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
  • G03F7/004—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
• • 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
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes

Definitions

• the present invention relates to a composition for forming a wet-removable silicon-containing resist underlayer film.
• Microfabrication is a processing method in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and then the thin film is irradiated with active light such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developed, and the substrate is etched using the obtained photoresist pattern as a protective film, thereby forming fine projections and recesses corresponding to the pattern on the substrate surface.
• a film known as a hard mask which contains metal elements such as silicon and titanium, is used as an underlayer film between the semiconductor substrate and the photoresist.
• a hard mask which contains metal elements such as silicon and titanium
• the speed at which they are removed by dry etching depends greatly on the type of gas used in dry etching.
• the type of gas By appropriately selecting the type of gas, it is possible to remove the hard mask by dry etching without a significant decrease in the thickness of the photoresist.
• a resist underlayer film has come to be placed between the semiconductor substrate and the photoresist to achieve various effects, including an anti-reflection effect.
• compositions for resist underlayer films have been studied to date, but the diversity of required properties has led to a demand for the development of new materials for resist underlayer films.
• a coating-type BPSG (boron phosphorus glass) film-forming composition containing a specific silicic acid-based structure Patent Document 1
• Patent Document 2 silicon-containing resist underlayer film-forming composition containing a carbonyl structure
• multi-layer processes are often used due to the miniaturization of implant layers.
• transfer to the lower layer is usually performed by the above-mentioned dry etching, and the final processing of the substrate and removal of mask residues after substrate processing, such as underlayer films including resist films and resist underlayer films, may also be performed by dry etching or ashing.
• dry etching and ashing processes cause considerable damage to the substrate, and improvements in this regard are required.
• the present invention has been made in consideration of the above circumstances, and aims to provide a composition for forming a silicon-containing resist underlayer film that can form a resist underlayer film that can be stripped not only by the conventional dry etching method in the processing of semiconductor substrates, etc., but also by a wet etching method using a chemical solution such as dilute hydrofluoric acid, buffered hydrofluoric acid, or an alkaline chemical solution (basic chemical solution), and that has excellent solubility in an alkaline chemical solution (basic chemical solution), in particular; a silicon-containing resist underlayer film formed from the composition for forming a silicon-containing resist underlayer film, that has excellent storage stability and has excellent solubility in chemical solutions; a laminate including the silicon-containing resist underlayer film; and a method for manufacturing a semiconductor element and a patterning method using the composition for forming a silicon-containing resist underlayer film.
• a chemical solution such as dilute hydrofluoric acid, buffered hydrofluoric acid, or an alkaline
• a composition for forming a silicon-containing resist underlayer film comprising a hydrolysis condensate of a hydrolyzable silane mixture containing a hydrolyzable silane represented by the following formula (1-1) and a hydrolyzable silane represented by the following formula (2), for forming a silicon-containing resist underlayer film soluble in a basic chemical solution
• the hydrolyzable silane represented by formula (1-1) is (In formula (1-1), R 13 is a group or atom bonded to a silicon atom, and each independently represents a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom;
• the hydrolyzable silane represented by formula (2) is (In formula (2), R 1 is a group bonded to a silicon atom and represents an organic group containing a succinic anhydride skeleton; R2 is a group bonded to a silicon atom, and each independently represents an optionally
• the hydrolyzable silane mixture is The composition for forming a silicon-containing resist underlayer film according to [1], further comprising a hydrolyzable silane represented by the following formula (1):
• R 11 is a group bonded to a silicon atom and each independently represents a monovalent group represented by the following formula (2a) or a monovalent group represented by the following formula (2b).
• R 12 is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination of two or more thereof.
• R 13 is a group or atom bonded to a silicon atom, and each independently represents a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• a represents an integer of 0 to 2
• b represents an integer of 0 to 2
• 4-(a+b) represents an integer of 1 to 3.
• R 201 and R 202 each independently represent an organic group containing a hydrogen atom or an alkyl group which may be substituted
• R 203 represents an alkylene group which may be substituted
• * represents a bond bonded to the silicon atom.
• R 404 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an organic group having an epoxy group, or an organic group having a sulfonyl group
• R 405 each independently represents an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-) or an ester bond (-CO-O- or -O-CO-).
• * represents a bond.
• X 401 each independently represents any of the groups represented by the following formulae (4-3) to (4-5), and the carbon atom of the ketone group in the following formulae (4-4) and (4-5) is bonded to the nitrogen atom to which R 405 in the formula (2b) is bonded.
• R 406 to R 410 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group having an epoxy group or a sulfonyl group. * represents a bond.
• R 11 is the same as R 11 in the above formula (1).
• R 12 is the same as R 12 in the above formula (1).
• R 13 is the same as R 13 in the above formula (1).
• c is an integer of 0 to 2
• d is an integer of 0 to 2
• c+d 2.
• R 17 is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or represents an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group
• R 18 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• f represents an integer of 1 to 3.
• a method for manufacturing a semiconductor device comprising: [9] forming an organic underlayer film on a semiconductor substrate; A step of applying a composition for forming a silicon-containing resist underlayer film according to any one of [1] to [5] onto the organic underlayer film, and baking the composition to form a silicon-containing resist underlayer film; forming a resist film on the silicon-containing resist underlayer film; exposing and developing the resist film to obtain a resist pattern; Etching the silicon-containing resist underlayer film using the resist pattern as a mask; Etching the organic underlayer film using the patterned silicon-containing resist underlayer film as a mask;
• a pattern forming method comprising: [10] removing the silicon-containing resist underlayer film by
• the present invention provides a composition for forming a silicon-containing resist underlayer film that can be stripped not only by conventional dry etching methods in the processing of semiconductor substrates, etc., but also by wet etching methods using chemicals such as dilute hydrofluoric acid, buffered hydrofluoric acid, and alkaline chemicals (basic chemicals), and that can form a resist underlayer film that exhibits excellent solubility in alkaline chemicals (basic chemicals), in particular; a silicon-containing resist underlayer film formed from the composition for forming a silicon-containing resist underlayer film that has excellent storage stability and exhibits excellent solubility in chemicals; a laminate including the silicon-containing resist underlayer film; and a method for manufacturing a semiconductor element and a patterning method that use the composition for forming a silicon-containing resist underlayer film.
• the present invention is directed to a composition for forming a silicon-containing resist underlayer film that is strippable by a wet process and that exhibits excellent solubility, particularly in basic chemical solutions.
• the composition for forming a silicon-containing resist underlayer film of the present invention contains a product (hydrolysis condensate) obtained by hydrolysis and condensation of a hydrolyzable silane mixture containing a hydrolyzable silane.
• composition for forming a silicon-containing resist underlayer film of the present invention is characterized in that it contains a hydrolyzable silane of a tetrafunctional monomer and a hydrolyzable silane represented by a specific structural formula among the hydrolyzable silanes constituting the hydrolyzable silane mixture. This will be described in detail in the section "Composition for forming a silicon-containing resist underlayer film of the first embodiment" below.
• the composition for forming a silicon-containing resist underlayer film of the present invention preferably contains a hydrolyzable silane of a bifunctional monomer among the hydrolyzable silanes constituting the hydrolyzable silane mixture.
• composition for forming a silicon-containing resist underlayer film of the present invention may contain other components such as a solvent and various additives in addition to the hydrolysis condensate of the hydrolyzable silane mixture.
• the hydrolysis condensate includes not only polyorganosiloxane polymers which are condensates in which condensation is completely completed, but also polyorganosiloxane polymers which are partial hydrolysis condensates in which condensation is not completely completed.Similar to the condensates in which condensation is completely completed, such partial hydrolysis condensates are polymers obtained by hydrolysis and condensation of hydrolyzable silane compounds, but they are partially hydrolyzed and not condensed, and therefore Si-OH groups remain.
• the composition for forming a silicon-containing resist underlayer film of the present invention may contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silane compounds). In this specification, the "hydrolyzable silane” may also be simply referred to as a "silane compound.”
• the composition for forming a silicon-containing resist underlayer film of the present invention contains a hydrolyzed condensate of a hydrolyzable silane mixture containing a hydrolyzable silane of a tetrafunctional monomer and a hydrolyzable silane represented by a specific structural formula having an organic acid containing a succinic anhydride skeleton.
• the hydrolyzable silane mixture contains a hydrolyzable silane represented by the following formula (1-1) and a hydrolyzable silane represented by the following formula (2).
• the hydrolyzable silane mixture preferably contains, in addition to the hydrolyzable silane represented by formula (1-1) or formula (2), a hydrolyzable silane represented by formula (1) described below.
• the hydrolyzable silane mixture preferably contains, among the hydrolyzable silanes represented by formula (1), a difunctional hydrolyzable silane represented by formula (1-2).
• the hydrolyzable silane mixture preferably contains, among the hydrolyzable silanes represented by formula (1), a hydrolyzable silane represented by formula (1-3) in particular.
• the hydrolyzable silane mixture according to the present invention contains a hydrolyzable silane which is a tetrafunctional monomer represented by the following formula (1-1).
• R 13 is a group or atom bonded to a silicon atom, and each independently represents a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• Examples of the alkoxy group for R 13 include linear, branched, and cyclic alkoxy groups having 1 to 20 carbon atoms and at least any one of straight-chain, branched-chain, and cyclic alkyl moieties.
• linear or branched alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group,
• alkyl group examples include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.
• cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3 -dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl
• halogen atom in R 13 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• An aralkyloxy group is a monovalent group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol.
• the aralkyl group in the aralkyloxy group is an alkyl group substituted with an aryl group.
• the aryl group may be any of a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound, and the alkyl group may be linear, branched, or cyclic.
• the number of carbon atoms in the aralkyloxy group is not particularly limited, but may be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less.
• aralkyloxy groups include, but are not limited to, a phenylmethyloxy group (benzyloxy group), a 2-phenylethyleneoxy group, a 3-phenyl-n-propyloxy group, a 4-phenyl-n-butyloxy group, a 5-phenyl-n-pentyloxy group, a 6-phenyl-n-hexyloxy group, a 7-phenyl-n-heptyloxy group, an 8-phenyl-n-octyloxy group, a 9-phenyl-n-nonyloxy group, and a 10-phenyl-n-decyloxy group.
• the acyloxy group is a monovalent group derived by removing a hydrogen atom from a carboxyl group (-COOH) of a carboxylic acid compound, and typically includes, but is not limited to, an alkylcarbonyloxy group, an arylcarbonyloxy group, or an aralkylcarbonyloxy group derived by removing a hydrogen atom from a carboxyl group of an alkylcarboxylic acid, an arylcarboxylic acid, or an aralkylcarboxylic acid.
• alkyl group, aryl group, and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid, and aralkylcarboxylic acid will be described in detail in the description of R 12 in formula (1) below ( ⁇ R 12 >>>).
• acyloxy group examples include acyloxy groups having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-
• n-butylcarbonyloxy group 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group
• hydrolyzable silanes represented by formula (1-1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane.
• the content of the hydrolyzable silane represented by formula (1-1) in the hydrolyzable silane mixture is preferably more than 0 mol % and 30 mol % or less, based on 100 mol % of hydrolyzable silane contained in the hydrolyzable silane mixture.
• hydrolyzable silane mixture according to the present invention contains a hydrolyzable silane represented by the specific structural formula (2) below.
• R 1 is a group bonded to a silicon atom and represents an organic group containing a succinic anhydride skeleton
• R2 is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or an optionally substituted alkoxyalkyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination of two or more thereof
• R3 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom
• j represents 1, h represents an integer of 0 to 2
• 4-(j+h) represents an integer of 1 to
• R1 is a group bonded to a silicon atom and represents an organic group containing a succinic anhydride 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 whose hydrogen atom is substituted by the succinic anhydride skeleton or the like is not particularly limited and may be linear, branched, or cyclic, and the number of carbon atoms therein is usually 40 or less, for example 30 or less, more preferably 20 or less, or 10 or less. Specific examples of the linear or branched alkyl group and the cyclic alkyl group will be described in detail in the section ⁇ R 2 >>> below.
• Examples of the organic group containing a succinic anhydride skeleton for R 1 include monovalent groups represented by the following formula (A2).
• R 401 represents, for example, an alkylene group which is a divalent group derived by removing one hydrogen atom from the above-mentioned linear, branched or cyclic alkyl group. * represents a bond bonded to a silicon atom.
• R2 's are groups bonded to silicon atoms and each independently represent an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or an optionally substituted alkoxyalkyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination of two or more of these.
• the alkyl group may be linear, branched, or cyclic, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.
• linear or branched alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl ...
• cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4- Examples of such cycloalkyl groups include dimethyl-cyclobutyl group, 3,3-
• the halogenated alkyl group is an alkyl group substituted with one or more halogen atoms, and specific examples of such alkyl groups include the same as those mentioned above.
• Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the number of carbon atoms in the halogenated alkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.
• Specific examples of halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexa
• alkoxyalkyl group is an alkyl group substituted with one or more alkoxy groups, and specific examples of such alkyl groups include those mentioned above.
• alkoxy group as a substituent examples include alkoxy groups having at least one of a straight-chain, branched-chain, and cyclic alkyl moiety having 1 to 20 carbon atoms.
• linear or branched alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a
• alkyl group examples include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.
• cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3 -dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl
• alkoxyalkyl groups include, but are not limited to, lower (about 5 carbon atoms or less) alkyloxy-lower (about 5 carbon atoms or less) alkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl.
• examples of the substituent in the alkyl group, halogenated alkyl group, and alkoxyalkyl group include an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkoxyalkyl group, an aryloxy group, an alkoxyaryl group, an alkoxyaralkyl group, an alkenyl group, an alkoxy group, and an aralkyloxy group.
• Specific examples of these and suitable numbers of carbon atoms thereof are the same as those described above or below.
• the aryloxy group exemplified as the substituent is a group in which an aryl group is bonded via an oxygen atom (-O-).
• the number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples thereof include, but are not limited to, a phenoxy group and a naphthalene-2-yloxy group. When two or more substituents are present, the substituents may be bonded to each other to form a ring.
• Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.
• Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.
• Examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
• Examples of the organic group having a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and a mercaptophenyl group.
• Examples of the organic group having an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, etc. The organic group having an amino group will be described in more detail below.
• Examples of the organic group having an amide group include an amide group-containing aliphatic hydrocarbon group, an amide group-containing alicyclic hydrocarbon group, and an amide group-containing aromatic hydrocarbon group.
• Examples of organic groups having an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group, except for groups in which the alkoxy group is directly bonded to a silicon atom.
• Examples of the organic group having a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group.
• Examples of the organic group having a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.
• organic groups having an amino group examples include organic groups having at least one of a primary amino group, a secondary amino group, and a tertiary amino group.
• a hydrolysis condensate obtained by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid to produce a counter cation having a tertiary ammonium group is preferably used.
• the organic group can contain heteroatoms such as oxygen atoms and sulfur atoms.
• a preferred example of an organic group having an amino group is a group represented by the following formula (A1):
• R 101 and R 102 each independently represent a hydrogen atom or a hydrocarbon group
• L each independently represent an optionally substituted alkylene group.
• * represents a bond.
• the hydrocarbon group include, but are not limited to, an alkyl group, an alkenyl group, an aryl group, and the like.
• the alkylene group may be either linear or branched, and has a carbon number of usually 1 to 10, preferably 1 to 5.
• Examples of such alkylene groups include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene.
• organic group having an amino group examples include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group.
• R3 's are groups or atoms bonded to the silicon atom and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• the alkoxy group, aralkyloxy group, acyloxy group or halogen atom for R 3 in formula (2) is as explained in the section ⁇ R 13 >>>> of formula (1-1) above.
• j represents 1
• h represents an integer from 0 to 2
• 4-(j+h) represents an integer from 1 to 3.
• hydrolyzable silanes represented by formula (2) include silane compounds containing a succinic anhydride skeleton, such as [(3-trimethoxysilyl)propyl]succinic anhydride, [(3-triethoxysilyl)propyl]succinic anhydride, [(3-trimethoxysilyl)ethyl]succinic anhydride, and [(3-trimethoxysilyl)butyl]succinic anhydride.
• succinic anhydride skeleton such as [(3-trimethoxysilyl)propyl]succinic anhydride, [(3-triethoxysilyl)propyl]succinic anhydride, [(3-trimethoxysilyl)ethyl]succinic anhydride, and [(3-trimethoxysilyl)butyl]succinic anhydride.
• the crosslink density of the silicon-containing resist underlayer film obtained from the composition for forming the silicon-containing resist underlayer film can be improved, and the diffusion of the components of the resist film into the silicon-containing resist underlayer film can be suppressed, ensuring the maintenance and improvement of the properties of the resist film while providing the silicon-containing resist underlayer film with excellent solubility in an alkaline chemical solution (basic chemical solution).
• the peak intensity value of the siloxane bond in the silicon-containing resist underlayer film formed from a composition for forming a silicon-containing resist underlayer film containing a hydrolysis condensate of a hydrolyzable silane mixture containing these hydrolyzable silanes can be reduced (see the results of the Examples described below).
• the reduction in the peak intensity value of the siloxane bond in the silicon-containing resist underlayer film is believed to be effective in improving the solubility of the silicon-containing resist underlayer film in chemical solutions.
• the hydrolysis condensation product contained in the composition for forming a silicon-containing resist underlayer film of the present invention can be a product of hydrolysis condensation of a hydrolyzable silane mixture containing a silane compound represented by the following formula (1).
• the hydrolyzable silane mixture according to the present invention can contain a hydrolyzable silane represented by the following formula (1), in addition to the hydrolyzable silane of a tetrafunctional monomer represented by the above formula (1-1) and the hydrolyzable silane having an organic acid containing a succinic anhydride skeleton represented by the formula (2).
• R 11 is a group bonded to a silicon atom and each independently represents a monovalent group represented by the following formula (2a) or a monovalent group represented by the following formula (2b).
• R 12 is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an alkoxy group, a sulfonyl group, or a
• R 13 is a group or atom bonded to a silicon atom, and each independently represents a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• a represents an integer of 0 to 2
• b represents an integer of 0 to 2
• 4-(a+b) represents an integer of 1 to 3.
• R 11 is a group bonded to a silicon atom and each independently represents a monovalent group represented by the following formula (2a) or a monovalent group represented by the following formula (2b).
• R 201 and 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
• * represents a bond bonded to the silicon atom.
• R 404 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an organic group having an epoxy group, or an organic group having a sulfonyl group
• R 405 each independently represents an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-) or an ester bond (-CO-O- or -O-CO-).
• * represents a bond.
• X 401 each independently represents any of the groups represented by the following formulae (4-3) to (4-5), and the carbon atom of the ketone group in the following formulae (4-4) and (4-5) is bonded to the nitrogen atom to which R 405 in the formula (2b) is bonded.
• R 406 to R 410 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group having an epoxy group or a sulfonyl group. * represents a bond.
• R 11 is a monovalent group represented by formula (2a)
• R 201 and 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
• * represents a bond bonded to the silicon atom.
• the optionally substituted alkyl group in the monovalent group represented by formula (2a) of R 11 is as described in the ⁇ R 2 >>> column in formula (2) above.
• the organic group containing an optionally substituted alkyl group include an optionally substituted alkyl group.
• the optionally substituted alkylene group in the monovalent group represented by formula (2a) of R 11 refers to a divalent group derived by removing one hydrogen atom from the optionally substituted alkyl group.
• the alkylene group may be linear, branched, or cyclic.
• alkylene group examples include linear alkylene groups such as methylene, ethylene, trimethylene, methylethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkylene groups such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; and —CH 2 OCH 2 -, -CH 2 CH 2 OCH 2 -, -CH 2 CH
• R 11 is a monovalent group represented by formula (2b)
• formula (2b) specific examples and suitable carbon numbers of the optionally substituted alkyl group, optionally substituted alkenyl group, and organic group having an epoxy group for R 404 will be described in detail in the section ⁇ R 12 >>> described later.
• the optionally substituted alkyl group for R 404 is preferably an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group, and specific examples thereof include an allyl group, a 2-vinylethyl group, a 3-vinylpropyl group, and a 4-vinylbutyl group.
• the organic group having a sulfonyl group for R 404 is not particularly limited as long as it contains a sulfonyl group, and examples thereof include an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted aralkylsulfonyl group, an optionally substituted halogenated alkylsulfonyl group, an optionally substituted halogenated arylsulfonyl group, an optionally substituted halogenated aralkylsulfonyl group, an optionally substituted alkoxyalkylsulfonyl group, an optionally substituted alkoxyarylsulfonyl group, an optionally substituted alkoxyaralkylsulfonyl group, and an optionally substituted alkenylsulfonyl group.
• alkyl group aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group in these groups, as well as suitable carbon numbers of their substituents, will be described in detail in the section ⁇ R 12 >>> described later.
• the alkylene group of R 405 is a divalent group derived by removing one more hydrogen atom from an alkyl group, and may be linear, branched, or cyclic, and specific examples of such alkylene groups include those mentioned above.
• the number of carbon atoms in the alkylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.
• the alkylene group of R 405 may have one or more kinds selected from a sulfide bond, an ether bond and an ester bond at its terminal or in the middle, preferably in the middle.
• the alkylene group include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as methylethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkylene groups such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclo
• the hydroxyalkylene group of R 405 is an alkylene group in which at least one hydrogen atom has been replaced with a hydroxy group.
• a hydroxymethylene group a 1-hydroxyethylene group, a 2-hydroxyethylene group, a 1,2-dihydroxyethylene group, a 1-hydroxytrimethylene group, a 2-hydroxytrimethylene group, a 3-hydroxytrimethylene group, a 1-hydroxytetramethylene group, a 2-hydroxytetramethylene group, a 3-hydroxytetramethylene group, a 4-hydroxytetramethylene group, a 1,2-dihydroxytetramethylene group, a 1,3-dihydroxytetramethylene group, a 1,4-dihydroxytetramethylene group, a 2,3-dihydroxytetramethylene group, a 2,4-dihydroxytetramethylene group, and a 4,4-dihydroxytetramethylene group.
• X 401 each independently represents any of the groups represented by the following formulae (4-3) to (4-5), and the carbon atom of the ketone group in formulae (4-4) and (4-5) is bonded to the nitrogen atom to which R 405 in formula (4-2) is bonded.
• R 406 to R 410 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group having an epoxy group or a sulfonyl group.
• R 406 to R 410 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group having an epoxy group or a sulfonyl group.
• Specific examples of the optionally substituted alkyl group, the optionally substituted alkenyl group, and the organic group having an epoxy group or a sulfonyl group, as well as suitable carbon numbers, etc. will be described in detail in the section ⁇ R 12 >>> described later.
• Specific examples of the organic group having a sulfonyl group and the suitable carbon number, etc. are the same as those described above for R 404.
• * represents a bond.
• X 401 is preferably a group represented by formula (4-5).
• At least one of R 404 and R 406 to R 410 is an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group.
• R 12 is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination of two or more thereof.
• the explanation of R 12 in formula (1) partially overlaps with the explanation of R 2 in formula (2) above,
• the alkyl group may be linear, branched, or cyclic, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.
• linear or branched alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl ...
• cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl, 2,4- Examples of such cycloalkyl groups include dimethyl-cyclobutyl group, 3,3-
• the aryl group may be any of a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• the aryl group may be an aryl group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-naphthacenyl group, a 2-naphthacenyl group, a 5-naphthacenyl group, a 2-chrysenyl group, a 1-pyrenyl group, a 2-pyrenyl group, Examples of such groups include, but are not limited to, a pentacenyl group, a benzopyrenyl group, a triphenylenyl group, a biphenyl-2-yl group (
• the aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those described above.
• the number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• aralkyl groups include, but are not limited to, a phenylmethyl group (benzyl group), a 2-phenylethylene group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, a 6-phenyl-n-hexyl group, a 7-phenyl-n-heptyl group, an 8-phenyl-n-octyl group, a 9-phenyl-n-nonyl group, and a 10-phenyl-n-decyl group.
• halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are, respectively, alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms.
• alkyl groups, aryl groups, and aralkyl groups include the same as those described above.
• halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the number of carbon atoms in the halogenated alkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.
• Specific examples of halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexa
• the number of carbon atoms in the halogenated aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• Specific examples of the halogenated aryl group include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluoropheny
• fluoro-1-naphthyl group examples include, but are not limited to, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group).
• the number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• Specific examples of the halogenated aralkyl group include a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2,3-difluorobenzyl group, a 2,4-difluorobenzyl group, a 2,5-difluorobenzyl group, a 2,6-difluorobenzyl group, a 3,4-difluorobenzyl group, a 3,5-difluorobenzyl group, a 2,3,4-trifluorobenzyl group, a 2,3,5-trifluorobenzyl group, a 2,3,6-trifluorobenzyl group, a 2,4,5-trifluorobenzyl group, a Examples of the fluoro
• alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are, respectively, alkyl groups, aryl groups, and aralkyl groups substituted with one or more alkoxy groups, and specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above.
• alkoxy group as a substituent examples include an alkoxy group having at least one of a straight-chain, branched-chain, and cyclic alkyl moiety having 1 to 20 carbon atoms.
• linear or branched alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group,
• alkyl group examples include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.
• cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3 -dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl
• alkoxyalkyl groups include lower (having about 5 carbon atoms or less) alkyloxy-lower (having about 5 carbon atoms or less) alkyl groups such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group, but are not limited to these.
• alkoxyaryl groups include, but are not limited to, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-(1-ethoxy)phenyl group, a 3-(1-ethoxy)phenyl group, a 4-(1-ethoxy)phenyl group, a 2-(2-ethoxy)phenyl group, a 3-(2-ethoxy)phenyl group, a 4-(2-ethoxy)phenyl group, a 2-methoxynaphthalen-1-yl group, a 3-methoxynaphthalen-1-yl group, a 4-methoxynaphthalen-1-yl group, a 5-methoxynaphthalen-1-yl group, a 6-methoxynaphthalen-1-yl group, a 7-methoxynaphthalen-1-yl group, and the like.
• Specific examples of the alkoxyaralkyl group include, but are not
• the alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.
• Specific examples of the alkenyl group include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1- methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-
• examples of the substituent in the above-mentioned alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group include alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, aryloxy groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, alkoxy groups, aralkyloxy groups, and the like.
• the aryloxy group exemplified as the substituent is a group in which an aryl group is bonded via an oxygen atom (-O-), and specific examples of such an aryl group include the same as those described above.
• the number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less, and specific examples thereof include, but are not limited to, a phenoxy group, a naphthalene-2-yloxy group, and the like. When two or more substituents are present, the substituents may be bonded to each other to form a ring.
• Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.
• Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.
• Examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
• Examples of the organic group having a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and a mercaptophenyl group.
• Examples of the organic group having an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, etc. The organic group having an amino group will be described in more detail below.
• Examples of organic groups having an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group, except for groups in which the alkoxy group is directly bonded to a silicon atom.
• Examples of the organic group having a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group.
• Examples of the organic group having a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.
• organic groups having an amino group examples include organic groups having at least one of a primary amino group, a secondary amino group, and a tertiary amino group.
• a hydrolysis condensate obtained by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid to produce a counter cation having a tertiary ammonium group is preferably used.
• the organic group can contain heteroatoms such as oxygen atoms and sulfur atoms.
• a preferred example of an organic group having an amino group is a group represented by the following formula (A1):
• R 101 and R 102 each independently represent a hydrogen atom or a hydrocarbon group
• L each independently represent an optionally substituted alkylene group.
• * represents a bond.
• the hydrocarbon group include, but are not limited to, an alkyl group, an alkenyl group, an aryl group, etc. Specific examples of the alkyl group, the alkenyl group, and the aryl group are the same as those described above for R1 .
• the alkylene group may be either linear or branched, and has a carbon number of usually 1 to 10, preferably 1 to 5.
• alkylene groups include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene.
• organic group having an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group.
• R 13 is a group or atom bonded to a silicon atom, and each independently represents a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• R 13 in formula (1) is the same as R 13 in formula (1-1) above.
• a represents an integer of 0 to 2
• b represents an integer of 0 to 2
• 4-(a+b) represents an integer of 1 to 3.
• a preferably represents 0 or 1
• b preferably represents 1 or 2.
• hydrolyzable silanes represented by formula (1) specific examples include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, and methyltriphenethyl.
• glycidoxysilane glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysi
• T each independently represents an alkoxy group, an acyloxy group, or a halogen group, and preferably represents, for example, a methoxy group or an ethoxy group.
• hydrolyzable silanes represented by formula (1) specific examples of the hydrolyzable silanes having R 11 and in which R 11 is a monovalent group represented by formula (2a) include silane compounds containing alkylphosphonic acids, such as diethyl [(3-triethoxysilyl)ethyl]phosphonate.
• hydrolyzable silanes represented by formula (1) for example, when the hydrolyzable silane has R 11 and R 11 is a monovalent group represented by formula (2b), a commercially available product may be used, or the hydrolyzable silane may be synthesized by a known method described in, for example, WO 2011/102470.
• specific examples of the hydrolyzable silanes having R 11 and R 11 being a monovalent group represented by formula (2b) include silanes represented by the following formulas (4-1-1) to (4-1-29), and the like.
• the hydrolyzable silane mixture that forms the hydrolysis condensate contained in the composition for forming a silicon-containing resist underlayer film of the present invention preferably contains, among the hydrolyzable silanes represented by formula (1), a hydrolyzable silane that is a bifunctional monomer represented by the following formula (1-2):
• the hydrolyzable silane mixture according to the present invention preferably contains a hydrolyzable silane of a difunctional monomer represented by the following formula (1-2), in addition to a hydrolyzable silane of a tetrafunctional monomer represented by the formula (1-1) and a hydrolyzable silane of the following formula (2).
• the hydrolyzable silane mixture that forms the hydrolysis condensate contained in the composition for forming a silicon-containing resist underlayer film of the present invention preferably contains a hydrolyzable silane represented by the following formula (1-3) among the hydrolyzable silanes represented by formula (1).
• the hydrolyzable silane mixture according to the present invention preferably contains a hydrolyzable silane represented by the following formula (1-3) in addition to the tetrafunctional monomer hydrolyzable silane represented by formula (1-1) and the hydrolyzable silane represented by the following formula (2).
• the solubility in an alkaline chemical solution (basic chemical solution) of the silicon-containing resist underlayer film obtained from the composition for forming a silicon-containing resist underlayer film containing the hydrolyzed condensate of the hydrolyzable silane mixture can be made more excellent.
• the hydrolyzable silane mixture according to the present invention preferably contains, among the hydrolyzable silanes represented by the above formula (1), a hydrolyzable silane of a bifunctional monomer represented by the following formula (1-2):
• R 11 , R 12 and R 13 are the same as R 11 , R 12 and R 13 in formula (1).
• c is an integer of 0 to 2
• d is an integer of 0 to 2
• c+d 2.
• c is preferably 0 or 1
• d is preferably 1 or 2.
• hydrolyzable silane mixture according to the present invention preferably contains, among the hydrolyzable silanes represented by the above formula (1), a hydrolyzable silane represented by the following formula (1-3).
• R 17 is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group.
• R 18 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• f represents
• R 17 of formula (1-3) the same groups as R 12 of formula (1) are as explained above in the section ⁇ R 12 >>>>.
• R 18 of formula (1-3) the same groups as R 13 of formula (1) are as explained above in the section ⁇ R 13 >>>>.
• the peak intensity value of the siloxane bond in the silicon-containing resist underlayer film formed from the composition for forming the silicon-containing resist underlayer film containing the hydrolysis condensate of the hydrolyzable silane mixture can be reduced (see the results of the Examples described later).
• the reduction in the peak intensity value of the siloxane bond in the silicon-containing resist underlayer film is believed to be effective in improving the solubility of the silicon-containing resist underlayer film in chemical solutions.
• hydrolyzable silane of a bifunctional monomer with a high water contact angle among the hydrolyzable silanes contained in the hydrolyzable silane mixture showed good results in terms of the solubility of the silicon-containing resist underlayer film in the chemical solution (see the results of the Examples described below), it is more preferable to contain a hydrolyzable silane of a bifunctional monomer with a high water contact angle.
• a preferred embodiment of the composition for forming a silicon-containing resist underlayer film of the present invention is a composition containing a hydrolysis condensate of a hydrolyzable silane mixture containing a bifunctional hydrolyzable silane.
• the hydrolyzable silane mixture contains a hydrolyzable silane represented by the following formula (1-2), which is a difunctional monomer hydrolyzable silane among the hydrolyzable silanes represented by the above formula (1).
• the hydrolyzable silane mixture may contain, in addition to the hydrolyzable silane represented by formula (1-2), a hydrolyzable silane represented by formula (1-1) above, a hydrolyzable silane represented by formula (2) above, or a hydrolyzable silane represented by formula (1) above excluding the hydrolyzable silane represented by formula (1-2).
• R 11 , R 12 , R 13 , c, and d are as defined above.
• the solubility in an alkaline chemical solution (basic chemical solution) of the silicon-containing resist underlayer film obtained from a composition for forming a silicon-containing resist underlayer film containing a hydrolysis condensate of the hydrolyzable silane mixture can be made superior.
• the peak intensity value of the siloxane bond in the silicon-containing resist underlayer film formed from a composition for forming a silicon-containing resist underlayer film containing a hydrolysis condensate of the hydrolyzable silane mixture can be reduced (see the results of the Examples described later).
• the reduction in the peak intensity value of the siloxane bond in the silicon-containing resist underlayer film is believed to be effective in improving the solubility of the silicon-containing resist underlayer film in chemical solutions.
• hydrolyzable silane of a bifunctional monomer with a high water contact angle among the hydrolyzable silanes contained in the hydrolyzable silane mixture showed good results in terms of the solubility of the silicon-containing resist underlayer film in the chemical solution (see the results of the Examples described below), it is more preferable to contain a hydrolyzable silane of a bifunctional monomer with a high water contact angle.
• hydrolyzable silane mixture may contain other silane compounds (hydrolyzable silanes) in addition to the silane compounds exemplified in the first and second embodiments above, as long as the effects of the present invention are not impaired.
• the amount of the silane compound represented by formula (1-1) added is preferably more than 0 mol % and 30 mol % or less, relative to 100 mol % of the total amount of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture.
• the amount of the tetrafunctional monomeric silane compound represented by formula (1-1) can be 0.1 to 30 mol % relative to 100 mol % of the total amount of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture.
• the amount of the silane compound represented by formula (2) can be 0.1 to 20 mol % relative to 100 mol % of the total amount of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture.
• the amount of the bifunctional monomer silane compound represented by formula (1-2) among the hydrolyzable silanes represented by formula (1) can be 0.1 to 50 mol % relative to 100 mol % of the total amount of all silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture.
• the amount of the silane compound (hydrolyzable silane) represented by formula (1-3) among the hydrolyzable silanes represented by formula (1) can be 0.1 to 20 mol % relative to 100 mol % of the total amount of all the silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture.
• the hydrolysis condensate of the hydrolyzable silane mixture may 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 even more preferably 100,000 or less, and from the viewpoint of achieving both storage stability and coatability, the weight average molecular weight is preferably 700 or more, more preferably 1,000 or more.
• the weight average molecular weight is a molecular weight obtained by GPC analysis in terms of polystyrene.
• the GPC analysis can be performed, for example, using a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation) and a GPC column (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), setting the column temperature at 40° C., using tetrahydrofuran as an eluent (elution solvent), setting the flow rate (flow velocity) at 1.0 mL/min, and using polystyrene (manufactured by Showa Denko K.K.) as a standard sample.
• a GPC apparatus trade name HLC-8220GPC, manufactured by Tosoh Corporation
• GPC column trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.
• the hydrolysis condensate of the hydrolyzable silane mixture can be obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane).
• the silane compound (hydrolyzable silane) contains, for example, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom that is directly bonded to a silicon atom, that is, an alkoxysilyl group, an aralkyloxysilyl group, an acyloxysilyl group, or a halogenated silyl group, which are hydrolyzable groups.
• hydrolysis of these hydrolyzable groups usually 0.5 to 100 moles, preferably 1 to 10 moles, of water are used per mole of the hydrolyzable group.
• a hydrolysis catalyst may be used or may not be used for the purpose of promoting the reaction, etc.
• the amount of the hydrolysis catalyst that can be used is usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, per 1 mol of the hydrolyzable group.
• the reaction temperature in carrying out the hydrolysis and condensation is usually in the range of not less than room temperature but not more than the reflux temperature at normal pressure of the organic solvent that can be used for the hydrolysis, and can be, for example, 20 to 110° C., or, for example, 20 to 80° C.
• the hydrolysis may be complete, i.e., all hydrolyzable groups are converted to silanol groups, or may be partial, i.e., some hydrolyzable groups remain unreacted.
• hydrolysis catalysts that can be used in the 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(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di-i-propoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium, di-sec-butoxy bis(acetylacetonate)titanium, ) titanium, di-t-butoxy bis(ace
• Organic acids that can be used as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid,
• Inorganic acids that can be used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
• organic bases as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.
• inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the
• metal chelate compounds organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.
• nitric acid can be suitably used as a hydrolysis catalyst.
• 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 hydrolysis condensate can be suppressed. It is known that the stability of the hydrolysis condensate in the liquid depends on the pH of the solution. As a result of extensive investigation, it was found that the pH of the solution can be brought into a stable range by using an appropriate amount of nitric acid.
• an organic solvent may be used as the solvent.
• solvents include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, and n-amylnaphthalene; methanol, ethanol
• suitable solvents include,
• reaction solution can be used as is or after dilution or concentration, neutralized, and treated with an ion exchange resin to remove the hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation.
• hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation.
• by-products such as alcohol and water, and the hydrolysis catalysts used can be removed from the reaction solution by vacuum distillation or the like.
• the hydrolysis condensate (hereinafter also referred to as polysiloxane) thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, which can be used as is for the preparation of a composition for forming a silicon-containing resist underlayer film. That is, the reaction solution can be used as is (or diluted) for the preparation of a composition for forming a silicon-containing resist underlayer film, and at this time, the hydrolysis catalyst used in the hydrolysis and condensation, by-products, etc. may remain in the reaction solution as long as they do not impair the effects of the present invention.
• the hydrolysis catalyst and nitric acid used in the alcohol capping of silanol groups may remain in the polymer varnish solution at about 100 ppm to 5,000 ppm.
• the obtained polysiloxane varnish may be subjected to solvent replacement or may be diluted with a suitable solvent. If the obtained polysiloxane varnish has good storage stability, the organic solvent may be distilled off to make the film-forming component concentration 100%.
• the film-forming component refers to the components excluding the solvent component from all the components of the composition.
• the organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane.
• the dilution solvent is not particularly limited, and one or more kinds may be arbitrarily selected and used.
• composition for forming a silicon-containing resist underlayer film of the present invention can contain, in addition to the hydrolysis condensate (polysiloxane) of the hydrolyzable silane mixture, a solvent, a curing catalyst, nitric acid, an amine, a hydroxide, and other components.
• hydrolysis condensate polysiloxane
• the solvent used in the composition for forming a silicon-containing resist underlayer film of the present invention is not particularly limited as long as it is a solvent that can dissolve the solid content in the composition for forming a resist underlayer film. There are no limitations on such a solvent, so long as it dissolves the hydrolysis condensate of the hydrolyzable silane mixture, the curing catalyst, and other components.
• the solvent is preferably an alcohol-based solvent, more preferably an alkylene glycol monoalkyl ether, which is an alcohol-based solvent, and even more preferably a propylene glycol monoalkyl ether.
• These solvents are also capping agents for the silanol groups of the polysiloxane, so that the composition for forming a silicon-containing resist underlayer film can be prepared from the solution obtained by preparing the polysiloxane without the need for solvent replacement or the like.
• alkylene glycol monoalkyl ether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether.
• solvents include 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, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, Ethylene glycol
• the composition for forming a silicon-containing resist underlayer film of the present invention may also contain water as a solvent.
• water When water is contained as a solvent, the content of water can be, for example, 30% by mass or less, preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the solvents contained in the composition.
• ⁇ Curing catalyst> As the curing catalyst, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc.
• the following salts described as curing catalysts may be added in the form of a salt, or may form a salt in the composition (added as a separate compound and forming a salt in the system).
• the above ammonium salt has the formula (D-1):
• n a represents an integer of 2 to 3
• R 21 represents an alkyl group, an aryl group, or an aralkyl group
• Y ⁇ represents an anion
• Formula (D-6) (wherein m a represents an integer of 2 to 11, n a represents an integer of 2 or 3, and Y ⁇ represents an anion).
• the phosphonium salt may also be represented by the formula (D-7): (In the formula, R 31 , R 32 , R 33 , and R 34 each independently represent an alkyl group, an aryl group, or an aralkyl group; Y ⁇ represents an anion; and R 31 , R 32 , R 33 , and R 34 are each bonded to a phosphorus atom.)
• the sulfonium salt may also be represented by the formula (D-8): (In the formula, R 35 , R 36 , and R 37 each independently represent an alkyl group, an aryl group, or an aralkyl group, Y ⁇ represents an anion, and R 35 , R 36 , and R 37 are each bonded to a sulfur atom.)
• the compound of formula (D-1) is a quaternary ammonium salt derived from an amine, where m a represents an integer of 2 to 11, and n a represents an integer of 2 to 3.
• R 21 of this quaternary ammonium salt represents, for example, an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include linear alkyl groups such as ethyl, propyl, and butyl groups, benzyl groups, cyclohexyl groups, cyclohexylmethyl groups, and dicyclopentadienyl groups.
• anion (Y ⁇ ) examples include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodine ion (I ⁇ ), and acid groups such as carboxylate (-COO ⁇ ), sulfonate (-SO 3 ⁇ ), and alcoholate (-O ⁇ ).
• the compound of formula (D-2) 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 are, for example, an alkyl group having 1 to 18 carbon atoms, such as an ethyl group, a propyl group, a butyl group, a cyclohexyl group or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms, such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms, such as a benzyl group.
• anion (Y - ) examples include halide ions such as a chloride ion (Cl - ), a bromide ion (Br - ) or an iodine ion (I - ), and acid groups such as a carboxylate (-COO - ), a sulfonate (-SO 3 - ) or an alcoholate (-O - ).
• This quaternary ammonium salt is commercially available, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.
• the compound of formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, and the carbon numbers of R 26 and R 27 are, for example, 1 to 18, and the sum of the carbon numbers of R 26 and R 27 is preferably 7 or more.
• R 26 can be exemplified by alkyl groups such as methyl, ethyl, and propyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups
• R 27 can be exemplified by aralkyl groups such as benzyl groups, and alkyl groups such as octyl and octadecyl groups.
• anion (Y - ) examples include halide ions such as chloride ion (Cl - ), bromide ion (Br - ), and iodine ion (I - ), and acid groups such as carboxylate (-COO - ), sulfonate (-SO 3 - ), and alcoholate (-O - ).
• This compound is commercially available, but can also be produced by reacting, for example, an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an aralkyl halide, alkyl halide, or aryl halide such as benzyl bromide, methyl bromide, or benzene bromide.
• the compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, and R 28 is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, such as a butyl group, an octyl group, a benzyl group, or a lauryl group.
• Y ⁇ examples include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodide ion (I ⁇ ), and acid groups such as carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ), and alcoholate (—O ⁇ ).
• This compound is commercially available, but can be produced, for example, by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide, or an aryl halide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.
• the compound of formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline, and R 29 is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, such as a methyl group, an octyl group, a lauryl group, a benzyl group, etc.
• R 30 is, for example, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and when the compound represented by formula (D-5) is a quaternary ammonium derived from picoline, for example, R 30 is a methyl group.
• the anion (Y - ) include halide ions such as chloride ion (Cl - ), bromide ion (Br - ), and iodine ion (I - ), and acid groups such as carboxylate (-COO - ), sulfonate (-SO 3 - ), and alcoholate (-O - ).
• This compound is commercially available, but can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, and benzyl bromide, or an aryl halide.
• alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, and benzyl bromide
• an aryl halide examples include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.
• the compound of formula (D-6) is a tertiary ammonium salt derived from an amine, where m a is an integer of 2 to 11, and n a is 2 or 3.
• anion (Y ⁇ ) include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodide ion (I ⁇ ), and acid groups such as carboxylate (-COO ⁇ ), sulfonate (-SO 3 ⁇ ), and alcoholate (-O ⁇ ).
• This compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol.
• the carboxylic acid include formic acid and acetic acid.
• the anion (Y ⁇ ) is (HCOO ⁇ ), and when acetic acid is used, the anion (Y ⁇ ) is (CH 3 COO ⁇ ). When phenol is used, the anion (Y ⁇ ) is (C 6 H 5 O ⁇ ).
• the compound of formula (D-7) is a quaternary phosphonium salt having the structure R 31 R 32 R 33 R 34 P + Y - .
• R 31 , R 32 , R 33 , and R 34 are, for example, an alkyl group having 1 to 18 carbon atoms, such as an ethyl group, a propyl group, a butyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms, such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms, such as a benzyl group, and preferably three of the four substituents of R 31 to R 34 are unsubstituted phenyl groups or substituted phenyl groups, such as a phenyl group or a tolyl group, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an a
• anion (Y - ) examples include halide ions such as chloride ion (Cl - ), bromide ion (Br - ), and iodide ion (I - ), and acid groups such as carboxylate (-COO - ), sulfonate (-SO 3 - ), and alcoholate (-O - ).
• This compound is commercially available, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halides, tetraphenylphosphonium halides, tritolylmonoarylphosphonium halides, and tritolylmonoalkylphosphonium halides (wherein the halogen atom is a chlorine atom or a bromine atom).
• trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide
• triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide
• triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide
• tritolylmonoarylphosphonium halides such as tritolylmonophenylphosphonium halide
• tritolylmonoalkylphosphonium halides such as tritolylmonomethylphosphonium halide (wherein the halogen atom is a chlorine atom or a bromine atom).
• phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.
• primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphin
• the compound of formula (D-8) 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, for example, an alkyl group having 1 to 18 carbon atoms, such as an ethyl group, a propyl group, a butyl group, or a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms, such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms, such as a benzyl group, and preferably two of the three substituents of R 35 to R 37 are unsubstituted phenyl groups or substituted phenyl groups, such as a phenyl group or a tolyl group, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aral
• anion (Y ⁇ ) examples include halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodine ion (I ⁇ ), and acid groups such as carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ), alcoholate (—O ⁇ ), maleate anion, and nitrate anion.
• halide ions such as chloride ion (Cl ⁇ ), bromide ion (Br ⁇ ), and iodine ion (I ⁇ )
• acid groups such as carboxylate (—COO ⁇ ), sulfonate (—SO 3 ⁇ ), alcoholate (—O ⁇ ), maleate anion, and nitrate anion.
• This compound is available as a commercially available product, and examples thereof include trialkylsulfonium halides such as tri-n-butylsulfonium halides and tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halides and diphenylethylsulfonium halides, triphenylsulfonium halides (the halogen atom is a chlorine atom or a bromine atom in the above), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carb
• nitrogen-containing silane compound can be added as a curing catalyst.
• nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.
• the amount is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 25 parts by weight, and even more preferably 1 to 20 parts by weight, per 100 parts by weight of polysiloxane.
• the composition for forming a silicon-containing resist underlayer film preferably contains nitric acid.
• Nitric acid may be added during preparation of the composition for forming a silicon-containing resist underlayer film, but it may also be used as a hydrolysis catalyst or during alcohol capping of silanol groups in the production of the above-mentioned polysiloxane, and the resulting solution remaining in the polysiloxane varnish may be treated as nitric acid.
• the amount of nitric acid can be, for example, 0.0001% by mass to 1% by mass, or 0.001% by mass to 0.1% by mass, or 0.005% by mass to 0.05% by mass, based on the total mass of the composition for forming a silicon-containing resist underlayer film.
• the composition for forming a silicon-containing resist underlayer film preferably contains at least one selected from an amine and a hydroxide.
• Amines include ammonia; primary amines such as monomethanolamine, monoethanolamine, monopropanolamine, methylamine, ethylamine, propylamine, and butylamine; secondary amines such as dimethylamine, ethylmethylamine, and diethylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine, dimethylethylamine, methyldiisopropylamine, diisopropylethylamine, diethylethanolamine, and triethanolamine; amines such as ethylenediamine and tetramethylethylenediamine; and cyclic amines such as pyridine and morpholine.
• primary amines such as monomethanolamine, monoethanolamine, monopropanolamine, methylamine, ethylamine, propylamine, and butylamine
• secondary amines such as dimethylamine, ethylmethylamine, and diethyl
• the hydroxide includes inorganic alkali hydroxides and organic alkali hydroxides.
• inorganic alkali hydroxides include sodium hydroxide and potassium hydroxide.
• organic alkali hydroxides include tetraalkylammonium hydroxide, triarylsulfonium hydroxide, diaryliodonium hydroxide, etc.
• tetraalkylammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc.
• triarylsulfonium hydroxides examples include triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, etc.
• diaryliodonium hydroxides examples include diphenyliodonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, etc.
• the content of the amine and hydroxide components in the composition for forming a silicon-containing resist underlayer film can be preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, per 100 parts by mass of polysiloxane.
• the composition for forming a silicon-containing resist underlayer film of the present invention can contain various additives (also referred to as other additives) as other components depending on the application of the composition.
• additives also referred to as other additives
• other components (other additives) that can be blended into the composition for forming a resist underlayer film include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology adjusters, adhesion aids, and other known additives that are blended into materials (compositions) for forming various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, antireflective films, and pattern reversal films.
• Various additives are exemplified
• the stabilizer may be added for the purpose of stabilizing the hydrolysis condensate of the hydrolyzable silane mixture, and specific examples thereof include an organic acid, water, an alcohol, or a combination thereof.
• organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Of these, oxalic acid and maleic acid are preferred.
• the amount of the organic acid added is 0.1 to 5.0% by mass based on the mass of the hydrolysis condensate of the hydrolyzable silane mixture.
• These organic acids can also function as pH adjusters.
• As the water pure water, ultrapure water, ion-exchanged water, etc. can be used. When used, the amount of water 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.
• the alcohol is preferably one that easily dissipates (volatilizes) when heated after application, and examples thereof include methanol, ethanol, propanol, i-propanol, butanol, etc. When an alcohol is added, the amount of the alcohol 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 an organic polymer to the composition for forming a resist underlayer film, it is possible to adjust the dry etching rate (amount of film thickness reduction per unit time) of the film (resist underlayer film) formed from the composition, as well as the attenuation coefficient, refractive index, etc.
• the organic polymer compound is not particularly limited and is appropriately selected from various organic polymers (condensation polymerization polymers and addition polymerization polymers) depending on the purpose of addition.
• addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate.
• organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light absorbing moieties can also be suitably used when such a function is required.
• organic polymer compounds include addition polymerization polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymerization polymers such as phenol novolac and naphthol novolac, but are not limited to these.
• the polymer compound may be either a homopolymer or a copolymer.
• An addition polymerizable monomer is used to produce an addition polymer.
• Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.
• acrylic acid ester compounds include, but are not limited to, 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, and glycidy
• methacrylic acid ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthryl methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxy
• acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.
• methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide.
• vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc.
• 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, and N-hydroxyethylmaleimide.
• a condensation polymerization polymer when used as the polymer, such a polymer may be, for example, a condensation polymerization polymer of a glycol compound and a dicarboxylic acid compound.
• glycol compounds include diethylene glycol, hexamethylene glycol, butylene glycol, etc.
• dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc.
• polyesters, polyamides, and polyimides such as polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, but are not limited to these.
• the organic polymer compound contains a hydroxy group, this hydroxy group can undergo a crosslinking reaction with a hydrolysis condensation product or the like.
• the weight average molecular weight of the organic polymer compound can usually be 1,000 to 1,000,000.
• the weight average molecular weight can be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000.
• Such organic polymer compounds may be used alone or in combination of two or more.
• the composition for forming a silicon-containing resist underlayer film of the present invention contains an organic polymer compound
• its content cannot be generally defined because it is appropriately determined taking into consideration the function of the organic polymer compound, but it can usually be in the range of 1 to 200% by mass relative to the mass of the hydrolysis condensate of the hydrolyzable silane mixture.
• it can be, for example, 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less, and from the viewpoint of fully obtaining the effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.
• Examples of the acid generator include a thermal acid generator and a photoacid generator, and a photoacid generator is preferably used.
• Examples of the photoacid generator include, but are not limited to, an onium salt compound, a sulfonimide compound, a disulfonyldiazomethane compound, and the like.
• Examples of the thermal acid generator include, but are not limited to, tetramethylammonium nitrate.
• onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethan
• sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.
• disulfonyldiazomethane compounds include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, etc.
• the content thereof cannot be generally specified since it is appropriately determined taking into consideration the type of acid generator and the like; however, it is usually in the range of 0.01 to 5 mass % relative to the mass of the hydrolysis condensate of the hydrolyzable silane mixture, and from the viewpoint of suppressing precipitation of the acid generator in the composition, etc., it is preferably 3 mass % or less, more preferably 1 mass % or less, and from the viewpoint of fully obtaining the effect thereof, it is preferably 0.1 mass % or more, more preferably 0.5 mass % or more.
• the acid generators may be used alone or in combination of two or more kinds.
• a photoacid generator and a thermal acid generator may be used in combination.
• the surfactant is effective in suppressing the occurrence of pinholes, striations, etc., when the silicon-containing resist underlayer film forming composition is applied to a substrate.
• the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon surfactants, fluorine surfactants, UV-curable surfactants, etc.
• polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether
• polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether
• polyoxyethylene-polyoxypropylene block copolymers sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate
• sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,
• Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as oleate and polyoxyethylene sorbitan tristearate, trade names EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.
• surfactants include, but are not limited to, fluorine-based surfactants such as C430, FC431 (manufactured by 3M Japan Ltd.), trade name Asahi Guard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• the surfactants can be used alone or in combination of two or more.
• the content of the surfactant is usually 0.0001 to 5 mass %, preferably 0.001 to 4 mass %, and more preferably 0.01 to 3 mass %, relative to the mass of the hydrolysis condensate of the hydrolyzable silane mixture.
• the rheology control agent is added mainly for the purpose of improving the fluidity of the composition for forming a silicon-containing resist underlayer film, and improving the film thickness uniformity of the film formed, particularly in the baking step, and enhancing the filling property of the composition into the inside of the hole.
• phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate
• adipic acid derivatives such as di-n-butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyl decyl adipate
• maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate
• oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate
• stearic acid derivatives such as normal butyl stearate and glyceryl stearate.
• the amount added is usually less than 30 mass % based on the total film-forming components
• the adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the film (resist underlayer film) formed from the composition for forming a silicon-containing resist underlayer film, and particularly for the purpose of suppressing or preventing peeling of the resist during development.
• chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane
• alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane
• silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole
• ⁇ -chloropropyltrimethoxysilane examples include other silanes such as ⁇ -aminopropyltriethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-
• pH adjuster examples include acids having one or more carboxylic acid groups, such as the organic acids listed above as stabilizers.
• the amount of the pH adjuster added can be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, relative to 100 parts by mass of the polysiloxane.
• metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten
• semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).
• the concentration of the film-forming component in the composition for forming a silicon-containing resist underlayer film can be, for example, 0.1 to 50 mass %, 0.1 to 30 mass %, 0.1 to 25 mass %, or 0.5 to 20.0 mass % relative to the total mass of the composition.
• the content of polysiloxane in the film-forming component is usually 20% by mass to 100% by mass. From the viewpoint of reproducibly obtaining the effects of the present invention, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and still more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the additives described below.
• the composition for forming a silicon-containing resist underlayer film preferably has a pH of 2 to 5, and more preferably has a pH of 3 to 4.
• the composition for forming a silicon-containing resist underlayer film can be produced by mixing the hydrolysis condensate of the hydrolyzable silane mixture, a solvent, and, if desired, other components.
• a solution containing the hydrolysis condensate and the like may be prepared in advance, and this solution may be mixed with the solvent and other components.
• the order of mixing is not particularly limited.
• a solvent may be added to a solution containing the hydrolysis-condensation product and the like and then mixed, and other components may be added to the mixture, or the solution containing the hydrolysis-condensation product and the like, the solvent, and other components may be mixed simultaneously.
• a 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.
• the hydrolysis condensate, etc. may aggregate or precipitate when mixed depending on the type and amount of the solvent to be mixed with it, the amount and properties of other components, etc.
• heating may be performed appropriately within a range in which the components are not decomposed or deteriorated.
• the composition for forming a silicon-containing resist underlayer film may be filtered using a sub-micrometer filter or the like during the process of producing the composition, or after all the components have been mixed.
• the material of the filter used in this case is not important, but for example, a nylon filter, a fluororesin filter, etc. can be used.
• composition for forming a silicon-containing resist underlayer film of the present invention can be suitably used as a composition for forming a resist underlayer film used in a lithography process. Furthermore, the composition for forming a silicon-containing resist underlayer film of the present invention can be suitably used as a composition for forming a resist underlayer film used in an EUV or ArF lithography process.
• the silicon-containing resist underlayer film of the present invention is a cured product of the composition for forming a silicon-containing resist underlayer film of the present invention.
• the laminate of the present invention comprises, for example, a semiconductor substrate and the silicon-containing resist underlayer film of the present invention.
• the method for producing a semiconductor element of the present invention includes, for example, forming an organic underlayer film on a substrate; forming a silicon-containing resist underlayer film on an organic underlayer film using the composition for forming a silicon-containing resist underlayer film of the present invention; forming a resist film on the silicon-containing resist underlayer film; Includes.
• the pattern forming method of the present invention includes, for example, forming an organic underlayer film on a semiconductor substrate; A step of applying a composition for forming a silicon-containing resist underlayer film of the present invention onto an organic underlayer film and baking the composition to form a silicon-containing resist underlayer film; forming a resist film on the silicon-containing resist underlayer film; a step of exposing and developing the resist film to obtain a resist pattern; Etching the silicon-containing resist underlayer film using the resist pattern as a mask; Etching the organic underlayer film using the patterned silicon-containing resist underlayer film as a mask; Includes.
• the composition for forming a silicon-containing resist underlayer film of the present invention is applied onto a substrate used in the manufacture of a precision integrated circuit element (e.g., a semiconductor substrate such as a silicon wafer coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (including alkali-free glass, low-alkali glass, and crystallized glass), a glass substrate on which an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film is formed, a plastic (polyimide, PET, etc.) substrate, a substrate coated with a low dielectric constant material (low-k material), a flexible substrate, etc.) by a suitable application method such as a spinner or coater, and then the composition is cured by baking using a heating means such as a hot plate to form a resist underlayer film.
• the silicon-containing resist underlayer film refers to a film formed from the composition for forming a silicon-containing resist underlayer film of the present invention.
• the baking conditions are appropriately selected from a baking temperature of 40° C. to 400° C. or 80° C. to 250° C. and a baking time of 0.3 minutes to 60 minutes.
• the baking temperature is 150° C. to 250° C. and the baking time is 0.5 minutes to 2 minutes.
• the thickness of the resist underlayer film formed here is, for example, 10 nm to 1,000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 to 150 nm.
• composition for forming a silicon-containing resist underlayer film used in forming the resist underlayer film a composition for forming a silicon-containing resist underlayer film filtered through a nylon filter can be used.
• the composition for forming a silicon-containing resist underlayer film filtered through a nylon filter refers to a composition that is filtered through a nylon filter during the production of the composition for forming a silicon-containing resist underlayer film or after mixing all of the components.
• an organic underlayer film is formed on a substrate, and then a silicon-containing resist underlayer film is formed thereon.
• a silicon-containing resist underlayer film is formed thereon.
• the organic underlayer film used here is not particularly limited, and any film that has been conventionally used in the lithography process can be selected and used.
• the silicon-containing resist underlayer film can be processed by using a fluorine-based gas having a sufficiently high etching rate for the photoresist film as an etching gas
• the organic underlayer film can be processed by using an oxygen-based gas having a sufficiently high etching rate for the silicon-containing resist underlayer film as an etching gas
• the substrate can be processed by using a fluorine-based gas having a sufficiently high etching rate for the organic underlayer film as an etching gas.
• the substrate and coating method that can be used in this case are the same as those described above.
• a layer of a photoresist material is formed on the silicon-containing resist underlayer film.
• the resist film can be formed by a known method, that is, for example, by applying a coating type resist material (resist film forming composition) on the silicon-containing resist underlayer film and baking it.
• the thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.
• the photoresist material used in the resist film formed on the silicon-containing resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative photoresist materials and positive photoresist materials can be used.
• photoresist materials consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester
• chemically amplified photoresist materials consisting of a binder having a group that decomposes with acid to increase the alkaline dissolution rate and a photoacid generator
• chemically amplified photoresist materials consisting of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator
• chemically amplified photoresist materials consisting of a binder having a group that decomposes with acid to increase the alkaline dissolution rate, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist material, and a photoacid generator.
• fluorine-containing polymer photoresist materials include those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).
• a resist film for electron beam lithography also called an electron beam resist film
• a resist film for EUV lithography also called an EUV resist film
• a resist film for EUV lithography can be used as the resist film formed on the silicon-containing resist underlayer film instead of a photoresist film.
• the electron beam resist material for forming the electron beam resist film either a negative material or a positive material can be used.
• a chemically amplified resist material consisting of an acid generator and a binder having a group that decomposes with an acid to change the alkaline dissolution rate a chemically amplified resist material consisting of an alkali-soluble binder, an acid generator, and a low molecular weight compound that decomposes with an acid to change the alkaline dissolution rate of the resist material
• a chemically amplified resist material consisting of an acid generator, a binder having a group that decomposes with an acid to change the alkaline dissolution rate, and a low molecular weight compound that decomposes with an acid to change the alkaline dissolution rate of the resist material a non-chemically amplified resist material consisting of a binder having a group that decomposes with an electron beam to change the alkaline dissolution rate, and a non-
• a resist film pattern can be formed in the same way as when a photoresist material is used with an electron beam as the irradiation source.
• a photoresist material is used with an electron beam as the irradiation source.
• an EUV resist material for forming the EUV resist film a methacrylate resin-based resist material can be used.
• the resist material may be a metal-containing resist.
• Metal-containing resists are also called metal oxide resists (MOR), and a representative example is a tin oxide-based resist.
• MOR metal oxide resists
• metal oxide resist materials include coating compositions comprising metal oxo-hydroxo networks having organic ligands via metal carbon bonds and/or metal carboxylate bonds, as described in JP 2019-113855 A.
• An example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand.
• Peroxo-based metal oxo-hydroxo compounds are described in detail in, for example, the patent documents described in paragraph [0011] of Publication 2019-532489. Examples of such patent documents include U.S. Pat. No.
• the resist film formed on the silicon-containing resist underlayer film is exposed through a predetermined mask (reticle).
• a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), an EUV (wavelength 13.5 nm), an electron beam, or the like can be used.
• a post-exposure bake may be carried out as necessary under conditions appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 minutes to 10 minutes.
• a developer e.g., an alkaline developer
• the developer include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline, or an aqueous solution of an amine such as ethanolamine, propylamine, or ethylenediamine.
• 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 carried out with the developer (solvent) after exposure.
• developer solvent
• the photoresist film in the unexposed portion is removed, and a photoresist film pattern is formed.
• Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl a
• the pattern of the photoresist film (upper layer) thus formed is used as a protective film to remove the resist underlayer film (middle layer), then the film consisting of the patterned photoresist film and the patterned resist underlayer film (middle layer) is used as a protective film to remove the organic underlayer film (lower layer), and finally the substrate is processed using the patterned photoresist film (upper layer), patterned resist underlayer film (middle layer), and patterned organic underlayer film (lower layer) as protective films.
• the removal of the resist underlayer film (middle layer) using the pattern of the resist film (upper layer) as a protective film is carried out by dry etching, and gases such as tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. It is preferable to use a halogen-based gas for dry etching of the resist underlayer film.
• gases such as tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur
• a resist film made of an organic material is basically 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, the decrease in the thickness of the photoresist film caused by dry etching of the resist underlayer film can be suppressed. As a result, the photoresist film can be used as a thin film.
• a fluorine-based gas for dry etching of the resist underlayer film
• examples of the fluorine-based gas include, but are not limited to, tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, difluoromethane (CH 2 F 2 ), etc.
• the organic underlayer film (lower layer) is then removed using the patterned resist underlayer film (middle layer) (and the patterned resist film (upper layer) if any remains) as a protective film, and is preferably removed by dry etching with an oxygen-based gas (oxygen gas, oxygen/carbonyl sulfide (COS) mixed gas, etc.).
• oxygen-based gas oxygen gas, oxygen/carbonyl sulfide (COS) mixed gas, etc.
• processing (patterning) of the (semiconductor) substrate which is performed using the patterned silicon-containing resist underlayer film (middle layer) and, if desired, the patterned organic underlayer film (underlayer) as protective films, is preferably 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 ).
• removal of the resist underlayer film may be performed.
• Removal of the silicon-containing resist underlayer film may be performed by dry etching or wet etching. Dry etching of the silicon-containing resist underlayer film is preferably performed with a fluorine-based gas as described in the patterning, such as, but not limited to, tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, difluoromethane (CH 2 F 2 ), etc.
• CF 4 tetrafluoromethane
• C 4 F 8 perfluorocyclobutane
• C 3 F 8 perfluoropropane
• trifluoromethane difluoromethane
• Examples of chemical solutions used for wet etching of silicon-containing resist underlayer films include dilute hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (a mixed solution of HF and NH 4 F), an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution), and an alkaline solution such as a resist stripper (ST-120 (manufactured by Tokyo Ohka Co., Ltd.)).
• alkaline solution examples include ammonia hydrogen peroxide (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide, and water, as well as aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, tri
• an organic anti-reflective film can be formed on top of the silicon-containing resist underlayer film before the formation of the resist film.
• the anti-reflective film composition used therein and any composition that has been conventionally used in lithography processes can be selected and used, and the anti-reflective film can be formed by conventional methods, such as coating with a spinner or coater and baking.
• the substrate on which the silicon-containing resist underlayer film-forming composition is applied may have an organic or inorganic anti-reflective film formed on its surface by a CVD method or the like, and the silicon-containing resist underlayer film may be formed on top of it.
• the substrate used may also have an organic or inorganic anti-reflective film formed on its surface by a CVD method or the like.
• the silicon-containing resist underlayer film formed from the composition for forming a silicon-containing resist underlayer film may also absorb light depending on the wavelength of the light used in the lithography process, and in such a case, can function as an anti-reflection film having an effect of preventing light reflected from the substrate.
• the silicon-containing resist underlayer film can also be used as a layer for preventing interaction between a substrate and a resist film (such as a photoresist film), a layer having a function of preventing adverse effects on a substrate of materials used in the resist film or substances generated during exposure of the resist film, a layer having a function of preventing diffusion of substances generated from the substrate during heating and baking into the resist film, and a barrier layer for reducing the poisoning effect of a resist film due to a dielectric layer of a semiconductor substrate.
• a resist film such as a photoresist film
• a layer having a function of preventing adverse effects on a substrate of materials used in the resist film or substances generated during exposure of the resist film a layer having a function of preventing diffusion of substances generated from the substrate during heating and baking into the resist film
• a barrier layer for reducing the poisoning effect of a resist film due to a dielectric layer of a semiconductor substrate.
• the silicon-containing 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 surface of an uneven semiconductor substrate.
• the silicon-containing resist underlayer film of the present invention can prevent the reflection of undesirable exposure light, such as UV (ultraviolet) light or DUV (deep ultraviolet) light (ArF light, KrF light), from the substrate or interface during EUV exposure (wavelength 13.5 nm) without intermixing with the EUV resist film.
• the silicon-containing resist underlayer film forming composition of the present invention can be suitably used to form an underlayer anti-reflective film of the EUV resist film. That is, it can efficiently prevent reflection as the underlayer of the EUV resist film.
• the process can be carried out in the same manner as for the underlayer film for photoresist.
• the laminate comprising the silicon-containing resist underlayer film of the present invention and a semiconductor substrate as described above can be used to suitably process the semiconductor substrate. Furthermore, according to the method for producing a semiconductor device, which includes the steps of forming an organic underlayer film, 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, and forming a resist film on the silicon-containing resist underlayer film, as described above, highly accurate processing of a semiconductor substrate can be realized with good reproducibility, and therefore stable production of semiconductor devices can be expected.
• the hydrolysis condensation product of the hydrolyzable silane is a condensation product having 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 by GPC analysis in terms of polystyrene.
• the GPC measurement conditions may be, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40° C., an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow velocity) of 1.0 mL/min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.).
• a GPC apparatus trade name HLC-8220GPC, manufactured by Tosoh Corporation
• GPC column trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.
• a column temperature 40° C.
• an eluent elution solvent
• flow rate flow velocity
• Me represents a methyl group and Et represents an ethyl group.
• reaction solution was cooled to room temperature, 34 g of 1-ethoxy-2-propanol was added to the reaction solution, and water, nitric acid, and reaction by-products methanol and ethanol were distilled off under reduced pressure to obtain a concentrated solution of a hydrolysis condensate (polymer) in which 1-ethoxy-2-propanol was used as a solvent.
• the solid content concentration of the obtained concentrated solution exceeded 20% by mass in terms of solid residue when heated at 150°C.
• the resulting hydrolysis condensation product (polysiloxane) was represented by the following formula, and had a weight average molecular weight (Mw) of 1,539 as calculated using polystyrene standards by GPC.
• Mw weight average molecular weight
• Examples 1 to 9 and Comparative Example Evaluation of Siloxane Bond Strength Ratio by FT-IR
• the coating solution obtained in Preparation Example 1 was spin-coated on a silicon wafer and heated on a hot plate at 215° C. for 1 minute to form a silicon-containing resist underlayer film.
• lamination was further performed two times in the same process to obtain a silicon-containing resist underlayer film (80 nm thick) laminated three times.
• silicon-containing resist underlayer films were formed using each of the coating solutions obtained in Preparation Examples 2 to 9 and Comparative Preparation Example.
• the peak intensities of siloxane bonds observed at wave numbers of 1000 to 1250 cm ⁇ 1 were compared using Fourier transform infrared spectroscopy (FT/IR-6600 (manufactured by JASCO Corporation)).
• FT/IR-6600 manufactured by JASCO Corporation
• the peak intensities were compared using values normalized by setting the intensity of the silicon-containing resist underlayer film of the comparative example as 100.
• the bond intensity ratio to the comparative example is relatively low (for example, 60 or less), the solubility tends to be improved.
• Table 3 The obtained results are shown in Table 3.
• Examples 1 to 9 and Comparative Example Evaluation of Water Contact Angle
• the coating solution obtained in Preparation Example 1 was spin-coated on a silicon wafer, and heated on a hot plate at 215° C. for 1 minute to form a silicon-containing resist underlayer film.
• silicon-containing resist underlayer films were formed using each of the coating solutions obtained in Preparation Examples 2 to 9 and Comparative Preparation Example.
• Each of the obtained silicon-containing resist underlayer films was measured using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) with a liquid volume of 3 ⁇ L and after the film was left stationary for 7 seconds after application.
• the solubility tends to be improved.
• Table 3 The obtained measurement results are shown in Table 3.
• Examples 1 to 9 and Comparative Example Evaluation of removability using resist stripper ST-120 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)
• the coating solution obtained in Preparation Example 1 was spin-coated on a silicon wafer, and heated on a hot plate at 215° C. for 1 minute to form a silicon-containing resist underlayer film (20 nm).
• silicon-containing resist underlayer films were formed using each of the coating solutions obtained in Preparation Examples 2 to 9 and Comparative Preparation Example.
• the silicon wafers on which the silicon-containing resist underlayer films were formed were immersed in ST-120 adjusted to a liquid temperature of 40° C. for 60 seconds, then rinsed with water for 20 seconds, and then dried.
• the thickness of the silicon-containing resist underlayer film after immersion in ST-120 for 60 seconds was measured, and the change rate (%) of the film thickness was calculated.
• a film having a change rate of the film thickness after immersion of 80% or more relative to the film thickness of the silicon-containing resist underlayer film before immersion was evaluated as "very good", a film having a change rate of 5% or more but less than 80% was evaluated as “good”, and a film having a change rate of less than 5% was evaluated as "poor”.
• the obtained results are shown in Table 3.

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