Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
  • H10P50/283—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials by chemical means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials

Definitions

• the present invention relates to a composition for forming a resist underlayer film, which can form a low-roughness pattern in fine patterning, and is suitable for semiconductor substrates and coating-type organic underlayer films required in patterning processes and CVD films containing carbon as a main component.
• Formation of a silicon-containing resist underlayer film that can be easily stripped with a stripping solution that does not cause damage, is particularly soluble in alkaline chemicals (basic chemicals), and can form a silicon-containing film that can maintain strippability even after dry etching.
• Microfabrication by lithography using a photoresist has been conventionally performed in the manufacture of semiconductor devices.
• the fine processing is obtained by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating actinic rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developing.
• This is a processing method in which fine unevenness corresponding to the pattern is formed on the surface of the substrate by etching the substrate using the photoresist pattern as a protective film.
• a film known as a hard mask containing metal elements such as silicon and titanium is used as an underlayer film between the semiconductor substrate and the photoresist.
• the resist and the hard mask have a large difference in their constituent components, their removal rate by dry etching greatly depends on the type of gas used for dry etching.
• the hard mask can be removed by dry etching without significantly reducing the film thickness of the photoresist.
• a resist underlayer film has been placed between the semiconductor substrate and the photoresist in order to achieve various effects including an antireflection effect.
• compositions for resist underlayer films have been studied so far, but the development of new materials for resist underlayer films is desired due to the diversity of properties required thereof.
• coating-type BPSG (boron phosphorous glass) film-forming composition containing a structure having a specific silicic acid skeleton Patent Document 1
• Patent Document 2 A composition for forming a silicon-containing resist underlayer film containing a carbonyl structure (Patent Document 2) is disclosed for the purpose of removing a chemical solution.
• multi-layer processes are often used due to the miniaturization of implant layers.
• transfer to the lower layer is performed by the above-mentioned dry etching, and finally the substrate is processed and processed.
• Subsequent mask residues, such as resist films and underlayer films including resist underlayer films, may also be removed by dry etching or ashing.
• dry etching and ashing do damage substrates, and there is a demand for improvement.
• the present invention has been made in view of the above circumstances.
• a silicon-containing resist underlayer film-forming composition for forming a resist underlayer film that can be stripped by wet etching using a chemical such as
• Another object of the present invention is to provide a composition for forming a silicon-containing resist underlayer film which is excellent in storage stability and which leaves little residue in a dry etching step.
• a specific hydrolytic condensate obtained from a hydrolyzable silane having a succinic anhydride skeleton or a hydrolyzable silane having a phosphonic acid-derived group A film obtained from a composition containing ( polysiloxane) exhibits excellent solubility in an alkaline solution (basic chemical solution ) , and a specific additive (compound It was found that a film obtained from a composition containing a hydrolytic condensate (polysiloxane) obtained from a hydrolyzable silane containing A) exhibits excellent solubility in an alkaline solution (basic chemical solution), and the present invention is based on this finding. completed.
• R 1 is a group bonded to a silicon atom and represents an organic group containing a succinic anhydride skeleton
• R 2 is a group that binds to a silicon atom and is independently an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or an optionally substituted alkoxyalkyl group; or organic groups including epoxy, acryloyl, methacryloyl, mercapto, amino, amido, alkoxy, sulfonyl, or cyano groups, or combinations thereof
• R 3 is a group or atom bonded to a silicon atom and independently of each other represents an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom
• a represents 1
• b represents an integer of 0-2, and 4-(a+b) represents an integer of 1-3.
• R 4 is a group bonded to a silicon atom and represents a monovalent group represented by the following formula (2-1), (In formula (2-1), R 201 to R 202 each independently represent an organic group containing a hydrogen atom or an optionally substituted alkyl group, R 203 represents an optionally substituted alkylene group, and * is bonded to a silicon atom. Represents a bond.
• R 5 is a group that binds to a silicon atom and is independently an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or an optionally substituted alkoxyalkyl group; or organic groups including epoxy, acryloyl, methacryloyl, mercapto, amino, amido, alkoxy, sulfonyl, or cyano groups, or combinations thereof;
• R 6 is a group or atom bonded to a silicon atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom; a represents 1, b represents an integer of 0-2, and 4-(a+b) represents an integer of 1-3.
• composition for forming a silicon-containing resist underlayer film has a chemical structure containing a cation AX + and an anion AZ ⁇ , and further contains a compound A in which the anion has a molecular weight of 65 or more.
• a composition for forming a silicon-containing resist underlayer film [3]
• the anion AZ ⁇ is at least one anion selected from the group consisting of anions represented by (A) to (E) below. Composition.
• Z represents an aromatic ring, a cyclic alkane, or a cyclic alkene in a non-aromatic ring;
• R 501 represents an alkyl group that may be partially or wholly substituted with a fluorine atom,
• R 302 and R 303 independently represent an alkyl group,
• R 304 and R 305 independently represent an alkyl group.
• a composition for forming a silicon-containing resist underlayer film for forming a silicon-containing resist underlayer film soluble in a basic chemical A composition for forming a silicon-containing resist underlayer film, comprising a compound A having a chemical structure containing a cation AX + and an anion AZ ⁇ , wherein the anion has a molecular weight of 65 or more.
• the anion AZ ⁇ is at least one anion selected from the group consisting of anions represented by (A) to (E) below. Composition.
• Z represents an aromatic ring, a cyclic alkane, or a cyclic alkene in a non-aromatic ring;
• R 501 represents an alkyl group that may be partially or wholly substituted with a fluorine atom,
• R 302 and R 303 independently represent an alkyl group,
• R 304 and R 305 independently represent an alkyl group.
• a hydrolytic condensate obtained by using a silane compound having a specific structure containing a succinic anhydride skeleton or a group derived from phosphonic acid as a hydrolyzable silane is used as a composition for forming a resist underlayer film.
• a silane compound having a specific structure containing a succinic anhydride skeleton or a group derived from phosphonic acid is used as a composition for forming a resist underlayer film.
• a specific additive (compound A) having a chemical structure containing a cation AX + and an anion AZ ⁇ is used for forming a resist underlayer film containing a hydrolysis condensate obtained by using a silane compound.
• compound A a specific additive having a chemical structure containing a cation AX + and an anion AZ ⁇ is used for forming a resist underlayer film containing a hydrolysis condensate obtained by using a silane compound.
• the film formed from the composition even a silicon-based film, exhibits excellent solubility in a basic chemical solution, and can be improved in removability by a wet method. . Therefore, when the composition for forming a resist underlayer film of the present invention is used to form a pattern using a photoresist film or the like or to process a semiconductor substrate or the like, the residue of the mask after processing is removed.
• composition for forming silicon-containing resist underlayer film is directed to a composition for forming a silicon-containing resist underlayer film that can be stripped by a wet method and that exhibits excellent solubility in basic chemical solutions.
• the composition for forming a resist underlayer film of the present invention contains a hydrolytic condensate of a hydrolyzable silane mixture.
• One feature of the composition for forming a resist underlayer film of the present invention is that it contains a product (hydrolytic condensate) obtained by hydrolytic condensation of a hydrolyzable silane mixture containing a hydrolyzable silane having a specific structure. do.
• composition for forming a silicon-containing resist underlayer film of the first aspect contains a hydrolytic condensate of a hydrolyzable silane mixture and a specific additive (compound A) having a chemical structure containing a cation AX + and an anion AZ ⁇ . is one of the features.
• compound A a specific additive having a chemical structure containing a cation AX + and an anion AZ ⁇ .
• the composition for forming a resist underlayer film of the present invention may contain a solvent and other components described later in addition to the hydrolytic condensate of the hydrolyzable silane mixture and the specific additive (compound A).
• the hydrolytic condensate includes not only a polyorganosiloxane polymer that is a condensate in which the condensation is completely completed, but also a polyorganosiloxane polymer that is a partially hydrolytic condensate in which the condensation is not completely completed.
• a partially hydrolyzed condensate is also a polymer obtained by hydrolysis and condensation of a hydrolyzable silane compound like the condensate in which the condensation is completely completed, but the hydrolysis stops partially and the condensation does not occur. not, and therefore the Si--OH groups remain.
• composition for forming a resist underlayer film of the present invention contains, in addition to the hydrolytic condensate, an uncondensed hydrolyzate (complete hydrolyzate, partial hydrolyzate) and a monomer (hydrolyzable silane compound). It may remain.
• hydrolyzable silane may be simply referred to as "silane compound”.
• composition for forming a silicon-containing resist underlayer film of the first aspect contains a hydrolytic condensate of a hydrolyzable silane mixture containing a hydrolyzable silane having a specific structure.
• the hydrolyzable silane mixture contains a hydrolyzable silane represented by the following formula (1) or a hydrolyzable silane represented by the following formula (2), and optionally a hydrolyzable silane represented by the following formula (3). It may contain a decomposable silane, a hydrolyzable silane of tetraalkoxysilane represented by the following formula (4), a hydrolyzable silane represented by the following formula (5), and other hydrolyzable silanes.
• the hydrolytic condensation product used in the composition for forming a resist underlayer film of the present invention can be a product of hydrolytic condensation of a hydrolyzable silane mixture containing a silane compound represented by the following formula (1). .
• R 1 is a group bonded to a silicon atom and represents an organic group containing a succinic anhydride skeleton.
• the organic group for R 1 is not particularly limited as long as it is an organic group containing the above skeleton.
• organic groups containing a succinic anhydride skeleton include not only the skeleton itself, but also organic groups in which one or more hydrogen atoms in an alkyl group are substituted with a succinic anhydride skeleton.
• the alkyl group in which a hydrogen atom is substituted by the succinic anhydride skeleton or the like is not particularly limited, and may be linear, branched, or cyclic, and usually has 40 carbon atoms. Below, for example, 30 or less, more for example, 20 or less, or 10 or less. Specific examples of the linear or branched alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl and t-butyl.
• n-pentyl group 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl -n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3- methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2 , 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group
• cyclic alkyl group examples include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group and a 2-methyl-cyclobutyl group.
• Examples of the organic group for R 1 include monovalent groups represented by the following formula (1-1).
• R 401 represents, for example, a divalent alkylene group derived by removing one hydrogen atom from the linear, branched or cyclic alkyl group described above. * represents a bond that bonds with a silicon atom.
• R 2 is a group that bonds to a silicon atom and is independently of each other an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or a substituted alkoxyalkyl groups, or organic groups including epoxy, acryloyl, methacryloyl, mercapto, amino, amido, alkoxy, sulfonyl, or cyano groups, or combinations thereof.
• alkyl group for R 2 in formula (1) examples include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n -butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group , 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,
• Cyclic alkyl groups can also be used.
• Examples of cyclic alkyl groups having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1 -methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2- ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group , 1,2-dimethyl-cyclobutyl group, 1,3-di
• a halogenated alkyl group for R 2 in formula (1) refers to an alkyl group substituted with a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and specific examples of the alkyl group are the same as those described above.
• the number of carbon atoms in the halogenated alkyl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, still more preferably 10 or less.
• halogenated alkyl groups include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, bromodifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 1,1-difluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl group, 2,2 , 3,3-tetrafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1,1,1,3,3,3-hexafluoropropan-2-yl group, 3- Examples include, but are not limited to, bromo-2-methylpropyl group, 4-bromobutyl group, perfluoropentyl group and the like.
• An alkoxyalkyl group for R 2 in formula (1) refers to an alkyl group substituted with an alkoxy group. Specific examples of the alkyl group are the same as those mentioned above. Specific examples of alkoxy groups include alkoxy groups having straight, branched or cyclic alkyl moieties having 1 to 20 carbon atoms.
• linear or branched alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n- pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n -pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2- dimethyl-n-butoxy group, 2,3-
• cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl- cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclo butoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobut
• the number of carbon atoms in the alkoxyalkyl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, still more preferably 10 or less.
• Specific examples of the alkoxyalkyl group include, but are not limited to, lower alkyloxy lower alkyl groups such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group and ethoxymethyl group. .
• substituents in the alkyl group, halogenated alkyl group, or alkoxyalkyl group include alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, aryl oxy group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, alkoxy group, aralkyloxy group and the like.
• specific examples of the alkyl group, halogenated alkyl group, alkoxyalkyl group, and alkoxy group and the preferred number of carbon atoms thereof are the same as those described above.
• Examples of the aryl group mentioned in the above substituent include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, and a p-chlorophenyl group.
• Examples of the aralkyl group mentioned in the above substituent include phenylmethyl group (benzyl group), 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n -pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, 10-phenyl-n-decyl group, etc. These include, but are not limited to:
• the halogenated aryl group mentioned in the above substituent is an aryl group substituted with a halogen atom, and specific examples of such an aryl group are the same as those mentioned above.
• Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.
• the number of carbon atoms in the halogenated aryl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• halogenated aryl groups include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group and 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2, 3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5- tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2-fluoro
• the halogenated aralkyl group mentioned in the above substituent is an aralkyl group substituted with a halogen atom, and specific examples of such an aralkyl group and a halogen atom are the same as those mentioned above.
• the number of carbon atoms in the halogenated aralkyl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• Specific examples of halogenated aralkyl groups include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl and 2,5-difluorobenzyl.
• the aryloxy group mentioned in the above substituent is a group to which an aryl group is bonded through an oxygen atom (--O--), and specific examples of such an aryl group include the same as those mentioned above.
• the number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less. Specific examples thereof include a phenoxy group, naphthalene- Examples include, but are not limited to, 2-yloxy groups and the like.
• the substituents may be combined to form a ring.
• the alkoxyaryl group mentioned in the above substituent is an aryl group substituted with an alkoxy group, and specific examples of such alkoxy group and aryl group are the same as those mentioned above.
• the number of carbon atoms in the alkoxyaryl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• alkoxyaryl groups include, for example, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-(1-ethoxy)phenyl group, 3-(1-ethoxy)phenyl group, 4 -(1-ethoxy)phenyl group, 2-(2-ethoxy)phenyl group, 3-(2-ethoxy)phenyl group, 4-(2-ethoxy)phenyl group, 2-methoxynaphthalen-1-yl group, 3 -Methoxynaphthalen-1-yl group, 4-methoxynaphthalen-1-yl group, 5-methoxynaphthalen-1-yl group, 6-methoxynaphthalen-1-yl group, 7-methoxynaphthalen-1-yl group and the like Examples include, but are not limited to:
• the alkoxyaralkyl group mentioned in the above substituent is an aralkyl group substituted with an alkoxy group, and specific examples of such alkoxy group and aralkyl group are the same as those mentioned above.
• the number of carbon atoms in the alkoxyaralkyl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• Specific examples of the alkoxyaralkyl group include, but are not limited to, 3-(methoxyphenyl)benzyl group, 4-(methoxyphenyl)benzyl group and the like.
• alkenyl groups mentioned in the above substituents include optionally substituted alkenyl groups, for example, alkenyl groups having 2 to 10 carbon atoms. More specifically, ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl -1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3- pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2- propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group
• the aralkyloxy group mentioned in the above substituent is a group derived by removing a hydrogen atom from the hydroxy group of aralkyl alcohol, and specific examples of such an aralkyl group are the same as those mentioned above. .
• the number of carbon atoms in the aralkyloxy group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• Specific examples of aralkyloxy groups include phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group and 5-phenyl-n.
• -pentyloxy group 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, 10-phenyl-n- Examples include, but are not limited to, a decyloxy group and the like.
• Examples of the organic group containing an epoxy group for R 2 in formula (1) include glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group and epoxycyclohexyl group. It is not limited to these.
• Examples of the organic group containing an acryloyl group for R 2 in formula (1) include, but are not limited to, an acryloylmethyl group, an acryloylethyl group, an acryloylpropyl group, and the like.
• Examples of the organic group containing a methacryloyl group for R 2 in formula (1) include, but are not limited to, a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
• the organic group containing a mercapto group in R 2 of formula (1) includes, but is not limited to, an ethylmercapto group, a butylmercapto group, a hexylmercapto group, an octylmercapto group, and the like.
• the organic group containing an amino group in R 2 of formula (1) includes, but is not limited to, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, and the like.
• Examples of the organic group containing an alkoxy group for R 2 in the above formula (1) include, but are not limited to, a methoxymethyl group and a methoxyethyl group. However, groups in which an alkoxy group is directly bonded to a silicon atom are excluded.
• the organic group containing a sulfonyl group for R 2 in formula (1) includes, but is not limited to, a sulfonylalkyl group and a sulfonylaryl group.
• Examples of the organic group containing a cyano group for R 2 in formula (1) include, but are not limited to, a cyanoethyl group and a cyanopropyl group.
• R 3 is a silicon-bonded group or atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom.
• alkoxy group and halogen atom include the same ones as described above.
• An aralkyloxy group is a group derived by removing a hydrogen atom from a hydroxy group of an aralkyl alcohol, and specific examples of such an aralkyl group are the same as those described above.
• the number of carbon atoms in the aralkyloxy group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• Specific examples of aralkyloxy groups include phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group and 5-phenyl-n.
• -pentyloxy group 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, 10-phenyl-n- Examples include, but are not limited to, a decyloxy group and the like.
• An acyloxy group is a group derived by removing a hydrogen atom from a carboxylic acid group of a carboxylic acid compound, typically by removing a hydrogen atom from a carboxylic acid group of an alkylcarboxylic acid, an arylcarboxylic acid or an aralkylcarboxylic acid.
• Examples include, but are not limited to, derivatized alkylcarbonyloxy, arylcarbonyloxy or aralkylcarbonyloxy groups.
• Specific examples of the alkyl group, aryl group and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid and aralkylcarboxylic acid are the same as those mentioned above.
• acyloxy groups include acyloxy groups having 2 to 20 carbon atoms.
• a represents 1, b represents an integer of 0-2, and 4-(a+b) represents an integer of 1-3.
• b preferably represents 0 or 1, more preferably 0;
• the compound represented by the above formula (1) include, for example, [(3-trimethoxysilyl)propyl]succinic anhydride, [(3-triethoxysilyl)propyl]succinic anhydride, [( Examples include silane compounds containing a succinic anhydride skeleton such as 3-trimethoxysilyl)ethyl]succinic anhydride and [(3-trimethoxysilyl)butyl]succinic anhydride.
• the hydrolytic condensation product used in the composition for forming a resist underlayer film of the present invention can be a product of hydrolytic condensation of a hydrolyzable silane mixture containing a silane compound represented by the following formula (2). .
• R 4 is a group bonded to a silicon atom and represents a monovalent group represented by the following formula (2-1).
• R 201 to R 202 each independently represent an organic group containing a hydrogen atom or an optionally substituted alkyl group, and R 203 represents an optionally substituted alkylene group.
• * represents a bond that bonds to a silicon atom.
• the optionally substituted alkyl group in the monovalent group represented by formula (2-1) for R 4 is the substituted alkyl group described for R 2 in formula (1) above. It is the same as the alkyl group which is good.
• organic groups containing optionally substituted alkyl groups include optionally substituted alkyl groups.
• the optionally substituted alkylene group in the monovalent group represented by the formula (2-1) of R 4 means that the optionally substituted alkyl group further has one hydrogen atom.
• linear alkylene group 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group , 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, branched alkylene groups such as 1-ethyltrimethylene group, 1,2-cyclopropipanediyl group, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl group, cyclic alkylene such as 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, etc., -CH 2 OCH 2 -, -CH 2 CH 2 OCH 2 -, -CH 2 CH 2 OCH2CH2- , -CH2CH2CH2OCH2CH2- , -CH2CH2OCH2CH2CH2- , -CH2CH2CH2OCH2CH2CH
• R 5 is the same as R 2 in formula (1) above.
• R6 is the same as R3 in formula (1) above.
• a represents 1, b represents an integer of 0-2, and 4-(a+b) represents an integer of 1-3.
• b preferably represents 0 or 1, more preferably 0;
• Specific examples of the compound represented by the above formula (2) include silane compounds containing alkylphosphonic acids such as diethyl [(3-triethoxysilyl)ethyl]phosphonate.
• the hydrolytic condensate used in the composition for forming a resist underlayer film of the present invention can further contain a hydrolyzable silane represented by the following formula (3).
• R7 is a group bonded to a silicon atom and represents an organic group containing an alkenyl group.
• the organic group for R 7 is not particularly limited as long as it is an organic group containing the above groups.
• an organic group containing an alkenyl group includes not only the alkenyl group itself, but also an organic group in which one or more hydrogen atoms in an alkyl group are substituted with an alkenyl group.
• alkenyl group for R 7 examples include optionally substituted alkenyl groups as described for R 2 in formula (1) above.
• alkenyl groups having 2 to 10 carbon atoms are mentioned. More specifically, ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl -1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3- pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2- propenyl group, 2-methyl-1-butenyl group,
• R 8 is the same as R 2 in formula (1) above.
• R9 is the same as R3 in formula (1) above.
• a represents 1, b represents an integer of 0-2, and 4-(a+b) represents an integer of 1-3.
• b preferably represents 0 or 1, more preferably 0;
• the compound represented by formula (3) examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyl Dichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, ⁇ -glycide Xypropylvinyldimethoxysilane, ⁇ -glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyl
• the hydrolytic condensate used in the composition for forming a resist underlayer film of the present invention can further contain a hydrolyzable silane represented by the following formula (4).
• R 10 is a silicon-bonded group or atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. Specific examples of the alkoxy group, aralkyloxy group, and acyloxy group are the same as those described above.
• hydrolyzable silanes represented by formula (4) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n- Butoxysilane can be mentioned.
• the hydrolytic condensate used in the composition for forming a resist underlayer film of the present invention can further contain a hydrolyzable silane represented by the following formula (5).
• R 11 is a group that bonds to a silicon atom and is at least one selected from the group consisting of an aryl group, an optionally substituted amino group, and a group represented by formula (5-2) described later. represents an organic group containing groups.
• the organic group for R 11 is not particularly limited as long as it is an organic group containing the above groups.
• an aryl group and an organic group containing a group represented by the formula (5-2) described later, not only the group itself, but also one or more hydrogen atoms in the alkyl group are an aryl group and a group represented by the formula (5) described later.
• Alkyl groups are preferred as substituents for the optionally substituted amino group defined by R 11 . It is particularly preferred that an alkyl group having 1 to 4 carbon atoms is substituted.
• aryl group for R 11 examples include optionally substituted aryl groups, such as aryl groups having 6 to 20 carbon atoms. More specifically, the aryl group includes a phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, as described for R 2 in formula (1) above.
• the group containing the aryl group includes an optionally substituted aralkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyaryl groups, optionally substituted alkoxyaralkyl groups, and the like.
• the aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such an aryl group and an alkyl group are the same as those described above.
• the number of carbon atoms in the aralkyl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• aralkyl groups include phenylmethyl group (benzyl group ), 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl- n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, Examples include, but are not limited to, 10-phenyl-n-decyl group and the like.
• the above halogenated aryl group is an aryl group substituted with a halogen atom, and specific examples of such an aryl group include the same groups as those described above.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• the number of carbon atoms in the halogenated aryl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• halogenated aryl groups include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, as described for R 2 in formula (1) above.
• the halogenated aralkyl group is an aralkyl group substituted with a halogen atom, and specific examples of such an aralkyl group and a halogen atom are the same as those described above.
• the number of carbon atoms in the halogenated aralkyl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• Specific examples of halogenated aralkyl groups include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, as described for R 2 in formula (1) above.
• 2,4-difluorobenzyl group 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group , 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,4,6-trifluorobenzyl group, 2,3,4 ,5-tetrafluorobenzyl group, 2,3,4,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluorobenzyl group, 2,3,4,5,6-pentafluorobenzyl group and the like
• Examples include, but are not limited to:
• alkoxyaryl group is an aryl group substituted with an alkoxy group, and specific examples of such aryl groups and alkoxy groups are the same as those described above.
• the number of carbon atoms in the alkoxyaryl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• Specific examples of the alkoxyaryl group include, for example, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-(1-ethoxy), as described for R 2 in formula (1) above.
• phenyl group 3-(1-ethoxy)phenyl group, 4-(1-ethoxy)phenyl group, 2-(2-ethoxy)phenyl group, 3-(2-ethoxy)phenyl group, 4-(2-ethoxy) phenyl group, 2-methoxynaphthalene-1-yl group, 3-methoxynaphthalene-1-yl group, 4-methoxynaphthalene-1-yl group, 5-methoxynaphthalene-1-yl group, 6-methoxynaphthalene-1- Examples include, but are not limited to, an yl group, a 7-methoxynaphthalen-1-yl group, and the like.
• the alkoxyaralkyl group is an aralkyl group substituted with an alkoxy group, and specific examples of such alkoxy and aralkyl groups are the same as those described above.
• the number of carbon atoms in the alkoxyaralkyl group is not particularly limited, it is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.
• Specific examples of the alkoxyaralkyl group include, but are not limited to, 3-(methoxyphenyl)benzyl group, 4-(methoxyphenyl)benzyl group and the like.
• Examples of the optionally substituted amino group for R 11 include an amino group and an alkylamino group substituted with an alkyl group having 1 to 4 carbon atoms. More specific examples include amino group, aminomethyl group, aminoethyl group, dimethylaminoethyl group, dimethylaminopropyl group and the like.
• X 101 independently represents any one of the following formulas (5-3) to (5-5), and the ketone group in the following formulas (5-4) and (5-5)
• the carbon atom is bonded to the nitrogen atom to which R 102 in formula (5-2) is bonded.
• R 103 to R 107 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an epoxy or an organic group containing a sulfonyl group, specific examples of an optionally substituted alkyl group and an optionally substituted alkenyl group, and suitable number of carbon atoms, etc. are related to R 1 , succinic anhydride skeleton, etc.
• Examples of the alkyl group and the alkenyl group mentioned above as the alkyl group in which the hydrogen atom is substituted with are the same as those mentioned above.
• the organic group containing an epoxy group includes, but is not limited to, glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, epoxycyclohexyl group, and the like.
• organic groups containing a sulfonyl group include, but are not limited to, sulfonylalkyl groups and sulfonylaryl groups.
• each R 101 independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group.
• specific examples of an optionally substituted alkyl group, an optionally substituted alkenyl group, an epoxy group or an organic group containing an epoxy group preferred number of carbon atoms, etc
• alkyl group which may be substituted an alkyl group having a terminal hydrogen atom substituted with a vinyl group is preferable, and specific examples thereof include an allyl group, a 2-vinylethyl group, and a 3-vinylpropyl group. , 4-vinylbutyl group and the like.
• the alkylene group is a divalent group derived by removing one more hydrogen atom from the alkyl group, and may be linear, branched, or cyclic, and the number of carbon atoms in the alkylene group is particularly Although not limited, it is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and still more preferably 10 or less.
• the alkylene group of R 102 may have one or more selected from a sulfide bond, an ether bond and an ester bond at the terminal or in the middle, preferably in the middle.
• alkylene groups include linear groups such as methylene, ethylene, trimethylene, methylethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and decamethylene groups.
• alkylene group 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1 , 2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, branched alkylene groups such as 1-ethyltrimethylene group, 1,2-cyclopropipanediyl group, 1,2-cyclobutanediyl, 1, 3-cyclobutanediyl group, cyclic alkylene such as 1,2-cyclohexanediyl and 1,3-cyclohexanediyl, -CH 2 OCH 2 -, -CH 2 CH 2 OCH 2 -, -CH 2 CH 2 OCH 2 CH2- , -CH2CH2CH2OCH2CH2- , -CH2CH2OCH2CH2CH2- , -CH2CH2CH2OCH2CH2CH2- ,
• the hydroxyalkylene group is obtained by replacing at least one hydrogen atom of the above alkylene group with a hydroxy group.
• a hydroxymethylene group a 1-hydroxyethylene group, a 2-hydroxyethylene group, a -dihydroxyethylene group, 1-hydroxytrimethylene group, 2-hydroxytrimethylene group, 3-hydroxytrimethylene group, 1-hydroxytetramethylene group, 2-hydroxytetramethylene group, 3-hydroxytetramethylene group, 4-hydroxy tetramethylene group, 1,2-dihydroxytetramethylene group, 1,3-dihydroxytetramethylene group, 1,4-dihydroxytetramethylene group, 2,3-dihydroxytetramethylene group, 2,4-dihydroxytetramethylene group, 4 , 4-dihydroxytetramethylene group and the like, but are not limited to these.
• R 11 is selected from the group consisting of a phenyl group, a diaminopropyl group, and an isocyanuric acid skeleton (in formula (5-2), X 101 represents a group represented by formula (5-5)) A group containing at least one selected is preferred.
• R 12 is the same as R 2 in formula (1) above.
• R 13 is the same as R 3 in formula (1) above.
• a represents 1, b represents an integer of 0-2, and 4-(a+b) represents an integer of 1-3.
• b preferably represents 0 or 1, more preferably 0;
• the compound represented by formula (5) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyl Dichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane , diphenyldiethoxysilane, diphenyldichlorosilane, diphenyld
• a silane compound in which R 11 in the formula is an organic group containing a group represented by the above formula (5-2) is a commercially available product. You may use it and it can also synthesize
• Specific examples of the silane compound containing an organic group containing the group represented by the above formula (5-2) include, but are not limited to, the compounds shown below.
• examples of the silane compound represented by formula (5) above include aryl group-containing silane compounds represented by formulas (A-1) to (A-41).
• hydrolyzable silanes hydrolyzable silanes
• the above hydrolyzable silane mixture is added with the above formula (1) or (2), or optionally (3), (4) or (5).
• other silane compounds represented by the following formula (6) other hydrolyzable silanes can be used.
• R 14 is a group that bonds to a silicon atom and is independently of each other an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or a substituted or an organic group including an epoxy, acryloyl, methacryloyl, mercapto, amido, alkoxy, sulfonyl, or cyano group, or a combination thereof.
• R 15 is a group or atom bonded to a silicon atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. and c represents an integer of 1-3.
• each group in R 14 and the preferred number of carbon atoms thereof include the groups and the number of carbon atoms described above for R 2 .
• Specific examples of each group in R 15 and the preferred number of carbon atoms thereof include the groups and atoms and the number of carbon atoms described above for R 3 .
• hydrolyzable silanes represented by formula (6) include methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamine roxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane , ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -gly
• hydrolyzable silane mixture may contain other silane compounds (hydrolyzable silanes) other than those listed above as long as the effects of the present invention are not impaired.
• the composition for forming a resist underlayer film of the present invention contains the hydrolytic condensate of the hydrolyzable silane mixture.
• the composition for forming a resist underlayer film of the present invention contains at least a hydrolytic condensate of the hydrolyzable silane mixture.
• the hydrolytic condensate contained in the composition for forming a resist underlayer film of the present invention is a silane represented by formula (1) or formula (2), and optionally represented by formula (3).
• Hydrolyzable silanes represented by formula (4) hydrolyzable silanes represented by formula (5), other hydrolyzable silanes represented by formula (6), or Hydrolytic condensates obtained using hydrolyzable silanes other than those represented by these formulas are included.
• the charged amount of the silane compound represented by formula (1) is equal to all the silane compounds contained in the hydrolyzable silane mixture ( Hydrolyzable silane) can be, for example, 0.1 to 30 mol % with respect to 100 mol % charged amount.
• the charged amount of the silane compound represented by formula (2) is equal to all the silane compounds contained in the hydrolyzable silane mixture ( Hydrolyzable silane) can be, for example, 0.1 to 30 mol % with respect to 100 mol % charged amount.
• the charged amount of the silane compound represented by formula (3) is equal to all the silane compounds contained in the hydrolyzable silane mixture ( Hydrolyzable silane) can be, for example, 15 to 50 mol % with respect to 100 mol % charged amount.
• the charged amount of the silane compound represented by formula (4) is equal to all the silane compounds contained in the hydrolyzable silane mixture ( Hydrolyzable silane) can be, for example, 30 to 70 mol %, or 25 to 45 mol % with respect to 100 mol % charged amount.
• the compound represented by formula (5) is used in the hydrolyzable silane mixture (for example, when a silane compound represented by formula (5) in which R 11 is an aryl group is used), the compound represented by formula (5) is
• the charged amount of the silane compound can be, for example, 0.01 to 5 mol% with respect to 100 mol% charged amount of all the silane compounds (hydrolyzable silane) contained in the hydrolyzable silane mixture. .
• the hydrolytic condensate of the above hydrolyzable silane mixture can have a weight average molecular weight of, for example, 500 to 1,000,000.
• the weight average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and still more preferably 100,000 or less. It is preferably 700 or more, more preferably 1,000 or more, from the viewpoint of compatibility between storage stability and coatability.
• a weight average molecular weight is a molecular weight obtained by polystyrene conversion by GPC analysis.
• a GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.) is used, and the column temperature is adjusted to It can be carried out at 40° C., using tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 1.0 mL/min, and using polystyrene (manufactured by Showa Denko KK) as a standard sample.
• the hydrolytic condensate of the hydrolyzable silane mixture is obtained by hydrolyzing and condensing the above silane compound (hydrolyzable silane).
• the above silane compound (hydrolyzable silane) includes an alkoxy group, an aralkyloxy group, an acyloxy group, and a halogen atom directly bonded to a silicon atom, that is, an alkoxysilyl group, an aralkyloxysilyl group, and an acyloxysilyl group, which are hydrolyzable groups. groups, including silyl halide groups.
• water is usually used in an amount of 0.5 to 100 mol, preferably 1 to 10 mol, per 1 mol of hydrolyzable group.
• a hydrolysis catalyst may be used for the purpose of promoting the reaction, or the hydrolysis and condensation may be performed without using a hydrolysis catalyst.
• a hydrolysis catalyst it can be used in an amount of usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, per 1 mol of hydrolyzable group.
• the reaction temperature for hydrolysis and condensation is generally room temperature or higher and the reflux temperature or lower of the organic solvent that can be used for hydrolysis at normal pressure, for example, 20 to 110°C, or for example, 20 to 80°C.
• the hydrolysis can be either complete hydrolysis, i.e. converting all hydrolyzable groups to silanol groups, or partial hydrolysis, i.e. leaving unreacted hydrolyzable groups. good.
• Hydrolysis catalysts that can be used for hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
• Metal chelate compounds as hydrolysis catalysts include, for example, triethoxy mono(acetylacetonato)titanium, tri-n-propoxy mono(acetylacetonato)titanium, tri-i-propoxy mono(acetylacetonato)titanium, tri -n-butoxy mono(acetylacetonato)titanium, tri-sec-butoxy mono(acetylacetonato)titanium, tri-t-butoxy mono(acetylacetonato)titanium, diethoxy bis(acetylacetonato)titanium , di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonate) titanium, di-sec-butoxy bis (acetylacetonato)titanium, di-t-butoxy bis(acet
• Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacine.
• Acid gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Acids include, but are not limited to, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like.
• inorganic acids as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
• Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, dia Zabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide etc., but not limited to these.
• Inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide
• metal chelate compounds organic acids, and inorganic acids are preferred, and these may be used singly or in combination of two or more.
• nitric acid can be preferably used as a hydrolysis catalyst in the present invention.
• nitric acid By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, changes in the molecular weight of the hydrolyzed condensate can be suppressed. It has been found that the stability of hydrolytic condensates in liquid depends on the pH of the solution. As a result of intensive studies, it was found that the pH of the solution becomes a stable region by using an appropriate amount of nitric acid.
• An organic solvent may be used as a solvent for the hydrolysis and condensation, and specific examples include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2 , 2,4-trimethylpentane, n-octane, i-octane, cyclohexane, aliphatic hydrocarbon solvents such as methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i- Aromatic hydrocarbon solvents such as propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene; methanol, ethanol,
• reaction solution is diluted or concentrated, neutralized, and treated with an ion-exchange resin to hydrolyze the acids, bases, etc. used in the hydrolysis and condensation.
• Catalyst can be removed.
• by-products such as alcohol and water, and the used hydrolysis catalyst can be removed from the reaction solution by vacuum distillation or the like.
• the hydrolytic condensate (hereinafter also referred to as polysiloxane) thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and this is directly used in the composition for forming a resist underlayer film described later.
• the obtained polysiloxane varnish may be subjected to solvent replacement or may be diluted with a solvent as appropriate.
• the polysiloxane varnish thus obtained may have a solid concentration of 100% by distilling off the organic solvent if the storage stability is not poor.
• the organic solvent used for solvent substitution, dilution, etc. of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane mixture.
• the diluting solvent is not particularly limited, and one or two or more can be arbitrarily selected and used.
• composition for forming a resist underlayer film of the present invention has a specific additive having a chemical structure containing a solvent and a cation AX + and an anion AZ ⁇ in addition to the hydrolysis condensate (polysiloxane) of the above hydrolyzable silane mixture.
• Agent (Compound A) and other components can be included.
• the solvent used in the composition for forming a resist underlayer film of the present invention can be used without particular limitation as long as it can dissolve the solid content in the composition for forming a resist underlayer film.
• Such a solvent is not particularly limited as long as it dissolves the hydrolytic condensate of the hydrolyzable silane mixture, the specific additive (compound A), and other components.
• methyl cellosolve acetate ethyl cellosolve acetate
• propylene glycol propylene glycol monomethyl ether (1-methoxy-2-propanol)
• propylene glycol monoethyl ether 1,3-bis(trimethoxy-2-propanol)
• methyl isobutyl carbinol methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol.
• 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, cyclo pentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3- ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl
• the composition for forming a resist underlayer film of the present invention may contain water as a solvent.
• water When water is included as a solvent, its content is, for example, 30% by mass or less, preferably 20% by mass or less, and even more preferably 15% by mass or less, relative to the total mass of the solvent contained in the composition. can.
• the resist underlayer film-forming composition containing the hydrolytic condensate (polysiloxane) of the hydrolyzable silane mixture further contains a specific additive (compound A) having a chemical structure containing the cation AX + and the anion AZ ⁇ .
• a resist underlayer film exhibiting superior solubility in an alkaline solution (basic chemical solution) can be formed.
• a specific additive is a compound having a chemical structure comprising a cation AX + and an anion AZ ⁇ , the anion having a molecular weight of 65 or greater.
• cation means a positively charged atom or a positively charged group of atoms
• anion means a negatively charged atom or a negatively charged means an atomic group.
• the solubility of the resist underlayer film in an alkaline solution is increased because the anion of the specific additive (compound A) This is not because the three-dimensional cross-linking does not proceed due to the presence of the species between the hydrolyzed condensates (polymers), which inhibits the cross-linked bonds of the hydrolyzed condensates, or the anion species itself binds and caps. I'm guessing.
• the molecular weight of the anion AZ ⁇ is more preferably 65 or more from the viewpoint of suppressing condensation. Moreover, from the viewpoint of maintaining dry etching resistance, it is more preferably 500 or less.
• the anion AZ ⁇ may be present extramolecularly or intramolecularly with the cation AX + .
• the anion AZ ⁇ is present outside the cation AX + molecule means that the anion AZ ⁇ is not bound to the cation AX + via a covalent bond and is an independent structural unit from the cation AX + refers to the state of existence.
• Forms of compound A as described above include, for example, salts.
• the anion present outside the cation molecule is also referred to as a counter anion.
• the anion AZ ⁇ may be bonded to the cation AX + via a covalent bond. That is, the form of compound A may be an inner salt (also referred to as a zwitterion).
• the type of anion AZ ⁇ is not particularly limited as long as it satisfies the condition that the molecular weight of the anion is 65 or more.
• Z represents an aromatic ring, a cyclic alkane, or a cyclic alkene in a non-aromatic ring;
• R 501 represents an alkyl group that may be partially or wholly substituted with a fluorine atom,
• R 302 and R 303 independently represent an alkyl group,
• R 304 and R 305 independently represent an alkyl group.
• alkyl group aryl group, halogenated alkyl group, and aralkyl group are the same as those described above.
• substituent that may be substituted on the alkyl group or the like are the same as those described above.
• Specific additives include, for example, compounds having a sulfonate anion represented by the above formula (A).
• the compound having a sulfonate anion represented by the formula (A) includes not only compounds having an anion represented by the formula (A) outside the molecule, but also sulfobetaines such as laurylsulfobetaine and myristylsulfobetaine.
• it may be a compound having an anion represented by formula (A) in its molecule (see compounds (Add-6) and (Add-7) below).
• Specific additives include, for example, compounds having an anion containing a triazole skeleton represented by the above formula (B-1) or the above formula (B-2).
• Z represents an aromatic ring having 1 to 6 carbon atoms, a cyclic alkane, or a non-aromatic cyclic alkene.
• a compound having an anion represented by formula (B-2) is preferred, and Z is preferably an aromatic ring in formula (B-2). That is, a preferred embodiment of the specific additive (compound A) includes, for example, a compound having an anion containing a benzotriazole skeleton represented by (b-1) below.
• Specific additives include, for example, compounds represented by the above formula (C).
• R 501 represents an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group partially or wholly substituted with fluorine atoms, or a perfluoroalkyl group. Among them, R 501 is preferably a CF 3 group or a C 4 F 9 group.
• the specific additive (compound A) for example, a compound having an anion of bis(trifluoromethanesulfonyl)imide represented by (c-1) below is more preferable.
• Specific additives include, for example, compounds having a thiophosphate anion represented by the above formula (D).
• Specific additives include, for example, compounds having a phosphate anion represented by the above formula (E).
• Specific examples of the specific additive include, but are not limited to, compounds represented by the following formulas (Add-1) to (Add-11).
• the content thereof can be 1 to 30 parts by mass with respect to 100 parts by mass of the composition for forming a resist underlayer film.
• the composition for forming a resist underlayer film of the present invention can contain various additives (also referred to as other additives) that are components other than the specific additives described above, depending on the application of the composition.
• Other components (other additives) that can be blended in the composition for forming a resist underlayer film include, for example, curing catalysts (ammonium salts, phosphines, phosphonium salts, sulfonium salts, nitrogen-containing silane compounds, etc.), cross-linking agents, Cross-linking catalyst, stabilizer (organic acid, water, alcohol, etc.), organic polymer compound, acid generator, surfactant (nonionic surfactant, anionic surfactant, cationic surfactant, silicon surfactant agents, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, rheology adjusters, adhesion aids, resist underlayer films, anti-reflection films, pattern reversal films,
• Curing catalyst As the curing catalyst, ammonium salts, phosphines, phosphonium salts, sulfonium salts and the like can be used.
• the following salts described as curing catalysts may be added in the form of salts, or those that form salts in the composition (these are added as separate compounds at the time of addition, and those that form salts in the system ).
• n is an integer of 2 to 3
• H is a hydrogen atom
• N is a nitrogen atom
• Y - represents an anion
• R 31 , R 32 , R 33 and R 34 represent an alkyl group or an aryl group
• P represents a phosphorus atom
• Y- represents an anion
• R 31 , R 32 , R 33 and R 34 are each bonded to a phosphorus atom via a CP bond.
• R 35 , R 36 and R 37 represent an alkyl group or an aryl group
• S represents a sulfur atom
• Y- represents an anion
• R 35 , R 36 and R 37 each represent C—S and a tertiary sulfonium salt represented by ), which is bound to the sulfur atom by a bond.
• the compound of formula (D-1) above is a quaternary ammonium salt derived from an amine, where m is an integer of 2-11 and n is an integer of 2-3.
• R 21 of this quaternary ammonium salt represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms, such as ethyl group, propyl group, butyl group, etc. linear alkyl group, benzyl group, cyclohexyl group, cyclohexylmethyl group, dicyclopentadienyl group and the like.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ), alcoholate (—O ⁇ ) and other acid groups.
• the compound of formula (D-2) above is a quaternary ammonium salt represented by R 22 R 23 R 24 R 25 N + Y - .
• R 22 , R 23 , R 24 and R 25 of this quaternary ammonium salt are alkyl groups of 1 to 18 carbon atoms or aryl groups of 6 to 18 carbon atoms.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ). , alcoholate (—O ⁇ ) and other acid groups.
• the quaternary ammonium salts are commercially available, for example tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride. Ammonium, trimethylbenzylammonium chloride and the like are exemplified.
• the compound of formula (D-3) above is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 have 1 to 18 carbon atoms, and R 26 and R 27 The total number of carbon atoms is preferably 7 or more.
• R26 can be exemplified by a methyl group, ethyl group, propyl group, phenyl group and benzyl group, and R27 can be exemplified by a benzyl group, octyl group and octadecyl group.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ). , alcoholate (—O ⁇ ) and other acid groups.
• This compound can be obtained as a commercial product.
• imidazole compounds such as 1-methylimidazole and 1-benzylimidazole are reacted with alkyl and aryl halides such as benzyl bromide and methyl bromide. can be manufactured by
• the compound of formula (D-4) above is a quaternary ammonium salt derived from pyridine, wherein R 28 is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or It is an aryl group of numbers 6 to 18, and examples thereof include butyl, octyl, benzyl and lauryl groups.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ). , alcoholate (—O ⁇ ) and other acid groups.
• This compound can be obtained as a commercial product, and is produced, for example, by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide. can do.
• alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide.
• alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide.
• alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide.
• the compound of formula (D-5) above is a quaternary ammonium salt derived from a substituted pyridine typified by picoline and the like, and R 29 has 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms. or an aryl group having 6 to 18 carbon atoms such as a methyl group, an octyl group, a lauryl group and a benzyl group.
• R 30 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, for example, when it is a quaternary ammonium derived from picoline, R 30 is a methyl group.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ). , alcoholate (—O ⁇ ) and other acid groups.
• This compound is also commercially available, and for example, by reacting a substituted pyridine such as picoline with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or an aryl halide. can be produced by Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.
• the compound of formula (D-6) above is a tertiary ammonium salt derived from an amine, where m is an integer of 2-11 and n is an integer of 2-3.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ), alcoholate (—O ⁇ ) and other acid groups.
• This compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol.
• Carboxylic acids include formic acid and acetic acid.
• the anion (Y ⁇ ) is (HCOO ⁇ ), and when acetic acid is used, the anion (Y ⁇ ) is (CH 3 COO - ). Also, when phenol is used, the anion (Y ⁇ ) is (C 6 H 5 O ⁇ ).
• the compound of formula (D-7) above is a quaternary phosphonium salt having a structure of R 31 R 32 R 33 R 34 P + Y - .
• R 31 , R 32 , R 33 and R 34 are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms, preferably among the four substituents R 31 to R 34 and three are phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups can be exemplified, and the remaining one is an alkyl group having 1 to 18 carbon atoms, It is an aryl group.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ), alcoholate (—O ⁇ ) and other acid groups.
• This compound can be obtained as a commercial product, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, and trialkylbenzyl halides such as triethylbenzylphosphonium halide.
• Phosphonium triphenylmethylphosphonium halide, triphenylmonoalkylphosphonium halide such as triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritolylmonoarylphosphonium halide, or tritolylmonohalide
• Alkylphosphonium (wherein the halogen atom is a chlorine atom or a bromine atom) can be mentioned.
• triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide
• triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide
• halogens such as tritolylmonophenylphosphonium halide
• Tritolylmonoalkylphosphonium halides halogen atoms are chlorine atoms or bromine atoms
• tritolylmonoarylphosphonium halides and tritolylmonomethylphosphonium halides are preferred.
• Phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine and phenylphosphine, and secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine and diphenylphosphine. , trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine and the like.
• the compound of formula (D-8) above is a tertiary sulfonium salt having a structure of R 35 R 36 R 37 S + Y - .
• R 35 , R 36 and R 37 are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms, preferably two of the three substituents of R 35 to R 37 are phenyl or a substituted phenyl group such as a phenyl group and a tolyl group, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. be.
• Anions (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), iodine ion (I ⁇ ), carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ), alcoholate (—O ⁇ ), maleate anion, nitrate anion and the like.
• This compound is commercially available and includes trialkylsulfonium halides such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, and dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halide.
• diphenylmethylsulfonium halide, diphenylethylsulfonium halide and other diphenyl monoalkylsulfonium halides triphenylsulfonium halides (halogen atoms are chlorine atoms or bromine atoms), tri-n-butylsulfonium carboxylate, tri-n- trialkylsulfonium carboxylates such as propylsulfonium carboxylate; dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate; diphenylmethylsulfonium carboxylate; is mentioned.
• triphenylsulfonium halides and triphenylsulfonium carboxylates can be preferably used.
• Nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilipropyl)-4,5-dihydroimidazole.
• a curing catalyst When a curing catalyst is used, it is 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight, or 0.01 to 3 parts by weight, based on 100 parts by weight of polysiloxane. .
• the stabilizing agent can be added for the purpose of stabilizing the hydrolyzed condensate of the hydrolyzable silane mixture, and specific examples thereof include adding an organic acid, water, alcohol, or a combination thereof. can be done.
• the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid and salicylic acid. Among them, oxalic acid and maleic acid are preferred.
• the amount added is 0.1 to 5.0% by mass based on the mass of the hydrolytic condensate of the hydrolyzable silane mixture.
• These organic acids can also act as pH adjusters.
• water pure water, ultrapure water, ion-exchanged water, or the like can be used, and when used, the amount added is 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the composition for forming a resist underlayer film.
• the above alcohol is preferably one that is easily scattered (volatilized) by heating after application, and examples thereof include methanol, ethanol, propanol, i-propanol, and butanol.
• the amount added can be 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the composition for forming a resist underlayer film.
• Organic polymer By adding the organic polymer compound to the composition for forming a resist underlayer film, the dry etching rate (decrease in film thickness per unit time) of the film (resist underlayer film) formed from the composition, Also, the attenuation coefficient, refractive index, etc. can be adjusted.
• the organic polymer compound is not particularly limited, and is appropriately selected from various organic polymers (condensation polymer and addition polymer) depending on the purpose of addition.
• addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolak, naphthol novolak, polyether, polyamide, and polycarbonate.
• organic polymers containing aromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings and heteroaromatic rings that function as light-absorbing sites are also used when such functions are required. can be preferably used.
• organic polymeric compounds include addition polymerizable compounds such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether and N-phenylmaleimide.
• addition polymerized polymers containing monomers as their structural units and condensation polymerized polymers such as phenol novolacs and naphthol novolacs.
• the polymer compound may be either a homopolymer or a copolymer.
• Addition-polymerizable monomers are used in the production of addition-polymerized polymers, and specific examples of such addition-polymerizable monomers include acrylic acid, methacrylic acid, acrylic ester compounds, methacrylic ester compounds, acrylamide compounds, methacrylic Examples include, but are not limited to, amide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, and the like.
• acrylic acid ester compounds include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthryl 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-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, glycidyl acrylate, etc
• methacrylate compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate.
• acrylamide compounds include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, N-anthrylacrylamide and the like. Not limited.
• methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide. etc., but not limited to these.
• vinyl compounds include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, vinyl Examples include, but are not limited to, anthracene.
• styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.
• Maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-hydroxyethylmaleimide, and the like.
• a polycondensation polymer when used as the polymer, such a polymer includes, for example, polycondensation of a glycol compound and a dicarboxylic acid compound.
• Glycol compounds include diethylene glycol, hexamethylene glycol, butylene glycol and the like.
• Dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, maleic anhydride and the like.
• Further examples include, but are not limited to, polyesters such as polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, polyamides, and polyimides.
• the organic polymer compound contains a hydroxy group, this hydroxy group can undergo a cross-linking reaction with a hydrolytic condensate or the like.
• the weight-average molecular weight of the above organic polymer compound can be usually 1,000 to 1,000,000.
• the weight average molecular weight thereof is, for example, 3,000 to 300,000, or 5,000, from the viewpoint of suppressing precipitation in the composition while sufficiently obtaining the effect of the function as a polymer. It can be ⁇ 300,000, or 10,000 to 200,000, and so on.
• Such organic polymer compounds may be used singly or in combination of two or more.
• the content thereof is determined as appropriate in consideration of the function of the organic polymer compound, etc., and cannot be unconditionally defined.
• the mass of the hydrolytic condensate of the mixture it can be in the range of 1 to 200% by mass, and from the viewpoint of suppressing precipitation in the composition, for example, 100% by mass or less, preferably 50% by mass or less. , more preferably 30% by mass or less, and from the viewpoint of sufficiently obtaining the effect, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more.
• acid generators include thermal acid generators and photoacid generators, and photoacid generators can be preferably used.
• Photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, and the like.
• thermal acid generators include tetramethylammonium nitrate and the like, but are not limited thereto.
• onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octane sulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl ) iodonium salt compounds such as iodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium Examples include, but are not limited to,
• sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-normalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. etc., but not limited to these.
• disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, and bis(2,4-dimethylbenzene).
• sulfonyl)diazomethane methylsulfonyl-p-toluenesulfonyldiazomethane, and the like, but are not limited thereto.
• the content thereof is determined as appropriate in consideration of the type of the acid generator and the like, and cannot be categorically defined. is in the range of 0.01 to 5% by mass relative to the mass of the hydrolytic condensate of, preferably 3% by mass or less, more preferably 3% by mass or less, more preferably from the viewpoint of suppressing precipitation of the acid generator in the composition. It is 1% by mass or less, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of sufficiently obtaining the effect.
• the acid generator may be used singly or in combination of two or more, and a photoacid generator and a thermal acid generator may be used in combination.
• Surfactants are effective in suppressing the occurrence of pinholes, striations, etc. when the composition for forming a resist underlayer film is applied to a substrate.
• the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon surfactants, fluorochemical surfactants, and UV curable surfactants.
• polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol
• Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate
• Nonionic surfactants such as sorbitan fatty acid esters, trade name Ftop (registered trademark)
• the content thereof is usually 0.0001 to 5% by mass based on the mass of the hydrolytic condensate of the hydrolyzable silane mixture. , preferably 0.001 to 4% by mass, more preferably 0.01 to 3% by mass.
• the rheology modifier mainly improves the fluidity of the composition for forming a resist underlayer film. It is added for the purpose of enhancement.
• Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, butyl i-decyl phthalate, di-n-butyl adipate, di-i-butyl adipate, di-i-octyl adipate, Adipic acid derivatives such as octyldecyl adipate, maleic acid derivatives such as di-n-butyl maleate, diethyl maleate and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate, normal butyl stearate and glyceryl stearate Examples include stearoyl phthal
• the adhesion aid mainly improves the adhesion between the substrate or the resist and the film (resist underlayer film) formed from the resist underlayer film-forming composition, and particularly suppresses/prevents peeling of the resist during development. added for a purpose.
• chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane
• alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane
• Disilazane, N,N'-bis(trimethylsilyl)urea dimethyltrimethylsilylamine, silazanes such as trimethylsilylimidazole, ⁇ -chloropropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane
• Heterocyclic compounds such as other silanes such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-
• bisphenol S or a bisphenol S derivative can be added in addition to an acid having one or more carboxylic acid groups such as the organic acid exemplified above as the ⁇ stabilizer>.
• Bisphenol S or a bisphenol S derivative is 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or 0.01 to 100 parts by mass of the hydrolytic condensate of the hydrolyzable silane mixture. 5 parts by mass.
• bisphenol S and bisphenol S derivatives are given below, but are not limited to these.
• the concentration of solids in the resist underlayer film-forming composition is, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, 0 .5 to 20.0% by mass.
• the solid content refers to the components excluding the solvent component from all the components of the composition.
• the content of the hydrolytic condensate of the hydrolyzable silane mixture in the solid content is usually 20% by mass to 100% by mass. is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and still more preferably 80% by mass, and its upper limit is preferably 99% by mass.
• the content of the hydrolyzed condensate of the hydrolyzable silane mixture in the composition can be, for example, 0.5 to 20.0% by mass.
• the composition for forming a resist underlayer film preferably has pH 2-5, more preferably pH 3-4.
• the composition for forming a resist underlayer film contains a hydrolytic condensate of the hydrolyzable silane mixture, a solvent, and, if desired, a specific additive (compound A) and other components when the specific additive is included. It can be produced by mixing (compound A) and other components. At this time, a solution containing a hydrolytic condensate or the like may be prepared in advance, and this solution may be mixed with a solvent, a specific additive (compound A), or other components. The mixing order is not particularly limited.
• a solvent may be added to a solution containing a hydrolytic condensate or the like and mixed, and a specific additive (compound A) or other components may be added to the mixture, and the solution containing the hydrolytic condensate or the like, A solvent, a specific additive (compound A) and other components may be mixed together. If necessary, additional solvent may be added at the end, or some components that are relatively soluble in the solvent may be left out of the mixture and added at the end, but aggregation of the components may occur. From the viewpoint of suppressing the separation and reproducibly preparing a composition having excellent uniformity, it is preferable to prepare a solution in which the hydrolyzed condensate and the like are well dissolved in advance and use it to prepare the composition.
• the hydrolyzed condensate or the like may aggregate or precipitate when mixed, depending on the type and amount of the solvent mixed together, the amount and properties of other components, and the like. Further, when preparing a composition using a solution in which a hydrolytic condensate or the like is dissolved, the hydrolytic condensate or the like is added so that the amount of the hydrolytic condensate or the like in the finally obtained composition is a desired amount. Also note that the concentration of the solution and the amount to be used need to be determined. In the preparation of the composition, the composition may be appropriately heated as long as the components are not decomposed or altered.
• the composition for forming a resist underlayer film may be filtered using a submicrometer-order filter or the like in the middle of manufacturing the composition or after mixing all the components.
• composition for forming a resist underlayer film of the present invention can be suitably used as a composition for forming a resist underlayer film used in the lithography process.
• composition for forming a silicon-containing resist underlayer film of the second aspect contains a hydrolytic condensate of a hydrolyzable silane mixture and a specific additive (compound A) having a chemical structure containing a cation AX + and an anion AZ ⁇ .
• a composition for forming a resist underlayer film containing a hydrolytic condensate of a hydrolyzable silane mixture contains a specific additive (compound A) having a chemical structure containing a cation AX + and an anion AZ ⁇ .
• hydrolyzable silane that forms the hydrolytic condensate of the hydrolyzable silane mixture contained in the composition for forming a silicon-containing resist underlayer film of the second aspect is not particularly limited. All the silane compounds (hydrolyzable silanes) described in the section ⁇ Hydrolytic condensate of hydrolyzable silane mixture> in Containing resist underlayer film-forming composition) can be used.
• the hydrolyzable silane represented by the formula (1), the hydrolyzable silane represented by the formula (2), the hydrolyzable silane represented by the formula (3), and the hydrolyzable silane represented by the formula (4) Either a decomposable silane or a hydrolyzable silane represented by formula (5) may be included, or a hydrolyzable silane other than the hydrolyzable silanes represented by those formulas may be included.
• the difference between the hydrolytic condensate of the second aspect and the hydrolytic condensate of the first aspect is that the type of hydrolyzable silane contained in the hydrolyzable silane mixture is different from the specific hydrolyzable silane in the first aspect. is defined to include, whereas there is no particular limitation in the second aspect.
• the solubility of the resist underlayer film in an alkaline solution can be improved.
• the type of hydrolyzable silane contained in the decomposable silane mixture is not particularly limited. Any hydrolyzable silane can be used in the second aspect.
• the hydrolyzable silane mixture in the second aspect, the above ⁇ hydrolytic condensate of the hydrolyzable silane mixture of the composition for forming a silicon-containing resist underlayer film of the first aspect) >, various hydrolyzable silanes can be used.
• composition for forming a resist underlayer film of the second aspect also contains a solvent and other components in addition to the hydrolytic condensate of the hydrolyzable silane mixture (polysiloxane) and the specific additive (compound A). be able to.
• composition solid content concentration and preferred pH value of the composition for forming a resist underlayer film in the second aspect and the method for producing the composition for forming a resist underlayer film are described above (Formation of a silicon-containing resist underlayer film in the first aspect). composition).
• substrates used in the manufacture of precision integrated circuit elements e.g., semiconductor substrates such as silicon wafers coated with a silicon oxide film, silicon nitride film or silicon oxynitride film, silicon nitride substrates, quartz substrates, glass substrates (no Alkali glass, low alkali glass, crystallized glass), glass substrates with ITO (indium tin oxide) or IZO (indium zinc oxide) films, plastic (polyimide, PET, etc.) substrates, low dielectric
• the composition for forming a resist underlayer film of the present invention is applied onto a low-k material (low-k material) coated substrate, flexible substrate, etc.) by an appropriate coating method such as a spinner or a coater, and then applied on a hot plate or the like.
• the composition is cured to form a resist underlayer film.
• the resist underlayer film refers to a film formed from the composition for forming a resist underlayer film of the present invention.
• the firing conditions are appropriately selected from a firing temperature of 40° C. to 400° C. or 80° C. to 250° C. and a firing time of 0.3 minutes to 60 minutes.
• the firing temperature is 150° C. to 250° C. and the firing time is 0.5 minutes to 2 minutes.
• the film thickness of the resist underlayer film formed here is, for example, 10 nm to 1,000 nm, 20 nm to 500 nm, 50 nm to 300 nm, 100 nm to 200 nm, or 10 to 150 nm.
• the organic underlayer film is formed on the substrate, and then the resist underlayer film is formed thereon.
• the organic underlayer film used here is not particularly limited, and can be arbitrarily selected from those conventionally used in lithography processes.
• the pattern width of the photoresist film is narrowed, and the photoresist film is used to prevent pattern collapse. Even if the film is thinly coated, the substrate can be processed by selecting an appropriate etching gas, which will be described later.
• the resist underlayer film of the present invention can be processed by using a fluorine-based gas having a sufficiently high etching rate with respect to the photoresist film as an etching gas, and the resist underlayer film of the present invention can be sufficiently etched.
• a fluorine-based gas having a sufficiently high etching rate with respect to the photoresist film as an etching gas
• the resist underlayer film of the present invention can be sufficiently etched.
• an oxygen-based gas having a high etching rate as an etching gas
• the organic underlayer film can be processed.
• the substrate and coating method that can be used at this time are the same as those described above.
• a layer (resist film) of, for example, a photoresist material is formed on the resist underlayer film.
• the resist film can be formed by a well-known method, that is, by applying a coating-type resist material (for example, a composition for forming a photoresist film) on the resist underlayer film and baking it.
• the film thickness of the resist film is, for example, 10 nm to 10,000 nm, 100 nm to 2,000 nm, 200 nm to 1,000 nm, or 30 nm to 200 nm.
• the photoresist material used for the resist film formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure (for example, KrF excimer laser, ArF excimer laser, etc.). Both negative photoresist materials and positive photoresist materials can be used.
• a positive photoresist material composed of a novolac resin and a 1,2-naphthoquinonediazide sulfonic acid ester a chemically amplified photoresist composed of a binder having a group that decomposes with an acid to increase the alkali dissolution rate
• a photoacid generator for example, a positive photoresist material composed of a novolac resin and a 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist composed of a binder having a group that decomposes with an acid to increase the alkali dissolution rate.
• a chemically amplified photoresist material composed of a low-molecular-weight compound, an alkali-soluble binder, and a photoacid generator that decomposes with an acid to increase the alkali dissolution rate of the photoresist material
• a chemically amplified photoresist material composed of a binder having a group that causes a reaction, a low-molecular-weight compound that is decomposed by an acid to increase the alkali dissolution rate of the photoresist material, and a photoacid generator.
• the resist film formed on the resist underlayer film may be a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film) instead of the photoresist film.
• the composition for forming a silicon-containing resist underlayer film of the present invention can be used for forming a resist underlayer film for electron beam lithography or for forming a resist underlayer film for EUV lithography. It is particularly suitable as a composition for forming a resist underlayer film for EUV lithography.
• As the electron beam resist material either a negative type material or a positive type material can be used.
• Specific examples thereof include a chemically amplified resist material composed of an acid generator and a binder having a group that is decomposed by an acid to change the alkali dissolution rate;
• a chemically amplified resist material composed of a low-molecular-weight compound that changes the dissolution rate, a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, and a binder that decomposes with the acid to change the alkali dissolution rate of the resist material.
• non-chemically amplified resist materials made of binders Even when these electron beam resist materials are used, a resist film pattern can be formed in the same manner as when a photoresist material is used with an electron beam as the irradiation source.
• a methacrylate resin-based resist material can be used as the EUV resist material.
• the resist film formed on the resist underlayer film is exposed through a predetermined mask (reticle).
• KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), electron beam, etc. can be used for exposure.
• a post exposure bake can be performed if necessary.
• the post-exposure heating is performed under conditions appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 minutes to 10 minutes.
• a developer for example, an alkaline developer
• a developer for example, an alkaline developer
• alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
• alkaline aqueous solutions examples include alkaline aqueous solutions (alkali developers) such as aqueous solutions of amines such as amine, propylamine and ethylenediamine. Furthermore, a surfactant or the like can be added to these developers.
• alkali developers such as aqueous solutions of amines such as amine, propylamine and ethylenediamine.
• a surfactant or the like can be added to these developers.
• the development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.
• an organic solvent can be used as a developer, and development is performed with the developer (solvent) after exposure.
• the developer solvent
• the photoresist film in the unexposed portions is removed to form a pattern of the photoresist film.
• Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol mono Ethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl
• the resist underlayer film (intermediate layer) is removed, and then the patterned photoresist film and patterned resist underlayer film (intermediate layer) are removed.
• the organic underlayer film (lower layer) is removed, and finally, the patterned photoresist film (upper layer), the patterned resist underlayer film (intermediate layer), and the patterned
• the substrate is processed using the organic underlayer film (lower layer) as a protective film.
• gases such as ( C3F8 ), trifluoromethane, carbon monoxide, argon , oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane and dichloroborane can do. It is preferable to use a halogen-based gas for the dry etching of the resist underlayer film.
• a resist film (photoresist film) basically made of an organic substance is difficult to remove.
• a silicon-containing resist underlayer film containing a large amount of silicon atoms is quickly removed by a halogen-based gas. Therefore, reduction in the thickness of the photoresist film due to dry etching of the resist underlayer film can be suppressed. As a result, it becomes possible to use a thin photoresist film. Therefore, the dry etching of the resist underlayer film is preferably performed using a fluorine-based gas. 8 ), trifluoromethane, difluoromethane (CH 2 F 2 ), and the like, but are not limited to these.
• the removal of the organic underlayer film (lower layer) performed using a protective film is preferably performed by dry etching using an oxygen-based gas (oxygen gas, oxygen/carbonyl sulfide (COS) mixed gas, etc.). This is because the resist underlayer film of the present invention containing a large amount of silicon atoms is difficult to remove by dry etching with an oxygen-based gas.
• oxygen-based gas oxygen gas, oxygen/carbonyl sulfide (COS) mixed gas, etc.
• the patterned resist underlayer film (intermediate layer) and optionally the patterned organic underlayer film (lower layer) are used as protective films to process the (semiconductor) substrate, which is performed by dry etching using a fluorine-based gas.
• fluorine-based gases include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, and difluoromethane (CH 2 F 2 ). mentioned.
• the resist underlayer film after the step of etching (removing) the organic underlayer film, can be removed with a chemical solution.
• the removal of the resist underlayer film with the chemical solution can also be performed after processing the substrate with the patterned organic underlayer film.
• a composition for forming a resist underlayer film containing the hydrolytic condensate (polysiloxane) the solubility of the film formed from the condensate under alkaline conditions can be enhanced. .
• it exhibits excellent solubility in alkaline solutions (basic chemicals) such as aqueous solutions containing ammonia and hydrogen peroxide.
• the film exhibits good peelability when treated with an alkaline solution, and even silicon-based mask residues such as silicon-containing resist underlayer films can be easily removed with chemicals. It is possible to manufacture a semiconductor device with less Examples of the chemical solutions include dilute hydrofluoric acid, buffered hydrofluoric acid, an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), hydrofluoric acid and hydrogen peroxide.
• SC-2 chemical solution aqueous solution containing hydrochloric acid and hydrogen peroxide
• SPM chemical solution sulfuric acid and hydrogen peroxide
• Alkaline solutions such as an aqueous solution (FPM chemical solution) and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution) can be mentioned, and the use of an alkaline chemical solution (basic chemical solution) is preferable from the viewpoint of reducing the effect on the substrate. be.
• FPM chemical solution aqueous solution
• SC-1 chemical solution aqueous solution containing ammonia and hydrogen peroxide
• alkaline solution examples include ammonia hydrogen peroxide (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide, and water, as well as ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrroli dinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepiquat hydroxide, Mention may be made of aqueous solutions containing 1 to 99% by
• an organic antireflection film can be formed on the upper layer of the resist underlayer film before forming the resist film.
• the antireflection coating composition used there is not particularly limited, and can be used by arbitrarily selecting, for example, those conventionally used in lithographic processes. , a spinner, or a coater, and baking to form the antireflection film.
• the substrate to which the composition for forming a resist underlayer film of the present invention is applied may have an organic or inorganic antireflection film formed on its surface by a CVD method or the like.
• a resist underlayer film can also be formed.
• the substrate to be used has an organic or inorganic antireflection film formed on its surface by a CVD method or the like. may have.
• the resist underlayer film formed from the composition for forming a resist underlayer film of the present invention may also absorb light. In such a case, it can function as an antireflection film having an effect of preventing reflected light from the substrate.
• the resist underlayer film is a layer for preventing interaction between the substrate and the resist film (photoresist film, etc.), a material used for the resist film, or a substance generated when the resist film is exposed to an adverse effect on the substrate. a layer with a function to prevent diffusion of substances generated from the substrate during heating and baking into the upper resist film, and a barrier layer for reducing the poisoning effect of the resist film due to the dielectric layer of the semiconductor substrate, etc. It is also possible to use
• the resist underlayer film can be applied to a substrate having via holes formed therein for use in a dual damascene process, and can be used as a hole-filling material (embedding material) capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the uneven surface of a semiconductor substrate.
• the above-mentioned resist underlayer film does not intermix with the EUV resist film, for example, exposure light that is not preferable for EUV exposure (wavelength 13.5 nm), such as It can be used as a lower anti-reflection film of an EUV resist film that can prevent reflection of UV (ultraviolet) light and DUV (deep ultraviolet) light (:ArF light, KrF light) from a substrate or an interface. That is, it can efficiently prevent reflection as a lower layer of the EUV resist film.
• the process can be performed in the same manner as for the photoresist underlayer film.
• the semiconductor substrate can be suitably processed. Further, the steps of forming an organic underlayer film as described above, and forming a silicon-containing resist underlayer film on the organic underlayer film using the composition for forming a silicon-containing resist underlayer film of the present invention; According to the method of manufacturing a semiconductor device, which includes the step of forming a resist film on the silicon-containing resist underlayer film, highly accurate semiconductor substrate processing can be achieved with good reproducibility, thereby stably manufacturing semiconductor devices. I can expect it.
• hydrolytic condensate (polyorganosiloxane) of the above hydrolyzable silane can be obtained as a condensate with a weight average molecular weight of 1,000 to 1,000,000 or 1,000 to 100,000. These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis.
• GPC measurement conditions include, for example, a GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.), and a column temperature of 40. °C, the eluent (elution solvent) is tetrahydrofuran, the flow rate (flow rate) is 1.0 mL/min, and the standard sample is polystyrene (manufactured by Showa Denko KK).
• Me represents a methyl group
• Et represents an ethyl group
• reaction solution was cooled to room temperature, 56 g of 1-ethoxy-2-propanol was added to the reaction solution, and water and nitric acid as well as reaction by-products methanol and ethanol were distilled off under reduced pressure to obtain 1 -Ethoxy-2-propanol was used as a solvent to obtain a concentrated solution of a hydrolyzed condensate (polymer).
• the solid content concentration of the obtained concentrate exceeded 20% by mass in terms of solid residue when heated at 150°C.
• the obtained hydrolytic condensate (polysiloxane) corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,000 in terms of polystyrene.
• Mw weight average molecular weight
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitric acid, as well as ethanol as a reaction by-product, are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) was obtained using 1-ethoxy-2-propanol as a solvent.
• the solid content concentration of the obtained concentrate exceeded 20% by mass in terms of solid residue when heated at 150°C.
• the resulting hydrolyzed condensate (polysiloxane) corresponded to the following formula, and had a weight average molecular weight (Mw) of 2,700 in terms of polystyrene by GPC.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water, nitric acid, and reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolytic condensate (polymer) was obtained using 1-ethoxy-2-propanol as a solvent.
• the solid content concentration of the obtained concentrate exceeded 20% by mass in terms of solid residue when heated at 150°C.
• the hydrolyzed condensate polysiloxane obtained corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,900 in terms of polystyrene.
• Add-1 to Add-11 are additives represented by the following structural formulas.
• the solution was filtered using a polyethylene microfilter with a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter with a pore size of 0.05 ⁇ m to prepare a composition for forming an organic underlayer film.
• Examples 1-34, Comparative Examples 1-2 Resist pattern evaluation (PTD) by ArF exposure
• the composition for forming an organic underlayer film was applied onto a silicon wafer using a spinner and heated on a hot plate at 240° C. for 60 seconds to form an organic underlayer film (A layer) (thickness: 200 nm).
• a silicon-containing resist underlayer film (B layer) (20 nm) was formed thereon by spin-coating the coating solution obtained in Preparation Example 1 and heating on a hot plate at 215° C. for 1 minute.
• a commercially available ArF resist manufactured by JSR Corporation, trade name: AR2772JN was spin-coated thereon and heated on a hot plate at 110° C.
• C layer 120 nm
• C layer 120 nm
• post-exposure heating 110° C. for 1 minute was performed, cooled to room temperature on a cooling plate, developed with a 2.38% alkaline aqueous solution for 60 seconds, and rinsed to form a resist pattern.
• Examples 1 to 34, Comparative Examples 1 and 2 Evaluation of siloxane bond strength ratio by FT-IR
• the coating liquid obtained in Preparation Example 1 was spin-coated and placed on a hot plate at 215 ° C. to form a silicon-containing resist underlayer film (B layer).
• the B layer was further laminated twice in the same process to obtain a B layer (80 nm film thickness) laminated three times.
• Silicon-containing resist underlayer films were formed in the same manner using the coating solutions obtained in Preparation Examples 2-34 and Comparative Preparation Examples 1-2.
• Examples 1 to 34, Comparative Examples 1 and 2 Evaluation of removability by SC-1 chemical solution (ammonia/hydrogen peroxide aqueous solution) On a silicon wafer, the coating solution obtained in Preparation Example 1 was spin-coated, A silicon-containing resist underlayer film (B layer) (20 nm) was formed by heating on a hot plate at 215° C. for 1 minute. Silicon-containing resist underlayer films were formed in the same manner using the coating solutions obtained in Preparation Examples 2-34 and Comparative Preparation Examples 1-2.
• Examples 1 to 34, Comparative Examples 1 and 2 Evaluation of residue after dry etching
• the above composition for forming an organic underlayer film was applied onto a silicon wafer using a spinner, and heated on a hot plate. By heating at 240° C. for 60 seconds, an organic underlayer film (A layer) (thickness: 70 nm) was formed.
• a silicon-containing resist underlayer film (B layer) (20 nm) was formed thereon by spin-coating the coating solution obtained in Preparation Example 1 and heating on a hot plate at 215° C. for 1 minute.
• the silicon wafer surface from which the organic underlayer film (A layer) and the silicon-containing resist underlayer film (B layer) were removed was observed using a scanning probe microscope (AFM5000, manufactured by Hitachi High-Tech Co., Ltd.). If a convex etching residue with a width of 0.05 ⁇ m or more and a height of 2 nm or more was observed, it was evaluated as “bad”, and if not, it was evaluated as “good”. Table 3 shows the results obtained.

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• 2022
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