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 silicon-containing resist underlayer film, in particular a composition for forming a silicon-containing resist underlayer film that can be wet-removed.
• 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 on the substrate surface corresponding to the pattern.
• 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 and an organic solvent, In the hydrolysis condensation product, at least a part of the silanol groups is capped with an alcohol-based compound
• a composition for forming a silicon-containing resist underlayer film which is a composition for forming a silicon-containing resist underlayer film that is soluble in a basic chemical solution.
• a capping ratio of the alcohol-based compound in the hydrolysis condensate is 4% to 9%.
• composition for forming a silicon-containing resist underlayer film according to any one of [1] to [8], further comprising a compound A having a chemical structure containing a cation AX + and an anion AZ ⁇ , the molecular weight of the anion being 65 or more.
• Z represents an aromatic ring, a cyclic alkane, or a non-aromatic cyclic alkene
• R 501 represents an alkyl group which may be partially or completely substituted with a fluorine atom
• R 302 and R 303 each independently represent an alkyl group
• R 304 and R 305 each independently represent an alkyl group.
• Pattern formation method [14] The method further comprises removing the silicon-containing resist underlayer film by a wet method using a chemical solution after the step of etching the organic underlayer film.
• 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 composition for forming a silicon-containing resist underlayer film of the present invention is a composition for forming a silicon-containing resist underlayer film that is soluble in a basic chemical solution.
• the composition for forming a silicon-containing resist underlayer film contains a hydrolysis-condensation product and an organic solvent.
• the hydrolysis condensation product is a polysiloxane obtained by hydrolysis condensation of a hydrolyzable silane mixture. In the hydrolysis condensation product, at least a portion of the silanol groups is capped with an alcohol compound.
• the silanol groups are capped with an alcohol-based compound, so that the silicon-containing resist underlayer film formed from the composition for forming a silicon-containing resist underlayer film is soluble in a basic chemical solution and can be peeled off even by a method using wet etching.
• the inventors believe that this is because, when forming a silicon-containing resist underlayer film from the composition for forming a silicon-containing resist underlayer film, the condensation of the silanol groups is appropriately suppressed by the cap, which results in an appropriately suppressed crosslink density of the film.
• the number of carbon atoms in the alcohol-based compound is not particularly limited, but is preferably 1 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms.
• the alcohol-based compound is not particularly limited as long as it has one OH group, and may be an alcohol (R 1 -OH; R 1 represents an alkyl group) or an alkylene glycol monoalkyl ether. Among these, alkylene glycol monoalkyl ether is preferred.
• alkylene glycol monoalkyl ethers examples include propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.
• propylene glycol monoethyl ether (1-ethoxy-2-propanol) is preferred.
• R represents a residue obtained by removing an OH group from an alcohol compound. * represents a bond.
• R is preferably a -R a OR b group (R a represents an alkylene group having 2 to 3 carbon atoms, and R b represents an alkyl group having 1 to 4 carbon atoms).
• the capping ratio with an alcohol-based compound in the hydrolysis condensation product is not particularly limited, but from the viewpoint of favorably obtaining the effects of the present invention, it is preferably 2% to 15%, and more preferably 4% to 9%.
• the capping ratio with the alcohol-based compound can be calculated as follows.
• the capping ratio by the alcohol-based compound is calculated by 1 H NMR.
• JNM-ECA500 manufactured by JEOL
• Deuterated acetone is used as the deuterated solvent.
• the integral ratio of the chemical shift values of the reference protons is taken as the reference.
• the chemical shift value of the ⁇ -position methine proton of a secondary alcohol compound is detected at around 3.8 ppm, but when a bond is formed with a silicon atom by a dehydration condensation reaction with a silanol group, that is, when a capping reaction occurs with the silanol group, the chemical shift value of the methine proton moves to around 4.2 ppm.
• the integral ratio of the methine proton that has moved to around 4.2 ppm is measured.
• the integral ratio of the reference proton measured previously is compared to calculate the capping ratio due to the alcohol-based compound.
• the cap ratio can be calculated by the following formula (Cap).
• Cap ratio (%) [A/(B1/(C ⁇ D))] ⁇ 100 (Cap)
• the hydrolyzable silane mixture contains trialkoxymethylsilane, three protons of methyl group bonded to silicon atom of trialkoxymethylsilane are used as reference protons.
• the hydrolyzable silane mixture contains trialkoxyphenylsilane, five protons of phenyl group of trialkoxyphenylsilane are used as reference protons.
• the capping ratio is 10%.
• the silanol groups capped with an alcohol-based compound can be easily decapped by water.
• the alcohol-based compound capping the silanol groups can be easily detached from the silanol groups by water.
• the silanol groups are revealed. Therefore, if the composition for forming a silicon-containing resist underlayer film contains water, it is likely that all of the silanol groups will not be capped by decapsation, and in this case, the effects of the present invention will not be achieved. In this respect, it is preferable that the composition for forming a silicon-containing resist underlayer film contains as little water as possible.
• the content of water in the composition for forming a silicon-containing resist underlayer film is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably even less, relative to the hydrolysis condensate. That is, it is particularly preferable that the composition for forming a silicon-containing resist underlayer film does not substantially contain water.
• water is used to carry out hydrolysis.
• dehydration is carried out to promote the reaction.
• the product containing the hydrolysis condensate may contain a small amount of water, which may be carried into the composition for forming a silicon-containing resist underlayer film together with the hydrolysis condensate.
• compositions for forming a silicon-containing resist underlayer film may coexist with water.
• water-soluble organic solvents may contain water as an impurity at a commercially acceptable purity.
• unavoidable water carryover into the composition for forming a silicon-containing resist underlayer film is permitted.
• substantially free of water does not exclude unavoidable water carryover into the composition for forming a silicon-containing resist underlayer film.
• 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 the hydrolysis is partially stopped and the condensation is not completed, and therefore, Si-OH groups remain.
• the composition for forming the 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 hydrolyzable silane mixture includes a plurality of hydrolyzable silanes.
• the hydrolyzable silane mixture contains, for example, at least one of a hydrolyzable silane represented by the following formula (1), a hydrolyzable silane represented by the following formula (2), a hydrolyzable silane represented by the following formula (3), a hydrolyzable silane represented by the following formula (4), and a hydrolyzable silane represented by the following formula (5).
• the hydrolyzable silane mixture preferably contains a hydrolyzable silane represented by formula (1).
• the hydrolyzable silane mixture preferably contains a hydrolyzable silane represented by formula (4). More preferably, the hydrolyzable silane mixture contains a hydrolyzable silane represented by formula (1) and a hydrolyzable silane represented by formula (4).
• the hydrolyzable silane mixture may contain other hydrolyzable silanes.
• the hydrolyzable silane mixture preferably contains a hydrolyzable silane represented by formula (1).
• the hydrolyzable silane mixture contains the hydrolyzable silane represented by formula (4)
• the molar ratio of the hydrolyzable silane represented by formula (4) in the hydrolyzable silane mixture is not particularly limited from the viewpoint of dry etching resistance, but is preferably 50 mol% or more, more preferably 60 mol% or more.
• the molar ratio of the hydrolyzable silane represented by formula (4) in the hydrolyzable silane mixture is preferably 90 mol% or less, more preferably 85 mol% or less, and particularly preferably 80 mol% or less. Since the hydrolyzable silane represented by formula (4) described later is a component of Q unit, when the hydrolyzable silane mixture contains a large amount of the hydrolyzable silane represented by formula (4), the crosslink density of the silicon-containing resist underlayer film obtained tends to be high.
• the present invention is particularly useful when the hydrolyzable silane mixture contains the hydrolyzable silane represented by formula (4).
• the hydrolyzable silane mixture contains a hydrolyzable silane represented by formula (1) and a hydrolyzable silane represented by formula (4).
• R1 is a group bonded to a silicon atom and represents an organic group containing a succinic anhydride skeleton.
• R 1 is a group that does not hydrolyze, in other words, Si—R 1 does not dissociate by hydrolysis.
• the organic group for R1 is not particularly limited as long as it is an organic group containing the above skeleton.
• organic groups containing a succinic anhydride skeleton include not only the skeleton itself, but also organic groups in which one or more hydrogen atoms in an alkyl group are substituted with a succinic anhydride skeleton.
• the alkyl group 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.
• 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 group, a 3-methyl-n-pentyl group,
• the aryl group examples include, but are not limited to, a
• cyclic alkyl group examples include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a
• the organic group for R 1 above is, for example, a monovalent group represented by the following formula (1-1).
• 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 thereof.
• R2 is a group that does not hydrolyze. In other words, Si- R2 does not dissociate by hydrolysis.
• alkyl group for R 2 in formula (1) examples include linear or branched alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl
• the aryl group examples include a -n-pentyl
• Cyclic alkyl groups can also be used.
• Examples of cyclic alkyl groups having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl ...
• cyclopropyl groups include ethyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl groups.
• the halogenated alkyl group in R2 of formula (1) refers to an alkyl group substituted with a halogen atom.
• the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and specific examples of the alkyl group include the same as those mentioned above.
• 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.
• halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group,
• the alkoxyalkyl group for R2 in formula (1) refers to an alkyl group substituted with an alkoxy group.
• Specific examples of the alkyl group include the same as those mentioned above.
• Specific examples of the alkoxy group include alkoxy groups having a straight-chain, branched or cyclic alkyl moiety having 1 to 20 carbon atoms.
• Examples of the straight-chain or branched alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-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-
• 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-cyclo butoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-
• the number of carbon atoms in the alkoxyalkyl 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 alkoxyalkyl groups include lower alkyloxy-lower alkyl groups such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group, but are not limited to these.
• Examples of the substituents in the alkyl group, halogenated alkyl group, or alkoxyalkyl group include alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, aryloxy groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, alkoxy groups, and aralkyloxy groups.
• Specific examples of the alkyl groups, halogenated alkyl groups, alkoxyalkyl groups, and alkoxy groups and their preferred numbers of carbon atoms are the same as those mentioned above.
• aryl groups listed in the above substituents include, for example, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-mercaptophenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p-cyanophenyl, ⁇ -naphthyl, ⁇ -naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl groups, but are not limited to these.
• aralkyl groups listed in the above substituents include, but are not limited to, phenylmethyl (benzyl), 2-phenylethylene, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, and 10-phenyl-n-decyl groups.
• the halogenated aryl group mentioned as the above-mentioned substituent is an aryl group substituted with a halogen atom, and specific examples of such an aryl group 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 aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• halogenated aryl group examples include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group, a 2,3,4,6-tetrafluorophenyl group
• fluorophenyl group examples include, but are not limited to, a pentafluorophenyl group, a 2-fluoro-1-naphthyl group, a 3-fluoro-1-naphthyl group, a 4-fluoro-1-naphthyl group, a 6-fluoro-1-naphthyl group, a 7-fluoro-1-naphthyl group, an 8-fluoro-1-naphthyl group, a 4,5-difluoro-1-naphthyl group, a 5,7-difluoro-1-naphthyl group, a 5,8-difluoro-1-naphthyl group, a 5,6,7,8-tetrafluoro-1-naphthyl group, a heptafluoro-1-naphthyl group, a 1-fluoro-2-naphthy
• the halogenated aralkyl groups exemplified as the above substituents are aralkyl groups substituted with a halogen atom, and specific examples of such aralkyl groups and halogen atoms are the same as those mentioned above.
• 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.
• halogenated aralkyl groups include, but are not limited to, 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,4,6-trifluorobenzyl group, 2,3,4,5-tetrafluorobenzyl group, 2,3,4,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluorobenzyl group, and 2,3,4,5,6-pentafluorobenzyl group.
• the aryloxy group mentioned as the above 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 mentioned above.
• the number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less, and specific examples thereof include, but are not limited to, a phenoxy group, a naphthalene-2-yloxy group, and the like. When two or more substituents are present, the substituents may be bonded to each other to form a ring.
• the alkoxyaryl group exemplified as the above substituent is an aryl group substituted with an alkoxy group, and specific examples of such alkoxy groups and aryl groups include the same as those mentioned above.
• the number of carbon atoms in the alkoxyaryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• 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, and a 7-methoxynaphthalen-1-yl group.
• the alkoxyaralkyl group exemplified as the above substituent is an aralkyl group substituted with an alkoxy group, and specific examples of such alkoxy groups and aralkyl groups include the same as those mentioned above.
• the number of carbon atoms in the alkoxyaralkyl 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 alkoxyaralkyl group include, but are not limited to, a 3-(methoxyphenyl)benzyl group, a 4-(methoxyphenyl)benzyl group, and the like.
• alkenyl groups listed in the above substituents include alkenyl groups which may be substituted, for example, alkenyl groups having 2 to 10 carbon atoms. More specifically, ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-but ...2-methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-prop
• the aralkyloxy group mentioned as the above substituent is a group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol, and specific examples of such an aralkyl group include the same as those mentioned above.
• the number of carbon atoms in the aralkyloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even 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.
• Examples of the organic group containing an epoxy group in R2 of the above formula (1) include, but are not limited to, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.
• Examples of the organic group containing an acryloyl group in R2 of the above formula (1) include, but are not limited to, an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.
• Examples of the organic group containing a methacryloyl group in R2 of the above formula (1) include, but are not limited to, a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
• Examples of the organic group containing a mercapto group in R2 of the above formula (1) include, but are not limited to, an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, and an octyl mercapto group.
• Examples of the organic group containing an amino group in R2 of the above formula (1) include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group.
• Examples of the organic group containing an alkoxy group in R2 of the above formula (1) 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 containing a sulfonyl group in R2 of the above formula (1) include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group.
• Examples of the organic group containing a cyano group in R2 of the above formula (1) include, but are not limited to, a cyanoethyl group and a cyanopropyl group.
• 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.
• alkoxy group and halogen atom include the same as those described above.
• An aralkyloxy group is a group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol, and specific examples of such aralkyl groups include the same as those mentioned above.
• the number of carbon atoms in the aralkyloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even 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 group derived by removing a hydrogen atom from the carboxylic acid group of a carboxylic acid compound, and typically includes, but is not limited to, an alkylcarbonyloxy group, an arylcarbonyloxy group, or an aralkylcarbonyloxy group derived by removing a hydrogen atom from the carboxylic acid group of an alkylcarboxylic acid, an arylcarboxylic acid, or an aralkylcarboxylic acid.
• Specific examples of the alkyl group, aryl group, and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid, and aralkylcarboxylic acid are the same as those mentioned above.
• acyloxy group examples include acyloxy groups having 2 to 20 carbon atoms.
• a represents 1, b represents an integer of 0 to 2, and 4-(a+b) represents an integer of 1 to 3.
• b preferably represents 0 or 1, and more preferably 0.
• compounds represented by the above formula (1) 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 molar ratio of the hydrolyzable silane represented by formula (1) in the hydrolyzable silane mixture is not particularly limited, but is preferably 0.1 mol% to 10 mol%, more preferably 0.3 mol% to 5 mol%, and particularly preferably 0.5 mol% to 3 mol%.
• R4 represents an organic group that is bonded to a silicon atom and includes an optionally substituted amino group.
• R4 is a group that does not hydrolyze. In other words, Si- R4 does not dissociate by hydrolysis.
• Examples of the substituent in the optionally substituted amino group include an alkyl group having 1 to 4 carbon atoms, a phenyl group, and the like.
• Examples of the optionally substituted amino group include an amino group (—NH 2 ), and a mono- or di-substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms or a phenyl group.
• Examples of the organic group containing an optionally substituted amino group include an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, and a 3-phenylaminopropyl group.
• R5 is the same as R2 in formula (1) above.
• R 6 is the same as R 3 in formula (1) above.
• a represents 1, b represents an integer of 0 to 2, and 4-(a+b) represents an integer of 1 to 3.
• b preferably represents 0 or 1, and more preferably 0.
• compounds represented by the above formula (2) include dimethylaminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and 3-phenylaminopropyltriethoxysilane.
• the molar ratio of the hydrolyzable silane represented by formula (2) in the hydrolyzable silane mixture is not particularly limited, but is preferably 0.01 mol% to 10 mol%, more preferably 0.03 mol% to 5 mol%, and particularly preferably 0.05 mol% to 3 mol%.
• R7 is a group bonded to a silicon atom and represents an organic group containing an alkenyl group.
• R7 is a group that does not hydrolyze. In other words, Si- R7 does not dissociate by hydrolysis.
• the organic group of R7 is not particularly limited as long as it is an organic group containing an alkenyl group.
• organic groups containing an alkenyl group include not only the alkenyl group itself, but also organic groups in which one or more hydrogen atoms in an alkyl group are substituted with an alkenyl group.
• an alkenyl group which may be substituted can be mentioned, for example, an alkenyl group having 2 to 10 carbon atoms. More specifically, an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-ethylethenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-n-propylethenyl group, a 1-methyl-1- butenyl group,
• R 8 is the same as R 2 in formula (1) above.
• R 9 is the same as R 3 in formula (1) above.
• a represents 1, b represents an integer of 0 to 2, and 4-(a+b) represents an integer of 1 to 3.
• b preferably represents 0 or 1, and more preferably 0.
• the compound represented by the above formula (3) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, ⁇ -glycidoxypropylvinyldimethoxysilane, ⁇ -glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, Examples of silane compounds containing an al
• the molar ratio of the hydrolyzable silane represented by formula (3) in the hydrolyzable silane mixture is not particularly limited, but is preferably 30 mol% or less, more preferably 25 mol% or less, and particularly preferably 20 mol% or less.
• the lower limit of the molar ratio of the hydrolyzable silane represented by formula (3) is, for example, 1 mol%, 3 mol%, or 5 mol%.
• R 10 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• Specific examples of the alkoxy group, the aralkyloxy group, and the acyloxy group include the same as those mentioned above.
• hydrolyzable silanes represented by formula (4) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane.
• a tetrafunctional silane such as tetramethoxysilane or tetraethoxysilane represented by formula (4).
• R 11 represents an organic group which is a group bonded to a silicon atom and contains at least one group selected from the group consisting of aryl groups and groups represented by the formula (5-2) described below.
• R 11 is a group that does not undergo hydrolysis. In other words, Si—R 11 does not dissociate by hydrolysis.
• the organic group for R 11 is not particularly limited as long as it is an organic group containing the above groups.
• the organic group containing an aryl group and a group represented by formula (5-2) described later can be not only the group itself, but also an organic group in which one or more hydrogen atoms in an alkyl group are substituted with at least one selected from the group consisting of aryl groups and groups represented by formula (5-2) described later.
• the aryl group in R 11 may be an optionally substituted aryl group, for example, an aryl group having 6 to 20 carbon atoms. More specifically, as explained in relation to R 2 in formula (1), examples of the aryl group include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-mercaptophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-aminophenyl group, a p-cyanophenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, an o-biphenylyl group, an m-b
• examples of the group containing the aryl group include an aralkyl group which may be substituted, an aryl halide group which may be substituted, an aralkyl group which may be substituted, an alkoxyaryl group which may be substituted, and an alkoxyaralkyl group which may be substituted.
• 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 mentioned above.
• the number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• aralkyl group examples 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.
• a phenylmethyl group benzyl group
• 2-phenylethylene 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
• the halogenated aryl group is an aryl group substituted with a halogen atom, and specific examples of such aryl 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 aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• halogenated aryl group examples include, as explained in relation to R 2 in the above formula (1), a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group,
• the halogenated aralkyl group is an aralkyl group substituted with a halogen atom, and specific examples of such aralkyl groups and halogen atoms are the same as those mentioned above.
• 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.
• halogenated aralkyl group examples include, but are not limited to, a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2,3-difluorobenzyl group, a 2,4-difluorobenzyl group, a 2,5-difluorobenzyl group, a 2,6-difluorobenzyl group, a 3,4-difluorobenzyl group, a 3,5-difluorobenzyl group, a 2,3,4-trifluorobenzyl group, a 2,3,5-trifluorobenzyl group, a 2,3,6-trifluorobenzyl group, a 2,4,5-trifluorobenzyl group, a 2,4,6-trifluorobenzyl group, a 2,3,4,5-tetrafluorobenzyl group, a 2,3,4,6-fluor-
• the above alkoxyaryl group is an aryl group substituted with an alkoxy group, and specific examples of such aryl groups and alkoxy groups are the same as those mentioned above.
• the number of carbon atoms in the alkoxyaryl 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 alkoxyaryl group include, for example, as explained in relation to R 2 in the above formula (1), 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-
• the alkoxyaralkyl group is an aralkyl group substituted with an alkoxy group, and specific examples of such alkoxy groups and aralkyl groups are the same as those mentioned above.
• the number of carbon atoms in the alkoxyaralkyl 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 alkoxyaralkyl group include, but are not limited to, a 3-(methoxyphenyl)benzyl group, a 4-(methoxyphenyl)benzyl group, and the like.
• X 101 each independently represent any one of the following formulae (5-3) to (5-5), and the carbon atom of the ketone group in the following formulae (5-4) and (5-5) is bonded to the nitrogen atom to which R 102 in the formula (5-2) is bonded.
• R 103 to R 107 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group.
• Specific examples of the optionally substituted alkyl group and the optionally substituted alkenyl group and suitable numbers of carbon atoms therein are the same as those exemplified above for the alkyl group in which a hydrogen atom is substituted by a succinic anhydride skeleton or the like for R 1 , and the same as those exemplified above for the alkenyl group.
• Examples of the organic group containing an epoxy group include, but are not limited to, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.
• Examples of the organic group containing a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group.
• R 101 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group
• the optionally substituted alkyl group is preferably an alkyl group in which a 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, a 4-vinylbutyl group, etc.
• the alkylene group is a divalent group derived by removing one more hydrogen atom from the alkyl group, and may be linear, branched, or cyclic.
• 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 still more preferably 10 or less.
• the alkylene group of R 102 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.
• 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
• Hydroxyalkylene groups are those in which at least one of the hydrogen atoms of the alkylene groups has been replaced with a hydroxy group, and specific examples include, but are not limited to, hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxytrimethylene, 2-hydroxytrimethylene, 3-hydroxytrimethylene, 1-hydroxytetramethylene, 2-hydroxytetramethylene, 3-hydroxytetramethylene, 4-hydroxytetramethylene, 1,2-dihydroxytetramethylene, 1,3-dihydroxytetramethylene, 1,4-dihydroxytetramethylene, 2,3-dihydroxytetramethylene, 2,4-dihydroxytetramethylene, and 4,4-dihydroxytetramethylene groups.
• R 11 is preferably a group containing at least one selected from the group consisting of a phenyl group, a diaminopropyl group, and an isocyanuric acid skeleton (in formula (5-2), X 101 represents a group represented by formula (5-5)).
• R 12 is the same as R 2 in formula (1) above.
• R 13 is the same as R 3 in formula (1) above.
• a represents 1
• b represents an integer of 0 to 2
• 4-(a+b) represents an integer of 1 to 3.
• b preferably represents 0 or 1, and more preferably 0.
• the compound represented by the above formula (5) include, for example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane,
• Silane compounds containing phenyl groups such as phenyl silane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane; methoxy
• a silane compound in which R 11 is an organic group containing a group represented by the above formula (5-2) may be a commercially available product, or may be synthesized by a known method described in, for example, WO 2011/102470.
• Specific examples of the silane compound containing an organic group containing a group represented by the above formula (5-2) include the compounds exemplified below, but are not limited to these.
• examples of the silane compound represented by the above formula (5) include aryl group-containing silane compounds represented by formulas (A-1) to (A-41).
• the molar ratio of the hydrolyzable silane represented by formula (5) in the hydrolyzable silane mixture is not particularly limited, but is preferably 5 mol% to 35 mol%, more preferably 7 mol% to 30 mol%, and particularly preferably 10 mol% to 25 mol%.
• hydrolyzable silanes for the purpose of adjusting the film properties such as the film density, other silane compounds (other hydrolyzable silanes) represented by the following formula (6) can be used in the above hydrolyzable silane mixture together with at least one of the hydrolyzable silanes represented by formulas (1) to (5).
• the hydrolyzable silane represented by formula (6) is a compound other than the hydrolyzable silanes represented by formulas (1) to (5).
• R 14 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 amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof.
• R 15 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. and c represents an integer of 1 to 3.
• each group in R 14 and the suitable number of carbon atoms therefor include the groups and the numbers of carbon atoms described above for R 2 in formula (1).
• Specific examples of each group in R 15 and the suitable number of carbon atoms therefor include the groups, atoms, and numbers of carbon atoms described above for R 3 in formula (1).
• hydrolyzable silanes represented by formula (6) include methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxy ...
• Glycidoxysilane ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltripoxysilane, ⁇ -glycidoxypropyltributoxysilane Silane, ⁇ -glycidoxybutyltrimethoxysilane, ⁇ -glycidoxybutyltriethoxysilane, ⁇ -glycidoxybutyltriethoxysilane, ⁇ -glycidoxybutyltrime
• hydrolyzable silane mixture may contain other silane compounds (hydrolyzable silanes) other than the above examples, as long as the effects of the present invention are not impaired.
• 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 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 that is a hydrolyzable group.
• 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.
• At least some of the silanol groups can be capped by including an alcohol-based compound in the system. Capping occurs through a reaction between at least some of the silanol groups and the hydroxyl groups of the alcohol-based compound.
• the reaction between the silanol groups and the hydroxyl groups of an alcohol-based compound can be carried out, for example, by contacting the uncapped hydrolysis condensate with the alcohol-based compound and reacting for 0.1 to 48 hours, for example 24 hours, at a temperature of 40 to 160°C, for example 60°C, to obtain a modified polysiloxane in which the silanol groups are capped.
• the alcohol-based compound which is the capping agent, can be used as an organic solvent.
• the reaction solution can be used as is or after dilution or concentration, neutralized, and treated with an ion exchange resin to remove the hydrolysis catalyst, such as the acid or base, used in the hydrolysis and condensation.
• the hydrolysis catalyst such as the acid or base
• the by-product alcohol and water, and the hydrolysis catalyst used, etc. can be removed from the reaction solution by vacuum distillation or the like. This minimizes the amount of water mixed into the composition for forming a silicon-containing resist underlayer film.
• the hydrolysis condensate thus obtained (hereinafter also referred to as polysiloxane) is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and can be used as it is as a composition for forming a silicon-containing resist underlayer film described below.
• the obtained polysiloxane varnish may be solvent-substituted 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 solid concentration 100%.
• the organic solvent used for the 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 mixture.
• the dilution solvent is not particularly limited, and one or more kinds may be selected and used as desired.
• 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, an organic solvent, a specific additive (compound A) having a chemical structure containing a cation AX + and an anion AZ ⁇ , and other components.
• Organic 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 an organic solvent that can dissolve the solid content in the composition for forming a silicon-containing resist underlayer film. There are no limitations on such organic solvents as long as they dissolve the hydrolysis condensate of the hydrolyzable silane mixture, the specific additive (compound A), and other components.
• the organic solvent may be the above-mentioned alcohol-based compound.
• the organic solvent 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-methylpropionat
• the specific additive is a compound having a chemical structure containing a cation AX + and an anion AZ ⁇ , and the molecular weight of the anion is 65 or more.
• cation means a positively charged atom or a group of atoms
• anion means a negatively charged atom or a group of atoms.
• a specific additive compound A
• a composition for forming a silicon-containing resist underlayer film increases the solubility of the silicon-containing resist underlayer film in alkaline solutions (basic chemical solutions). This is presumably because the anion species in the specific additive (compound A) is present between the hydrolysis condensate (polymer) and inhibits the bonds that crosslink the hydrolysis condensate, or the anion species itself bonds and caps, preventing three-dimensional crosslinking from progressing.
• the molecular weight of the anion AZ ⁇ is more preferably 65 or more from the viewpoint of suppressing condensation, and more preferably 500 or less from the viewpoint of maintaining dry etching resistance.
• the anion AZ ⁇ may be present outside or inside the molecule of the cation AX + .
• the anion AZ- exists outside the molecule of the cation AX + " means that the anion AZ- is not bound to the cation AX + via a covalent bond and exists as a structural unit independent of the cation AX + .
• Examples of the form of the compound A as described above include salts.
• the anion existing outside the molecule of the cation is also referred to as a counter anion.
• the anion AZ ⁇ may be bound to the cation AX + via a covalent bond, that is, compound A may be in the form of an inner salt (also called a zwitterion).
• anion AZ ⁇ is not particularly limited as long as it satisfies the condition that the molecular weight of the anion is 65 or more.
• anion include anions having the chemical structures represented by the following (A) to (E).
• Z represents an aromatic ring, a cyclic alkane, or a non-aromatic cyclic alkene;
• R 501 represents an alkyl group which may be partially or completely substituted with a fluorine atom;
• R 302 and R 303 each independently represent an alkyl group;
• R 304 and R 305 each independently represent an alkyl group.
• alkyl group aryl group, halogenated alkyl group, and aralkyl group are the same as those described above.
• substituent that may be substituted on the alkyl group and the like are the same as those described above.
• An example of the specific additive (compound A) is a compound having a sulfonate anion represented by the above formula (A).
• the compound having the sulfonate anion represented by the above formula (A) may be not only a compound having the anion represented by the formula (A) outside the molecule, but also a compound having the anion represented by the formula (A) inside the molecule, such as sulfobetaines such as lauryl sulfobetaine and myristyl sulfobetaine (see compounds (Add-6) and (Add-7) below).
• the specific additive (compound A) is, for example, a compound having an anion containing a triazole skeleton represented by the above formula (B-1) or (B-2).
• Z represents an aromatic ring having 1 to 6 carbon atoms, a cyclic alkane, or a non-aromatic cyclic alkene.
• a compound having an anion represented by formula (B-2) is preferred, and in particular, in formula (B-2), Z is preferably an aromatic ring. That is, a preferred embodiment of the specific additive (compound A) is, for example, a compound having an anion containing a benzotriazole skeleton represented by the following (b-1).
• R 501 represents an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group in which the alkyl group is partially or entirely substituted with a fluorine atom, or a perfluoroalkyl group.
• R 501 is preferably a CF 3 group or a C 4 F 9 group.
• the specific additive (compound A) is more preferably a compound having a bis(trifluoromethanesulfonyl)imide anion represented by the following (c-1).
• An example of a specific additive is a compound having a thiophosphate anion represented by the above formula (D).
• An example of a specific additive is a compound having a phosphate anion represented by the above formula (E).
• Specific examples of the specific additive include, but are not limited to, compounds represented by the following formulas (Add-1) to (Add-12).
• composition for forming a silicon-containing resist underlayer film of the present invention contains a specific additive, the content thereof can be 1 to 30 parts by mass per 100 parts by mass of the hydrolysis condensation product.
• additives also referred to as other additives
• various additives that are components other than the above-mentioned specific additives can be blended depending on the application of the composition.
• Examples of other components (other additives) that can be blended into the composition for forming a silicon-containing resist underlayer film include curing catalysts (ammonium salts, phosphines, phosphonium salts, sulfonium salts, nitrogen-containing silane compounds, etc.), 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, rheology adjusters, adhesion aids, and other known additives that are blended into materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films.
• Various additives are exemplified below, but are not limited to these.
• 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 is an integer of 2 to 3
• H is a hydrogen atom
• N is a nitrogen atom
• Y 1 ⁇ is an anion
• R 31 , R 32 , R 33 , and R 34 represent an alkyl group or an aryl group
• P represents a phosphorus atom
• Y ⁇ represents an anion
• R 31 , R 32 , R 33 , and R 34 are each bonded to the phosphorus atom via a C—P bond).
• R 35 , R 36 , and R 37 represent an alkyl group or an aryl group
• S represents a sulfur atom
• Y ⁇ represents an anion
• R 35 , R 36 , and R 37 are each bonded to the sulfur atom via a C—S bond).
• the compound of formula (D-1) above is a quaternary ammonium salt derived from an amine, in which m is an integer from 2 to 11 and n is an integer from 2 to 3.
• R 21 in this quaternary ammonium salt represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples of such groups include linear alkyl groups such as ethyl, propyl, and butyl groups, benzyl, cyclohexyl, cyclohexylmethyl, 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) above is a quaternary ammonium salt represented by R 22 R 23 R 24 R 25 N + Y - .
• R 22 , R 23 , R 24 and R 25 are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms.
• 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 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) above is a quaternary ammonium salt derived from 1-substituted imidazole, and R 26 and R 27 each have 1 to 18 carbon atoms, and it is preferable that the sum of the carbon atoms of R 26 and R 27 is 7 or more.
• R 26 can be methyl, ethyl, propyl, phenyl, or benzyl, and R 27 can be benzyl, octyl, or octadecyl.
• anion (Y - ) examples include halide ions such as chloride ion (Cl - ), bromide ion (Br - ), or iodine ion (I - ), and acid groups such as carboxylate (-COO - ), sulfonate (-SO 3 - ), or alcoholate (-O - ).
• This compound is commercially available, but can also be produced by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an alkyl halide or aryl halide such as benzyl bromide or methyl bromide.
• the compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and R 28 is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, such as a butyl group, an octyl group, a benzyl group, or a lauryl group.
• 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, and octyl bromide, or an aryl halide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.
• the compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline
• R 29 is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, such as a methyl group, an octyl group, a lauryl group, or a benzyl group.
• R 30 is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and in the case of a quaternary ammonium derived from picoline, R 30 is a methyl group.
• 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, a substituted pyridine such as picoline with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or an aryl halide, etc.
• Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.
• the compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, where m is an integer of 2 to 11 and n is an integer of 2 to 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.
• Examples of the carboxylic acid include formic acid and acetic acid.
• the anion (Y ⁇ ) is (HCOO ⁇ )
• the anion (Y ⁇ ) is (CH 3 COO ⁇ )
• the anion (Y ⁇ ) is (C 6 H 5 O ⁇ ).
• the compound of the above formula (D-7) is a quaternary phosphonium salt having a structure of R 31 R 32 R 33 R 34 P + Y -.
• R 31 , R 32 , R 33 , and R 34 are alkyl groups having 1 to 18 carbon atoms, or aryl groups having 6 to 18 carbon atoms, and preferably three of the four substituents of R 31 to R 34 are phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
• 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 available as a commercially available product, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halides, tetraphenylphosphonium halides, tritolylmonoarylphosphonium halides, and tritolylmonoalkylphosphonium halides (all of which the halogen atom is a chlorine atom or a bromine atom).
• trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide
• triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide
• triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide
• triitolylmonoarylphosphonium halides such as triphenylmonophenylphosphonium halide
• triitolylmonoalkylphosphonium halides such as triitolylmonomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom) are preferred.
• 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 the above 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 alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms, and preferably two of the three substituents of R 35 to R 37 are phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.
• 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 - ), maleic acid 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 - ), maleic acid 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
• a 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 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass, per 100 parts by mass of the hydrolysis condensation product.
• 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, an alcohol, or a combination thereof.
• the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. 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.
• the alcohol is preferably one that easily dissipates (volatilizes) when heated after application, and examples thereof include methanol, ethanol, propanol, i-propanol, butanol, etc.
• the amount added can be 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the composition for forming a silicon-containing resist underlayer film.
• Organic Polymers can be added to a silicon-containing resist underlayer film-forming composition 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 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 polymers 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 When an addition polymerization polymer is used as the organic polymer, the polymer may be either a homopolymer or a copolymer.
• An addition polymerizable monomer is used to produce 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 contains a hydroxy group, the hydroxy group can undergo a crosslinking reaction with a hydrolysis condensation product or the like.
• the weight average molecular weight of the organic polymer 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 polymers may be used alone or in combination of two or more.
• the composition for forming a resist underlayer film of the present invention contains an organic polymer
• its content cannot be generally defined because it is appropriately determined taking into consideration the function of the organic polymer, 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 in consideration of 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, etc., 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 composition for forming a silicon-containing resist underlayer film 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 adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the film (silicon-containing 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-
• bisphenol S or bisphenol S derivatives can be added as pH adjusters.
• the amount of bisphenol S or bisphenol S derivative is 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass per 100 parts by mass of the hydrolysis condensate of the hydrolyzable silane mixture.
• bisphenol S and bisphenol S derivatives are given below, but are not limited to these.
• the concentration of the solid content 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 solid content refers to all components of the composition excluding the solvent component.
• the content of the hydrolysis condensate of the hydrolyzable silane mixture in the solid content is usually 20% by mass to 100% by mass.
• 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
• the upper limit is preferably 99% by mass, with the remainder being a specific additive (compound A) described below and other components.
• the content of the hydrolysis condensate of the hydrolyzable silane mixture in the composition can be, for example, 0.5 to 20.0% by mass.
• the composition for forming a 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, an organic solvent, and, if desired, a specific additive (compound A) or other components, the specific additive (compound A) and other components.
• a solution containing the hydrolysis condensate or the like may be prepared in advance, and this solution may be mixed with the organic solvent, the specific additive (compound A), and other components.
• the order of mixing is not particularly limited.
• an organic solvent may be added to a solution containing the hydrolysis-condensation product and the like, and then the specific additive (compound A) and other components may be added to the mixture, or the solution containing the hydrolysis-condensation product and the like, the organic solvent, the specific additive (compound A) and other components may be mixed simultaneously.
• an organic solvent may be added at the end, or some components that are relatively soluble in an organic 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 organic 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 silicon-containing resist underlayer film used in a 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 silicon-containing 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.
• an organic underlayer film is formed on the 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 (for example, a photoresist film-forming composition) on the 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.
• the 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 silicon-containing resist underlayer film (middle layer) is removed using the pattern of the photoresist film (upper layer) thus formed as a protective film, then the organic underlayer film (lower layer) is removed using the film consisting of the patterned photoresist film and the patterned silicon-containing resist underlayer film (middle layer) as a protective film, and finally the substrate is processed using the patterned photoresist film (upper layer), the patterned silicon-containing resist underlayer film (middle layer), and the patterned organic underlayer film (lower layer) as protective films.
• the removal (patterning) of the silicon-containing resist underlayer film (middle layer) using the pattern of the resist film (upper layer) as a protective film is performed 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.
• 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
• a halogen-based gas for dry etching of the silicon-containing resist underlayer film.
• the resist film (photoresist film) made of an organic material is basically difficult to remove.
• the silicon-containing resist underlayer film containing a large amount of silicon atoms is quickly removed by the halogen-based gas. Therefore, the decrease in the thickness of the photoresist film caused by the dry etching of the resist underlayer film can be suppressed. As a result, the photoresist film can be used as a thin film.
• the dry etching of the silicon-containing resist underlayer film is preferably performed by a fluorine-based gas
• fluorine-based gas examples 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 removal (patterning) of the organic underlayer film (lower layer) is preferably performed using a film consisting of the patterned silicon-containing resist underlayer film (middle layer) (and the patterned resist film (upper layer) if any remains) as a protective film by dry etching using 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.
• the processing of the (semiconductor) substrate using the patterned silicon-containing resist underlayer film (intermediate 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 ).
• the patterned silicon-containing resist underlayer film can be removed by a chemical solution.
• the removal of the silicon-containing resist underlayer film by a chemical solution can also be performed after processing the substrate with the patterned organic underlayer film.
• the solubility of the film formed from the condensate can be increased under alkaline conditions.
• the film shows excellent solubility in an alkaline solution (basic chemical solution) such as an aqueous solution containing ammonia and hydrogen peroxide.
• the film shows good peelability when treated with an alkaline solution, and even silicon-based mask residues such as the silicon-containing resist underlayer film can be easily removed by a chemical solution, so that a semiconductor device with less substrate damage can be manufactured by using the silicon-containing resist underlayer film.
• Examples of the above-mentioned chemical liquid include alkaline solutions such as dilute 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 liquid), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical liquid), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical liquid), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical liquid). From the viewpoint of minimizing the effect on the substrate, the use of an alkaline chemical liquid (basic chemical liquid) is preferable.
• alkaline chemical liquid basic chemical liquid
• the alkaline solution may be an ammonia hydrogen peroxide solution (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide, and water, as described above, or an aqueous solution containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide, 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
• 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 of the present invention is applied may have an organic or inorganic anti-reflective film formed on its surface by a CVD method or the like, and a 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 of the present invention may also absorb light depending on the wavelength of light used in the lithography process, and in such a case, it can function as an anti-reflection film having the 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 can be used as an underlayer anti-reflection film of an EUV resist film, which can prevent the reflection of undesirable exposure light, such as UV (ultraviolet) light or DUV (deep ultraviolet) light (ArF light, KrF light), from a substrate or interface during EUV exposure (wavelength 13.5 nm) without intermixing with the EUV resist film. That is, it can efficiently prevent reflection as a underlayer of an EUV resist film.
• the process can be carried out in the same manner as for a photoresist underlayer film.
• 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 (polyorganosiloxane) of the hydrolyzable silane can have a weight average molecular weight of 1,000 to 1,000,000 or 1,000 to 100,000. These molecular weights are the 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, 40 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 weight average molecular weight (Mw) of the resulting hydrolysis condensation product (polysiloxane) measured by GPC was 2,000 in terms of polystyrene.
• ⁇ Synthesis Example 2> to ⁇ Synthesis Example 7> were carried out using the compounds (monomers) shown in Table 1 under the same conditions as Synthesis Example 1, and the target products, hydrolysis condensation products (polysiloxane compounds) 2 to 7, were obtained, respectively.
• Comparative Synthesis Example 1 14.58 g of compound 1, 5.35 g of compound 2, and 30 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred. The resulting solution was stirred with a magnetic stirrer, and 12.6 g of a 0.2 mol/L aqueous solution of nitric acid was added dropwise thereto. After the dropwise addition, the flask was transferred to an oil bath adjusted to 65°C and reacted for 20 hours.
• reaction solution was cooled to room temperature, 40 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 weight average molecular weight (Mw) of the resulting hydrolysis condensation product (polysiloxane) determined by GPC was 3,200 in terms of polystyrene.
• Preparation Examples 1 to 20 and Comparative Preparation Example 1 Preparation of compositions (coating solutions) for forming silicon-containing resist underlayer films
• the hydrolysis condensates (polymers) 1 to 7 obtained in the above synthesis examples and the hydrolysis condensate (polymer) of Comparative Synthesis Example 1 were mixed with additives and solvents in the ratios shown in Table 2-1 or Table 2-2, and filtered through a 0.02 ⁇ m polyethylene filter to prepare polysiloxane underlayer film-forming composition solutions.
• the amounts of each additive in Table 2-1 and Table 2-2 are shown in parts by mass.
• the chemical shift value of the ⁇ -position methine proton of 1-ethoxy-2-propanol is detected near 3.8 ppm, but when a bond with a silicon atom is formed by a dehydration condensation reaction with a silanol group, that is, when a capping reaction occurs with a silanol group, the chemical shift value of the methine proton moves to near 4.2 ppm.
• the integral ratio of the methine proton that moved to near 4.2 ppm was measured, and the integral ratio of the proton of trimethoxyphenylsilane measured earlier was compared to calculate the capping ratio with 1-ethoxy-2-propanol using the above-mentioned formula (Cap).
• the proton of the methyl group of triethoxymethylsilane was used as the reference proton for Comparative Preparation Example 1.
• the chemical shift value is 0.0-0.3 ppm.
• resist patterns were formed using each of the coating solutions obtained in Preparation Examples 2 to 20 and Comparative Preparation Example 1.
• the experimental results using Preparation Examples 1 to 20 are set as Examples 1 to 20, respectively, and the experimental results using Comparative Preparation Example 1 are set as Comparative Example 1.
• the obtained photoresist patterns were evaluated by observing the cross-sections of the patterns to confirm the pattern shapes, and those without pattern collapse (significant pattern peeling, undercut, thickening of the line bottom (footing)) were evaluated as "good", and those with pattern collapse were evaluated as "poor”. The obtained results are shown in Table 3.
• the thickness of the silicon-containing resist underlayer film after immersion was measured, and the change rate (%) of the film thickness was calculated.
• the change rate of the film thickness after immersion relative to the film thickness of the silicon-containing resist underlayer film before immersion was evaluated as "very good” when it was 90% or more, "good” when it was 80% or more and less than 90%, and "bad” when it was less than 80%.
• the obtained results are shown in Table 3.
• B Thickness of silicon-containing resist underlayer film before immersion
• the thickness of the silicon-containing resist underlayer film after immersion in the SC-1 chemical solution was measured, and the rate of change in film thickness (%) was calculated. Films in which the rate of change in film thickness after immersion relative to the film thickness of the silicon-containing resist underlayer film before immersion was 15% or more were evaluated as "good", and films in which the rate of change was less than 15% were evaluated as "poor".
• the results are shown in Table 3.
• B Film thickness of silicon-containing resist underlayer film before immersion

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