), maleic acid anion, nitrate anion, etc. This compound is available in commercially available forms, including, for example: tri-n-butyl strontium halide, tri-n-propyl strontium halide, and other trialkyl strontium halides; dialkyl benzyl strontium halide, diethylbenzyl strontium halide, and other dialkyl benzyl strontium halides; diphenylmethyl strontium halide, diphenylethyl strontium halide, and other dialkyl monoalkyl strontium halides; triphenyl strontium halide (all of which have chlorine or bromine atoms); tri-n-butyl strontium carboxylate, tri-propyl strontium carboxylate, and other trialkyl strontium carboxylates; diethyl benzyl strontium carboxylate, dialkyl benzyl strontium carboxylate, diphenylmethyl strontium carboxylate, diphenylethyl strontium carboxylate, and other dialkyl monoalkyl strontium carboxylates; and triphenyl strontium carboxylate. Furthermore, triphenyl strontium halide and triphenyl strontium carboxylate are particularly desirable.

[0181] Furthermore, nitrogen-containing silane compounds can be added as curing catalysts in this invention. Examples of nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0182] When using a hardening catalyst, the amount is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass relative to 100 parts by mass of polysiloxane.

[0183] Stabilizers The aforementioned stabilizer can be added for purposes such as stabilizing the hydrolyzed condensate of the aforementioned hydrolyzable silane mixture. As a specific example, organic acids, water, alcohols, or combinations thereof can be added. Examples of the aforementioned 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. Oxalic acid and maleic acid are preferred. When adding organic acids, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the aforementioned hydrolyzable silane mixture. These organic acids can also be used as pH adjusters. The water mentioned above can be pure water, ultrapure water, ion-exchange water, etc.; when used, its addition amount can be 1 to 20 parts by mass relative to 100 parts by mass of the composition for forming the lower layer of photoresist film. The alcohols mentioned above are ideally those that are easily dispersed (volatile) by heating after coating, and examples include methanol, ethanol, propanol, isopropanol, butanol, etc. When adding alcohol, the amount added is 1 to 20 parts by mass relative to 100 parts by mass of the composition for forming the lower layer of photoresist film.

[0184] <<Organic Polymers>> The aforementioned organic polymer compound can be added to the composition for forming the photoresist underlayer film to adjust the dry etching rate (the amount of film thickness reduction per unit time), as well as the attenuation coefficient or refractive index of the film (photoresist underlayer film) formed by the composition. There are no particular limitations on the organic polymer compound, and it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on the purpose of its addition. Specific examples include: polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyethylene ether, phenolic varnish, naphthol varnish, polyether, polyamide, polycarbonate, and other addition polymers and condensation polymers. In this invention, organic polymers containing aromatic or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoline rings that function as light-absorbing sites can also be appropriately used when such function is required. Specific examples of such organic polymer compounds include: addition polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as their structural units; and condensation polymers such as phenolic varnish and naphtholic varnish, but are not limited to these.

[0185] When addition polymers are used as organic polymers, the polymer compound can be either a homopolymer or a copolymer. Addition polymers are used in the manufacture of addition polymers. Specific examples of such addition polymers include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0186] Specific examples of acrylate compounds include: methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl 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-adamantane acrylate, 5-acryloyloxy-6-hydroxynorcamphene-2-carboxylic acid-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0187] Specific examples of methacrylate compounds include: methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene 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-adamantane methacrylate, 5-methacryloxy-6-hydroxynorcamphen-2-carboxylic acid-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0188] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0189] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, N-anthraylmethacrylamide, etc.

[0190] 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, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc.

[0191] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc.

[0192] Maleimine compounds include, but are not limited to, maleimine, N-methylmaleimine, N-phenylmaleimine, N-cyclohexylmaleimine, N-benzylmaleimine, and N-hydroxyethylmaleimine.

[0193] When condensation polymers are used as polymers, examples of such polymers include condensation polymers of diol compounds and dicarboxylic acid compounds. Examples of diol compounds include diethylene glycol, hexamethylene glycol, and butanediol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Furthermore, examples of polyesters, polyamides, and polyimides include, but are not limited to, poly(pyromellitic terephthalamide), poly(p-phenylene terephthalate), polybutylene terephthalate, and polyethylene terephthalate. When an organic polymer compound contains hydroxyl groups, these hydroxyl groups can undergo cross-linking reactions with hydrolysates and the like.

[0194] The weight-average molecular weight of the aforementioned organic polymer compounds is typically 1,000 to 1,000,000. When combined with organic polymer compounds, from the viewpoint of fully obtaining the function of a polymer while simultaneously suppressing precipitation in the composition, the weight-average molecular weight may be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000. Such organic polymer compounds can be used alone or in combination of two or more.

[0195] When the composition for forming the photoresist lower layer film of the present invention contains an organic polymer compound, its content is appropriately determined considering the function of the organic polymer compound, etc., and therefore cannot be specified in general. However, relative to the mass of the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture, it can generally be in the range of 1 to 200% by mass. From the viewpoint of inhibiting precipitation in the composition, it can be, for example, 100% by mass or less, ideally 50% by mass or less, and more ideally 30% by mass or less. From the viewpoint of fully obtaining its effect, it can be, for example, 5% by mass or more, ideally 10% by mass or more, and more ideally 30% by mass or more.

[0196] <<Acid Generating Agents>> Acid generating agents include thermal acid generating agents and photoacid generating agents, with photoacid generating agents being the ideal choice. Photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. In addition, examples of hot acid generating agents include tetramethylammonium nitrate, but are not limited to these.

[0197] Specific examples of onium salt compounds include: diphenylmenium hexafluorophosphate, diphenylmenium trifluoromethanesulfonate, diphenylmenium nonafluoron-butanesulfonate, diphenylmenium perfluoron-octanesulfonate, diphenylmenium camphor sulfonate, bis(4-tert-butylphenyl)menium camphor sulfonate, bis(4-tert-butylphenyl)menium trifluoromethanesulfonate, etc.; triphenylstrontium hexafluoroantimonate, triphenylstrontium nonafluoron-butanesulfonate, triphenylstrontium camphor sulfonate, triphenylstrontium trifluoromethanesulfonate, triphenylstrontium nitrate, triphenylstrontium trifluoroacetate, triphenylstrontium maleate, triphenylstrontium chloride, etc., but are not limited to these.

[0198] Specific examples of sulfonamide compounds include, but are not limited to, N-(trifluoromethanesulfonoxy)succinimide, N-(nonafluorobutanoxy)succinimide, N-(camphorsulfonoxy)succinimide, and N-(trifluoromethanesulfonoxy)naphthalenedimethylimide.

[0199] Specific examples of disulfonyldiazomethane compounds include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylsulfonyl)diazomethane, methanesulfonyl-p-toluenesulfonyldiazomethane, etc.

[0200] When the composition for forming the photoresist lower layer film of the present invention contains an acid-generating agent, its content is appropriately determined by considering the type of acid-generating agent, etc., and therefore cannot be specified in general. However, relative to the mass of the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture, it is generally in the range of 0.01 to 5% by mass. From the viewpoint of inhibiting the precipitation of acid-generating agents in the composition, it is ideal to be 3% by mass or less, and more ideal to be 1% by mass or less. From the viewpoint of fully obtaining its effect, it is ideal to be 0.1% by mass or more, and more ideal to be 0.5% by mass or more. Furthermore, acid generating agents can be used alone or in combination with two or more. In addition, photoacid generating agents and thermal acid generating agents can be used together.

[0201] <<Surfactants>> Surfactants, when used to coat the aforementioned photoresist underlayer film formation components onto a substrate, can effectively suppress the occurrence of pinholes, streaks, etc. Examples of such surfactants include: nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, and UV-curable surfactants. More specifically, examples include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; and sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate. Sorbitan fatty acid esters, including polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters and other nonionic surfactants; trade names EFTOP (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronics & Chemicals Co., Ltd. (formerly Tohkem)). Fluorinated surfactants such as MEGAFACE (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Corporation of Japan), AsahiGuard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimei Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), but not limited to these. Surfactants can be used alone or in combination of two or more.

[0202] When the composition for forming the photoresist lower layer film of the present invention contains a surfactant, its content, relative to the mass of the hydrolyzed condensate of the above-mentioned hydrolyzed silane mixture, is typically 0.0001 to 5% by mass, ideally 0.001 to 4% by mass, and more ideally 0.01 to 3% by mass.

[0203] <<Rheology Modifiers>> The above-mentioned rheology modifiers are mainly added for the purpose of enhancing the fluidity of the composition for forming the lower layer film of the photoresist. Especially in the baking step, they are added for the purpose of enhancing the film thickness uniformity of the formed film and improving the filling property of the composition into the pores. Specific examples include: phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, etc.; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, etc.; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, dinonyl maleate, etc.; oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, etc.; or stearic acid derivatives such as n-butyl stearate, glyceryl stearate, etc. When using these rheology modifiers, the addition amount is usually less than 30% by mass relative to all the solid components of the composition for forming the lower layer film of the photoresist.

[0204] <<Adhesion aid>> The above-mentioned adhesion aid is mainly added for the purpose of enhancing the adhesion between the substrate or the photoresist and the film formed by the composition for forming the lower layer film of the photoresist (lower layer film of the photoresist). Especially in development, it is added for the purpose of suppressing and preventing the peeling of the photoresist. Specific examples include: chlorosilanes such as trimethylchlorosilane, dimethylethenylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, etc.; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylethenylethoxysilane, etc.; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, etc.; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc.; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc.; and ureas such as 1,1-dimethylurea, 1,3-dimethylurea, etc., or thiourea compounds. When using these adhesion aids, the addition amount is usually less than 5% by mass relative to all the solid components of the composition for forming the lower layer film of the photoresist, and preferably less than 2% by mass.

[0205] <<pH adjuster>> In addition, besides the organic acids with one or more carboxylic acid groups listed in the aforementioned <stabilizers>, bisphenol S or bisphenol S derivatives may also be added as pH adjusters. The amount of bisphenol S or bisphenol S derivatives relative to 100 parts by weight of the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture is 0.01 to 20 parts by weight, or 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight.

[0206] The following are specific examples of bisphenol S or bisphenol S derivatives, but are not limited to these.

[0207] [Chemistry 61]

[0208] The concentration of the solid component in the composition for forming the photoresist lower layer film, relative to the total mass of the composition, may 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. The solid component refers to the component from all components of the composition except for the solvent component. The content of the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture in the solid component is generally 20% to 100% by mass. From the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is ideally 50% by mass, more ideally 60% by mass, even more ideally 70% by mass, and even more ideally 80% by mass; the upper limit is ideally 99% by mass; the remainder may be used as a special additive (compound A) or other component described later. Furthermore, the content of the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture in the composition may, for example, be 0.5 to 20.0% by mass. Furthermore, the composition used to form the photoresist lower layer film ideally has a pH of 2 to 5, and more ideally has a pH of 3 to 4.

[0209] The composition for forming the lower layer of photoresist film can be manufactured by mixing the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture with a solvent, and, if necessary, by mixing in a specific additive (compound A) and other components. Alternatively, a solution containing the hydrolyzed condensate can be prepared in advance, and this solution can be mixed with a solvent and a specific additive (compound A) and other components. There is no particular restriction on the mixing order. For example, a solvent can be added to a solution containing hydrolysate and mixed, and then a specific additive (compound A) and other components can be added to the mixture. Alternatively, a solution containing hydrolysate, a solvent, a specific additive (compound A), and other components can be mixed simultaneously. If necessary, additional solvent may be added at the end, or the mixture may initially contain components that are relatively easily soluble in the solvent, which are then added at the end. However, from the viewpoint of suppressing the aggregation and separation of constituent components and producing a homogeneous composition with good reproducibility, it is ideal to prepare a solution in which hydrolytic condensates are well dissolved beforehand and use this solution to prepare the composition. Furthermore, it should be noted that hydrolytic condensates may aggregate or precipitate during mixing, depending on the type and amount of solvent being mixed, and the amount and properties of other components. Additionally, it should be noted that when using a solution containing dissolved hydrolytic condensates to prepare the composition, the concentration and amount of the solution must be determined to ensure that the final composition contains the required amount of hydrolytic condensates. In the preparation of the composition, heating can be applied appropriately within a range that will not decompose or deteriorate the components.

[0210] In this invention, filtration can also be performed using a submicron-sized filter or the like during the intermediate stage of manufacturing the composition for forming the photoresist lower layer film, or after all the components have been mixed.

[0211] The composition for forming a photoresist underlayer film of the present invention can be appropriately used as a composition for forming a photoresist underlayer film in the lithography process.

[0212] (Composition for forming the silicon-containing photoresist underlayer film of the second state) The composition for forming the photoresist lower layer film of the present invention comprises a hydrolyzed condensate of a mixture of hydrolyzable silanes and a specific additive (compound A) having a chemical structure containing cations AX+ and anions AZ-. By using a composition for forming a photoresist underlayer film containing a hydrolytic condensate (polysiloxane) of a mixture of hydrolyzable silanes, and a specific additive (compound A) having a chemical structure containing cations AX+ and anions AZ-, a photoresist underlayer film exhibiting excellent solubility in alkaline solutions (basic pharmaceutical solutions) can be formed.

[0213] <Hydrolysis condensate of hydrolyzable silane mixtures> There are no particular restrictions on the hydrolyzable silanes in the hydrolyzable silane mixture hydrolysate contained in the composition for forming the silicon-containing photoresist underlayer film of the second state. All silane compounds (hydrolyzable silanes) listed in the <hydrolyzable silane mixture hydrolysate> section of the above-mentioned composition for forming the silicon-containing photoresist underlayer film of the first state can be used. That is, it may contain any one of the hydrolyzable silanes represented by formula (1), formula (2), formula (3), formula (4), and formula (5), or it may contain hydrolyzable silanes other than those represented by these formulas. The difference between the hydrolysis condensate of the second state sample and the hydrolysis condensate of the first state sample lies in the type of hydrolyzable silane contained in the hydrolyzable silane mixture. While the first state sample specifies the presence of certain hydrolyzable silanes, the second state sample does not have such restrictions. By including a specific additive (compound A) in the composition for forming the lower layer of the photoresist film, the solubility of the lower layer film in alkaline solutions (basic pharmaceutical solutions) can be improved. Therefore, the second state sample does not have any particular restrictions on the type of hydrolyzable silane contained in the hydrolyzable silane mixture. Any hydrolyzable silane can also be used in the second state sample. The "hydrolysis condensate of hydrolyzable silane mixture" in the second state sample can use various hydrolyzable silanes listed in the "hydrolysis condensate of hydrolyzable silane mixture" section of the above (the composition for forming the silicon-containing photoresist lower layer film of the first state sample).

[0214] <Specific additive (compound A)> The "specific additive (compound A)" ​​in the second state sample is as described in the "specific additive (compound A)" ​​section of the above-mentioned composition for forming the silicon-containing photoresist underlayer film of the first state sample.

[0215] In the composition for forming the photoresist lower layer film of the second state sample, in addition to the hydrolysis condensate of the hydrolyzable silane mixture (polysiloxane) and a specific additive (compound A), solvents and other components may also be contained.

[0216] Solvent The "solvent" in the second state sample is as described in the "solvent" column above (the composition for forming the silicon-containing photoresist underlayer film of the first state sample).

[0217] <Other Ingredients (Other Additives)> The "Other Components (Other Additives)" in the second state sample refers to the "Other Components (Other Additives)" section as described above in the composition for forming the silicon-containing photoresist underlayer film of the first state sample.

[0218] The description of the solid component concentration and ideal pH value of the composition for forming the photoresist underlayer in the second state sample, and the manufacturing method of the composition for forming the photoresist underlayer, is as described in the section above (composition for forming the silicon-containing photoresist underlayer in the first state sample).

[0219] [Pattern forming method and semiconductor device manufacturing method] Hereinafter, as one aspect of the present invention, a method for patterning a composition for forming a photoresist underlayer film using the present invention, and a method for manufacturing a semiconductor device will be described.

[0220] First, the composition for forming the photoresist lower layer film of the present invention is coated onto a substrate used for manufacturing precision integrated circuit elements using a suitable coating method such as a spinner or coating machine. This substrate may include semiconductor substrates such as silicon wafers covered with silicon oxide, silicon nitride, or silicon oxynitride films; silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates with ITO (indium tin oxide) or IZO (indium zinc oxide) films, plastic (polyimide, PET, etc.) substrates, substrates covered with low-k dielectric materials, flexible substrates, etc.). Then, the composition is hardened by heating using a heating plate or similar means, thereby forming the photoresist lower layer film. In this specification, the photoresist lower layer film refers to the film formed by the composition for forming the photoresist lower layer film of the present invention. The firing conditions can be selected from firing temperatures of 40℃~400℃ or 80℃~250℃, and firing times of 0.3 minutes~60 minutes. The ideal firing temperature is 150℃~250℃, and the firing time is 0.5 minutes~2 minutes. The thickness of the photoresist underlayer formed here is, for example, 10nm~1,000nm, or 20nm~500nm, or 50nm~300nm, or 100nm~200nm, or 10~150nm.

[0221] The present invention is a state in which an organic lower layer film is formed on the above-mentioned substrate, and then the above-mentioned photoresist lower layer film is formed on it. However, it is also possible to form a state in which no organic lower layer film is provided, depending on the situation. There are no particular restrictions on the organic underlayer film used here; any organic underlayer film commonly used in lithography processes to date can be selected. By forming an organic lower layer film on a substrate, a photoresist lower layer film on top of it, and then a photoresist film (described later) on top of it, even when the pattern width of the photoresist film becomes narrow and the photoresist film is thinly covered to prevent pattern collapse, the substrate can still be processed by selecting an appropriate etching gas (described later). For example, a fluorine-based gas with a sufficiently fast etching rate for the photoresist film can be used as the etching gas to process the photoresist lower layer film of the present invention; in addition, an oxygen-based gas with a sufficiently fast etching rate for the photoresist lower layer film of the present invention can be used as the etching gas to process the organic lower layer film; furthermore, a fluorine-based gas with a sufficiently fast etching rate for the organic lower layer film can be used as the etching gas to process the substrate. Furthermore, examples of substrates and coating methods that can be used at this time are the same as those described above.

[0222] Next, a layer of photoresist material (photoresist film) is formed on the aforementioned photoresist lower layer film. The photoresist film can be formed using conventional methods, i.e., by coating a coating-type photoresist material (e.g., a composition for photoresist film formation) onto the photoresist lower layer film and then firing it. The thickness of the photoresist film is, for example, 10nm~10,000nm, or 100nm~2,000nm, or 200nm~1,000nm, or 30nm~200nm.

[0223] The photoresist material used in the photoresist film formed on the aforementioned photoresist lower layer is not particularly limited as long as it is a material that is sensitive to the light used for exposure (such as KrF excimer laser, ArF excimer laser, etc.). Both negative and positive photoresist materials can be used. Examples include: positive photoresist materials made of phenolic varnish resin and 1,2-naphthoquinone diazidesulfonate; chemically amplified photoresist materials made of binders with groups that increase the alkali dissolution rate through acid decomposition and photoacid generating agents; chemically amplified photoresist materials made of low-molecular-weight compounds that increase the alkali dissolution rate of photoresist materials through acid decomposition, alkali-soluble binders, and photoacid generating agents; and chemically amplified photoresist materials made of binders with groups that increase the alkali dissolution rate through acid decomposition, low-molecular-weight compounds that increase the alkali dissolution rate of photoresist materials through acid decomposition, and photoacid generating agents, etc. Specific examples that can be obtained in the form of commercially available products include: APEX-E manufactured by Shipley Corporation, PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772JN manufactured by JSR Corporation, and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these. In addition, examples include: fluorinated atom polymer-based photoresist materials described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0224] Furthermore, the photoresist film formed on the aforementioned photoresist underlayer film can be replaced with an electron beam lithography photoresist film (also known as an electron beam photoresist film) or an EUV lithography photoresist film (also known as an EUV photoresist film). That is, the silicon-containing photoresist underlayer film forming composition of the present invention can be used to form an electron beam lithography photoresist underlayer film or to form an EUV lithography photoresist underlayer film. It is particularly ideal as a composition for forming an EUV lithography photoresist underlayer film. The aforementioned electron beam photoresist materials can be used for both negative and positive applications. Specific examples include: chemically amplified photoresist materials composed of an acid-generating agent and a binder having groups that alter the alkali dissolution rate through acid decomposition; chemically amplified photoresist materials composed of an alkali-soluble binder, an acid-generating agent, and a low-molecular-weight compound that alters the alkali dissolution rate of the photoresist material through acid decomposition; chemically amplified photoresist materials composed of an acid-generating agent, a binder having groups that alter the alkali dissolution rate through acid decomposition, and a low-molecular-weight compound that alters the alkali dissolution rate of the photoresist material through acid decomposition; non-chemically amplified photoresist materials composed of a binder having groups that alter the alkali dissolution rate through electron beam decomposition; and non-chemically amplified photoresist materials composed of a binder having a portion that alters the alkali dissolution rate through electron beam cleavage, etc. When using these electron beam photoresist materials, the same principle applies as when using photoresist materials with an irradiation source as an electron beam; both methods can form patterns on the photoresist film. In addition, the aforementioned EUV photoresist materials can be methacrylic resin-based photoresist materials.

[0225] Next, the upper photoresist film formed on the lower photoresist film is exposed using a designated reticle. Exposure can be performed using a KrF excimer laser (wavelength 248nm), an ArF excimer laser (wavelength 193nm), an F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), an electron beam, etc. After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under suitable conditions, ranging from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0226] Next, development is performed using a developer (e.g., an alkaline developer). In this way, for example, when using a positive photoresist film, the exposed portion of the photoresist film is removed, thereby forming a pattern of the photoresist film. Developers (alkaline developers) can be exemplified by, for example, 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 alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants may be added to these developers. Developing conditions are appropriately selected from a temperature of 5–50°C and a development time of 10–600 seconds.

[0227] Furthermore, in this invention, an organic solvent can also be used as the developing solution, and development is performed using the developing solution (solvent) after exposure. This allows, for example, when using a negative photoresist film, the unexposed portions of the photoresist film to be removed, thereby forming a pattern on the photoresist film. Developers (organic solvents) can include, for example, the following: 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 monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, etc. 4-Ethoxybutyl acetate, 4-Propoxybutyl acetate, 2-Methoxypentyl acetate, 3-Methoxypentyl acetate, 4-Methoxypentyl acetate, 2-Methyl-3-Methoxypentyl acetate, 3-Methyl-3-Methoxypentyl acetate, 3-Methyl-4-Methoxypentyl acetate, 4-Methyl-4-Methoxypentyl acetate, Propylene glycol diacetate, Methyl formate, Ethyl formate, Butyl formate, Propyl formate, Ethyl lactate Butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. Furthermore, surfactants may be added to these developing solutions. The developing conditions are appropriately selected from a temperature of 5°C to 50°C and a time of 10 seconds to 600 seconds.

[0228] The patterned photoresist film (upper layer) is used as a protective film to remove the lower photoresist film (intermediate layer). Then, the film formed by the patterned photoresist film and the patterned lower photoresist film (intermediate layer) is used as a protective film to remove the lower organic film (lower layer). Finally, the patterned photoresist film (upper layer), the patterned lower photoresist film (intermediate layer), and the patterned lower organic film (lower layer) are used as protective films for substrate processing.

[0229] The removal of the lower (intermediate) photoresist film, which uses the pattern of the upper photoresist film as a protective film, can be performed by dry etching. The following gases can be used: tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane. Furthermore, the dry etching of the photoresist underlayer is ideally performed using a halogen-based gas. In dry etching with a halogen-based gas, the photoresist film, which is essentially composed of organic matter, is not easily removed. In contrast, silicon-containing photoresist underlayers, which contain a large number of silicon atoms, are rapidly removed by halogen-based gases. Therefore, the reduction in photoresist film thickness associated with the dry etching of the photoresist underlayer can be suppressed. Furthermore, as a result, the photoresist film can be used as a thin film. Therefore, the dry etching of the photoresist underlayer is ideally performed using a fluorine-based gas, such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but not limited to these.

[0230] When an organic lower layer film exists between the substrate and the photoresist lower layer film, the removal of the organic lower layer film (lower layer), which is then formed by using the patterned photoresist lower layer film (intermediate layer) (and if there are any remaining patterned photoresist film (upper layer) as a protective film), is ideally performed by dry etching with an oxygen-based gas (a mixture of oxygen and oxygen / carbonyl sulfide (COS) gas). This is because the photoresist lower layer film of this invention, which contains a large number of silicon atoms, is not easily removed by dry etching with an oxygen-based gas.

[0231] Finally, the processing of the (semiconductor) substrate, which uses a patterned photoresist lower layer (intermediate layer) and a patterned organic lower layer (lower layer) as a protective film as needed, is ideally carried out by dry etching with fluorine-based gases. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0232] In this invention, the photoresist underlayer can be removed using a chemical solution after the etching (removal) step of the organic underlayer. Furthermore, the removal of the photoresist underlayer using a chemical solution can also be performed after the substrate processing using the patterned organic underlayer. In this invention, by using a composition for forming a photoresist underlayer containing the aforementioned hydrolytic condensate (polysiloxane), the solubility of the film formed by the condensate under alkaline conditions can be improved. For example, it exhibits excellent solubility in alkaline solutions (basic chemical solutions) such as aqueous solutions containing ammonia and hydrogen peroxide. Therefore, with the photoresist underlayer exhibiting good peelability when processed in alkaline solutions, even silicon-based photomask residues, such as silicon-containing photoresist underlayers, can be easily removed using the chemical solution, thus enabling the manufacture of semiconductor devices with minimal damage to the substrate. The aforementioned solutions include: dilute hydrofluoric acid, buffered hydrofluoric acid, aqueous solutions containing hydrochloric acid and hydrogen peroxide (SC-2 solution), aqueous solutions containing sulfuric acid and hydrogen peroxide (SPM solution), aqueous solutions containing hydrofluoric acid and hydrogen peroxide (FPM solution), and aqueous solutions containing ammonia and hydrogen peroxide (SC-1 solution), etc. From the viewpoint of reducing the impact on the substrate, it is ideal to use alkaline solutions (basic solutions). In addition to the aforementioned ammonia-water-hydrogen peroxide solution (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide water, and water, the alkaline solutions mentioned above may also include aqueous solutions containing 1 to 99% by mass of the following substances: ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidone hydroxide, 1-propyl-1-methylpyrrolidone hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepiquat hydroxide, trimethylammonium hydroxide, hydrazines, ethylenediamines, or guanidines.

[0233] Furthermore, an organic antireflective film can be formed on top of the photoresist film before the photoresist film is formed. There are no particular restrictions on the composition of the antireflective film used here; for example, it can be selected from any materials commonly used in lithography processes to date. In addition, the antireflective film can be formed by conventional methods such as coating and firing performed by a spinner or coating machine.

[0234] Furthermore, a substrate coated with the composition for forming the photoresist lower layer film of the present invention may have an organic or inorganic antireflective film formed by chemical vapor deposition (CVD) or similar methods on its surface, and a photoresist lower layer film may also be formed thereon. When an organic lower layer film is formed on the substrate, and then the photoresist lower layer film of the present invention is formed thereon, an organic or inorganic antireflective film formed by CVD or similar methods may also be formed on the surface of the substrate used.

[0235] The photoresist underlayer film formed by the composition for forming the photoresist underlayer film of the present invention has the ability to absorb light according to the wavelength of light used in the photolithography process. In this case, it can perform the function of preventing reflected light from the substrate as an anti-reflective film. Furthermore, the aforementioned photoresist lower layer film can also be used as: a layer to prevent interaction between the substrate and the photoresist film (photoresist film, etc.); a layer that prevents the material used in the photoresist film or substances generated during exposure of the photoresist film from adversely affecting the substrate; a layer that prevents substances generated from the substrate during heating and firing from diffusing to the upper photoresist film; and a barrier layer to reduce the poisoning effect of the photoresist film caused by the dielectric layer of the semiconductor substrate, etc.

[0236] The aforementioned photoresist lower layer film is applicable to substrates with through-holes used in dual damascene processes, and can be used as a hole-filling material (embedding material) capable of filling holes without gaps. Furthermore, it can also be used as a planarization material for planarizing the surface of uneven semiconductor substrates. Furthermore, the aforementioned photoresist underlayer film, as the underlayer film of EUV photoresist film, in addition to its function as a hard photomask, can also be used as an anti-reflective underlayer film of EUV photoresist film to prevent reflection of unwanted exposure light, such as UV (ultraviolet) light and DUV (deep ultraviolet) light (ArF light, KrF light), from the substrate or interface during EUV exposure (wavelength 13.5nm). That is, it can effectively prevent reflection as the underlayer of EUV photoresist film. When used as an EUV photoresist underlayer film, its fabrication process can be performed in the same way as that for photoresist underlayer films.

[0237] The semiconductor processing substrate described above, which incorporates the photoresist lower layer film and the semiconductor substrate of the present invention, can be used to appropriately process the semiconductor substrate. Furthermore, as described above, the semiconductor device manufacturing method includes: a step of forming an organic underlayer film, a step of forming a silicon-containing photoresist underlayer film using the silicon-containing photoresist underlayer film forming composition of the present invention on the organic underlayer film, and a step of forming a photoresist film on the silicon-containing photoresist underlayer film. According to this semiconductor device manufacturing method, high-precision semiconductor substrate processing can be achieved with good reproducibility, and therefore stable manufacturing of semiconductor devices can be expected. [Example]

[0238] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The hydrolytic condensates of the aforementioned hydrolyzable silanes (polyorganosiloxanes) can yield condensates with a weight average molecular weight of 1,000 to 1,000,000 or 1,000 to 100,000. These molecular weights are obtained by conversion to polystyrene using GPC analysis. The determination conditions for GPC are as follows: 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 Corporation), a column temperature of 40°C, tetrahydrofuran as the dissolution solvent, a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko Corporation) as the standard sample.

[0239] [1] Synthesis Examples 1-11 and Comparative Synthesis Examples 1-2: Synthesis of hydrolysis condensates (polysiloxanes) Compounds 1-8 used in each synthesis are shown below.

[0240] [Chemistry 62] In the above formulas, Me represents methyl and Et represents ethyl.

[0241] <Synthesis example 1> Compound 1: 20.8g, Compound 2: 21.9g, Compound 3: 8.8g, Compound 4: 0.1g, Compound 5: 0.9g, and 1-ethoxy-2-propanol 83g were placed in a 200mL flask and stirred. While stirring the obtained solution with a magnetic stirrer, 37g of 0.2mol / L nitric acid aqueous solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 65°C and reacted for 20 hours. Then, the reaction solution was cooled to room temperature, and 56 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol and ethanol (reaction byproducts) were removed by distillation under reduced pressure, thereby obtaining a concentrated solution of the hydrolysate (polymer) using 1-ethoxy-2-propanol as a solvent. Furthermore, the solids concentration of the obtained concentrate, when heated to 150°C, exceeded 20% by mass based on solid residue. The obtained hydrolysis condensate (polysiloxane) corresponds to the following formula, converted to polystyrene by the weight average molecular weight (Mw) of GPC, which is 2,000. Furthermore, in the chemical formulas described in the following synthetic examples and comparative synthetic examples, the numbers next to the siloxane units indicate molar ratios (total 100).

[0242] [Chemistry 63]

[0243] Under the same conditions as in Synthesis Example 1, using the compounds (monomers) shown in Table 1, <Synthesis Example 2> to <Synthesis Example 11> were carried out to obtain their respective target hydrolytic condensates (polysiloxane compounds) 2 to 11.

[0244] [Table 1]

[0245] <Comparative Synthesis Example 1> Compound 1: 20.8 g (70 mol%), compound 7: 7.6 g (30 mol%), and 42 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. While stirring the obtained solution with a magnetic stirrer, 19 g of 0.2 mol / L nitric acid aqueous solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 65°C and reacted for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and ethanol (a reaction byproduct) were removed from the reaction solution by vacuum distillation under reduced pressure, thereby obtaining a concentrated solution of the hydrolysate (polymer) using 1-ethoxy-2-propanol as a solvent. Furthermore, the solids concentration of the obtained concentrated solution, when heated to 150°C, exceeded 20% by mass based on solid residue. The obtained hydrolysis condensate (polysiloxane) corresponds to the following formula, which is converted to polystyrene by the weight average molecular weight (Mw) of GPC, which is 2,700.

[0246] [Chemistry 64]

[0247] <Comparative Synthesis Example 2> Compound 1: 12.5 g (40 mol%), Compound 7: 12.0 g (45 mol%), Compound 3: 3.6 g (12 mol%), Compound 8: 1.9 g (3 mol%), and 45 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. While stirring the obtained solution with a magnetic stirrer, 18 g of 0.2 mol / L nitric acid aqueous solution was added dropwise. After the addition, the flask was placed in an oil bath adjusted to 65°C and reacted for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water, nitric acid, and methanol and ethanol (reaction byproducts) were removed from the reaction solution by vacuum distillation under reduced pressure, thereby obtaining a concentrated solution of the hydrolysate (polymer) using 1-ethoxy-2-propanol as a solvent. Furthermore, the solids concentration of the obtained concentrated solution, when heated to 150°C, exceeded 20% by mass based on solid residue. The obtained hydrolysis condensate (polysiloxane) corresponds to the following formula, converted to polystyrene by the weight average molecular weight (Mw) of GPC, which is 1,900.

[0248] [Chemistry 65]

[0249] [2] Modulation Examples 1-34 and Comparative Modulation Examples 1-2: Modulation of the composition (coating solution) for forming the silicon-containing photoresist underlayer film The hydrolytic condensates (polymers) 1-11 obtained in the above synthetic examples and the hydrolytic condensates (polymers) of comparative synthetic examples 1-2 were mixed with additives and solvents in the proportions shown in Tables 2-1 and 2-2, and filtered through a 0.02 μm polyethylene filter to prepare separate composition solutions for forming polysiloxane lower membranes. The amounts added in Table 2 are expressed in parts by mass. Furthermore, in Table 2, each synthetic example listed in the composition column is 2 parts by mass, which refers to 2 parts by mass of the hydrolysis condensate. In addition, in Table 2, MA refers to maleic acid, TPSNO3 refers to triphenylsulfuric nitrate, PGEE refers to propylene glycol monoethyl ether, and PGME refers to propylene glycol monomethyl ether. In addition, in Table 2, Add-1 to 11 are each additives represented by the following structural formula.

[0250] [Chemistry 66]

[0251] [Chemistry 67]

[0252] [Table 2-1]

[0253] [Table 2-2]

[0254] [3] Modulation of components for organic sublayer film formation Under nitrogen atmosphere, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-furonone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL four-necked flask. Then, 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred. The mixture was then heated to 100 °C to dissolve the solid and begin polymerization. After 24 hours, the reaction mixture was cooled to 60°C, and chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added and diluted. The diluted reaction mixture was then added dropwise to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) for reprecipitation. The obtained precipitate was filtered and recovered, and the recovered solid was dried at 80°C for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter referred to as PCzFL). Furthermore, the 1H-NMR determination results of PCzFL are as follows. 1H-NMR (400MHz, DMSO-d 6): δ7.03-7.55 (br, 12H), δ7.61-8.10 (br, 4H), δ11.18 (br, 1H) Furthermore, the weight-average molecular weight (Mw) of PCzFL is 2,800 converted from GPC to polystyrene, and the polydispersity Mw / Mn is 1.77.

[0255] [Chemistry 68]

[0256] 20g of PCzFL, 3.0g of tetramethoxymethylethynylurea (manufactured by Cytec Industries Japan (formerly Mitsui Cytec Co., Ltd.), trade name Powderlink 1174) as a crosslinking agent, 0.30g of pyridinium p-toluenesulfonate as a catalyst, and 0.06g of Megaface R-30 (manufactured by DIC Co., Ltd., trade name) as a surfactant were mixed and dissolved in 88g of propylene glycol monomethyl ether acetate to form a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10μm, and further filtered using a polyethylene microfilter with a pore size of 0.05μm to prepare a composition for forming an organic lower membrane.

[0257] [4] Examples 1-34, Comparative Examples 1-2: Evaluation of photoresist patterns (PTD) exposed by ArF The above-mentioned organic lower layer film forming composition is coated onto a silicon wafer using a spinner, and heated at 240°C for 60 seconds on a hot plate to form an organic lower layer film (layer A) (film thickness 200 nm). The coating liquid obtained in Modulation Example 1 was spin-coated onto the coating and heated at 215°C for 1 minute on a heating plate to form a silicon-containing photoresist lower layer film (B layer) (20nm). Further, commercially available ArF photoresist (manufactured by JSR Corporation, trade name: AR2772JN) was spin-coated onto the surface and heated at 110°C for 90 seconds on a hot plate to form a photoresist film (C layer) (120nm). Then, using a Nikon NDR-S307E scanner (wavelength: 193nm, NA: 0.85, σ: 0.85 / 0.93), the image was exposed through a pre-set photomask to achieve a line width and line spacing of 0.065μm after development, thus forming dense lines with a line / spacing (L / S) of 0.065μm = 1 / 1. After exposure, post-exposure heating (110℃ for 1 minute) is performed, followed by cooling to room temperature on a cooling plate. Then, development is carried out using a 2.38% alkaline aqueous solution for 60 seconds, and a rinse process is performed to form a photoresist pattern. Photoresist patterns were formed by using the same procedure with each coating liquid obtained in Modulation Examples 2-34 and Comparative Modulation Examples 1-2. The experimental results using modulation examples 1 to 34 are respectively referred to as Examples 1 to 34, and the experimental results using comparative modulation examples 1 to 2 are respectively referred to as Comparative Examples 1 to 2. The obtained photoresist patterns were evaluated by confirming the pattern shape observed through the cross-section of the pattern. A state without pattern collapse (significant pattern peeling and undercutting, thickening of the line base (foot)) was rated as "good"; a state with pattern collapse was rated as "poor". The results are shown in Table 3. Furthermore, in the following description, the example numbers of the photoresist underlayer film formation composition used will also serve as example numbers for various evaluations carried out using the composition.

[0258] [5] Examples 1-34, Comparative Examples 1-2: Evaluation by FT-IR siloxane bond strength ratio The coating solution obtained in Modulation Example 1 was spin-coated onto a silicon wafer and heated at 215°C for 1 minute on a hot plate to form a silicon-containing photoresist lower layer (B layer). On the formed B layer, two more B layers were deposited in the same manner to obtain a B layer with 3 layers (80 nm film thickness). Silicon-containing photoresist underlayer films were formed by using the coating solutions obtained in Modulation Examples 2-34 and Comparative Modulation Examples 1-2 respectively, following the same procedure. For each silicon-containing photoresist underlayer film obtained, Fourier transform infrared spectroscopy (FT / IR-6600 (manufactured by Nippon Spectroradio Corporation)) was used to compare the peak intensities of siloxane bonds observed at wavenumbers of 1000–1250 cm⁻¹. The peak intensities were compared using the intensity of the silicon-containing photoresist underlayer film of Comparative Example 2 as a normalized value to 100. When the bond strength was relatively high compared to that of Comparative Example 2 (e.g., above 90), there was a tendency for decreased solubility. The results are shown in Table 3.

[0259] [6] Examples 1-34, Comparative Examples 1-2: Removal performance evaluation using SC-1 solution (ammonia / hydrogen peroxide aqueous solution) The coating solution obtained in Modulation Example 1 was spin-coated onto a silicon wafer and heated at 215°C for 1 minute on a hot plate to form a silicon-containing photoresist lower layer (B layer) (20nm). Silicon-containing photoresist underlayer films were formed by using the coating solutions obtained in Modulation Examples 2-34 and Comparative Modulation Examples 1-2 respectively, following the same procedure. Silicon wafers with obtained silicon-containing photoresist underlayers were immersed in SC-1 solution (28% ammonia / 33% hydrogen peroxide / water = 1 / 1 / 10 (v / v / v)) adjusted to a liquid temperature of 60°C for 180 or 300 seconds, followed by rinsing with water for 60 seconds and drying. The thickness of the silicon-containing photoresist underlayer after 300 seconds of immersion in SC-1 solution was then measured, and the thickness change rate (%) was calculated. A thickness change rate of 90% or more relative to the initial thickness after immersion was rated as "Good"; less than 90% was rated as "Poor". Furthermore, in cases where immersion for 300 seconds was rated as "Good", a thickness change rate of 90% or more after immersion for 180 seconds was rated as "Very Good". The results are shown in Table 3.

[0260] [7] Examples 1-34, Comparative Examples 1-2: Evaluation of residues after dry etching The above-mentioned organic lower layer film forming composition is coated onto a silicon wafer using a spinner, and heated at 240°C for 60 seconds on a hot plate to form an organic lower layer film (layer A) (film thickness 70 nm). The coating liquid obtained in Modulation Example 1 was spin-coated onto the coating and heated at 215°C for 1 minute on a heating plate to form a silicon-containing photoresist lower layer film (B layer) (20nm). Using a dry etching machine (LAM-2300) manufactured by Lam Research Corporation, a 20-second dry etching process was performed under CF4 gas conditions to remove the silicon-containing photoresist underlayer (B layer) from the resulting coated silicon wafer. Then, a 5-second dry etching process was performed under O2 / COS gas conditions to remove the organic underlayer (A layer). Using the same procedure, the coating solutions obtained in Modulation Examples 2-34 and Comparative Modulation Examples 1-2 were used to form silicon-containing photoresist underlayer films, and the silicon-containing photoresist underlayer film (layer B) and the organic underlayer film (layer A) were removed. The silicon wafer surface after the organic underlayer (layer A) and the silicon-containing photoresist underlayer (layer B) were removed was observed using a scanning probe microscope (Hitachi High Technology Co., Ltd., AFM5000). Cases with convex etching residues exceeding 0.05 μm in width and 2 nm in height were classified as "poor," while those without such residues were classified as "good." The results are shown in Table 3.

[0261] [Table 3]

Claims

1. A composition for forming a silicon-containing photoresist underlayer film, comprising a hydrolysis condensate containing a mixture of hydrolyzable silanes, the mixture of hydrolyzable silanes comprising at least one of a hydrolyzable silane represented by formula (1) and a hydrolyzable silane represented by formula (2); it is used to form a silicon-containing photoresist underlayer film soluble in an alkaline pharmaceutical solution; [Chemical 1] (in formula (1), R1 is a group bonded to silicon atoms, representing an organic group containing a succinic anhydride skeleton, and the carbon atom in the organic group containing the succinic anhydride skeleton is bonded to the silicon atom); R2 is a group bonded to a silicon atom, which independently represents an alkyl group that can be substituted by a substituent, a alkyl halide that can be substituted by a substituent, or an alkyl alkoxy group that can be substituted by a substituent, or an organic group containing an epoxy group, acrylonitrile, methacrylonitrile, mercapto, amino, acetamino, alkoxy, sulfonyl, or cyano, or a combination thereof. The substituent is selected from alkyl, aryl, aralkyl, alkyl halide, aryl halide, aralkyl halide, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxy, arylalkoxy; R3 is a group or atom bonded to a silicon atom, which independently represents an alkoxy, arylalkoxy, acetoxy, or halogen atom; a represents an integer of 1, b represents an integer from 0 to 2, 4-(a+b) represents an integer from 1 to 3); [Chemical 2] (In formula (2), R4 is a group bonded to a silicon atom, represented by the following formula (2-1): [Chemical 3] (In formula (2-1), R201~R202 independently represent hydrogen atoms and organic groups containing alkyl groups that can be substituted by substituents, R203 represents an alkyl group that can be substituted by substituents, the substituent being selected from alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxyaryl, arylalkoxy, * represents a bond bonded to a silicon atom, the carbon atom in R203 is bonded to the silicon atom). R5 is a group bonded to a silicon atom, which independently represents an alkyl group that can be substituted by a substituent, a halogenated alkyl group that can be substituted by a substituent, or an alkoxyalkyl group that can be substituted by a substituent, or an organic group containing an epoxy group, acrylonitrile, methacrylonitrile, mercapto, amino, acetamino, alkoxy, sulfonyl, or cyano, or a combination thereof. The substituent is selected from alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxy, and arylalkoxy; R6 is a group or atom bonded to a silicon atom, which independently represents an alkoxy, arylalkoxy, acetoxy, or halogen atom; a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3).

2. The composition for forming a silicon-containing photoresist underlayer film as described in claim 1, wherein, The silicon-containing photoresist lower layer film forming composition further contains: a compound A having a chemical structure comprising a cation AX+ and an anion AZ-, wherein the molecular weight of the anion AZ- is 65 or more; the cation AX+ is an organic cation that has a positive charge, any one of nitrogen, sulfur, and phosphorus; and the anion AZ- is an organic anion that has a negative charge.

3. The composition for forming a silicon-containing photoresist underlayer film as described in claim 2, wherein, The anion AZ- is an anion selected from at least one of the groups of anions represented by (A) to (E) below; [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] (In formulas (A) to (E), R301 represents an alkyl group that can be substituted by a substituent, an aryl group that can be substituted by a substituent, a haloalkyl group that can be substituted by a substituent, an aralkyl group that can be substituted by a substituent, or an organic group containing an ester bond (-C(=O)-O- or -OC(=O)-), or a combination thereof, wherein the substituent is selected from alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxy, arylalkoxy; Z represents an aromatic ring, a cyclic alkane, or a non-aromatic cyclic olefin; R501 represents an alkyl group that can be partially or completely substituted by a fluorine atom; R302 and R303 independently represent alkyl groups; R304 and R305 independently represent alkyl groups.

4. The composition for forming a silicon-containing photoresist underlayer film as described in claim 1, wherein, The hydrolyzable silane mixture further contains hydrolyzable silane represented by the following formula (3); [Chemical 10] (In formula (3), R7 is a group bonded to a silicon atom, representing an alkenyl-containing organic group, and the carbon atom in the alkenyl-containing organic group is bonded to the silicon atom; R8 is a group bonded to a silicon atom, which independently represents an alkyl group that can be substituted by a substituent, a halogenated alkyl group that can be substituted by a substituent, or an alkoxyalkyl group that can be substituted by a substituent, or an organic group containing an epoxy group, acrylonitrile, methacrylamide, mercapto, amino, acetamino, alkoxy, sulfonylutrile, or cyano, or a combination thereof, wherein the substituent is selected from alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxyaryl, arylalkoxy; R9 represents a group or atom bonded to a silicon atom, which can independently represent an alkoxy, arylalkoxy, acetoxy, or halogen atom; a represents an integer of 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3.

5. The composition for forming a silicon-containing photoresist underlayer film as described in claim 4, wherein, The hydrolyzable silane mixture further contains hydrolyzable silane represented by the following formula (4); [Chemical 11] (in formula (4), R10 is a group or atom bonded to a silicon atom, which independently represents an alkoxy, arylalkoxy, acetoxy, or halogen atom).

6. A silicon-containing photoresist underlayer film forming composition, which is used to form a silicon-containing photoresist underlayer film soluble in an alkaline solution, the silicon-containing photoresist underlayer film forming composition comprising: a compound A having a chemical structure comprising a cation AX+ and an anion AZ- and the molecular weight of the anion AZ- being 65 or more; the cation AX+ being an organic cation having a positive charge from nitrogen, sulfur, and phosphorus; and the anion AZ- being an organic anion having a negative charge.

7. The composition for forming a silicon-containing photoresist underlayer film as described in claim 6, wherein, The anion AZ- is an anion selected from at least one of the groups of anions represented by (A) to (E) below; [Chemical 12] [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] [Chemical 17] (In formulas (A) to (E), R301 represents an alkyl group that can be substituted by a substituent, an aryl group that can be substituted by a substituent, a haloalkyl group that can be substituted by a substituent, an aralkyl group that can be substituted by a substituent, or an organic group containing an ester bond (-C(=O)-O- or -OC(=O)-), or a combination thereof, wherein the substituent is selected from alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxy, arylalkoxy; Z represents an aromatic ring, a cyclic alkane, or a non-aromatic cyclic alkene; R501 represents an alkyl group that can be partially or completely substituted by a fluorine atom; R302 and R303 independently represent alkyl groups; R304 and R305 independently represent alkyl groups.

8. A silicon-containing photoresist underlayer film, formed using a composition for forming a silicon-containing photoresist underlayer film as described in any one of claims 1 to 7.

9. A pattern forming method comprising: forming an organic underlayer film on a semiconductor substrate; coating a silicon-containing photoresist underlayer film forming composition as described in any one of claims 1 to 7 onto the organic underlayer film, and firing it to form a silicon-containing photoresist underlayer film; coating a photoresist film forming composition onto the silicon-containing photoresist underlayer film to form a photoresist film; exposing and developing the photoresist film to obtain a photoresist pattern; using the photoresist pattern as a photomask and etching the silicon-containing photoresist underlayer film; and using the patterned silicon-containing photoresist underlayer film as a photomask and etching the organic underlayer film.

10. The pattern forming method as described in claim 9, wherein, The process further includes a step of removing the silicon-containing photoresist underlayer by using a wet method with a chemical solution after etching the organic underlayer.

11. The pattern forming method as described in claim 10, wherein, This medicine solution is an alkaline solution.

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