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WO2018123658A1 - Procédé de production d'un composé polysilane, composition, film et substrat - Google Patents

Procédé de production d'un composé polysilane, composition, film et substrat Download PDF

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Publication number
WO2018123658A1
WO2018123658A1 PCT/JP2017/045124 JP2017045124W WO2018123658A1 WO 2018123658 A1 WO2018123658 A1 WO 2018123658A1 JP 2017045124 W JP2017045124 W JP 2017045124W WO 2018123658 A1 WO2018123658 A1 WO 2018123658A1
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polysilane
compound
polysilane compound
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PCT/JP2017/045124
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English (en)
Japanese (ja)
Inventor
博樹 千坂
国宏 野田
大 塩田
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東京応化工業株式会社
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Priority to JP2018559050A priority Critical patent/JP6989525B2/ja
Publication of WO2018123658A1 publication Critical patent/WO2018123658A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing a polysilane compound, a composition containing the polysilane compound, a film, and a substrate.
  • Polysilane compounds include ceramic precursors, photoelectron materials (for example, photoelectrophotographic materials such as photoresists and organic photoreceptors, optical transmission materials such as optical waveguides, optical recording materials such as optical memories, and electroluminescent element materials), various elements. Used in applications such as interlayer insulating films, sealing materials for light emitting elements such as LED elements and organic EL elements, coating films for diffusion of impurities into semiconductor substrates, and gap fill materials for semiconductor processes. In the material field, there is a high demand for removing metal components from raw materials. In addition, in manufacturing processes including microfabrication and multilayer processes, gap fill characteristics for filling irregularities on a substrate are required, and chemical resistance and ease of workability are required.
  • Patent Document 1 discloses a method for producing polysilane by reacting metal magnesium with a halosilane compound in the presence of a metal halide such as zinc chloride.
  • a metal halide such as zinc chloride
  • a metal such as zinc remains in the polysilane after production due to a silicon-metal bond, and it is difficult to reduce the residual metal. It has been a problem that the remaining metal can impair the performance as an optoelectronic material such as a film containing the polysilane. Further, there has been a dilemma that gap fill characteristics deteriorate when a high molecular weight of polysilane produced for the purpose of reducing residual metal is increased.
  • Patent Document 2 describes a purification method in which residual metal is removed using a metal compound such as copper chloride after the production of polysilane.
  • the purification using a metal compound such as copper chloride has a problem that the terminal in polysilane is converted to silanol (Si—OH) by hydrolysis and polysilane is converted to siloxane.
  • silanolation in polysilane can also cause deterioration in performance (for example, generation of cracks) of the film containing polysilane.
  • the present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a method for producing a polysilane compound with little residual metal (eg, Zn, Cu, Fe), a composition containing the polysilane compound, a film, and a substrate.
  • a polysilane compound with little residual metal eg, Zn, Cu, Fe
  • the present inventors can achieve silencing of the produced polysilane compound and a mass average molecular weight of 5000 or less, and reduce the residual metal. As a result, the present invention has been completed.
  • the first aspect of the present invention is: It is a manufacturing method of the polysilane compound of the mass mean molecular weight 5000 or less including making a halosilane compound react in presence of the organometallic complex represented by the following general formula (A1), and magnesium.
  • A1 organometallic complex represented by the following general formula (A1), and magnesium.
  • M p L p / q (A1) In the general formula (A1), M p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represents an integer of 1 or more.
  • the second aspect of the present invention is: The peak areas of the following (1X) and (2X) obtained by separating the spectrum having the maximum detected peak height in the binding energy range of 99 eV or more and 104 eV or less measured by X-ray photoelectron spectroscopy in the polysilane compound.
  • the ratio of the following (2X) to the sum, the ratio represented by the following formula (3X) is 0.4 or less, and the metal content in the polysilane compound is 500 ppb or less, and the polysilane having a mass average molecular weight of 5000 or less A compound.
  • the third aspect of the present invention is a composition comprising the polysilane compound of the second aspect.
  • a fourth aspect of the present invention is a film containing the polysilane compound of the second aspect.
  • a fifth aspect of the present invention is a substrate comprising a film containing the polysilane compound of the second aspect.
  • a method for producing a polysilane compound with little residual metal for example, Zn, Cu, Fe
  • a composition containing the polysilane compound a film, and a substrate.
  • the manufacturing method of the polysilane compound which concerns on a 1st aspect is a manufacturing method of the polysilane compound including making a halosilane compound react in presence of the organometallic complex represented with the said general formula (A1), and magnesium.
  • a residual metal can be decreased by using the organometallic complex represented by the said general formula (A1).
  • the mass average molecular weight of the produced polysilane compound can be 5000 or less, and the gap fill characteristics can be improved.
  • q-valent organic ligand L is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 2 or 3.
  • q is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
  • ⁇ -diketonato ligands such as acetylacetonato, olefins, conjugated ketones, nitriles, amines, carboxylate ligands, carbon monoxide, phosphine, phosphinite, phosphonite, phosphite Organic ligands such as The q-valent organic ligand L may be a chelate ligand.
  • the organometallic complex is preferably an organometallic complex represented by the following general formula (A2).
  • M represents iron, silver, aluminum, bismuth, cerium, cobalt, copper, dysprosium, erbium, europium, gallium, gadolinium, hafnium, holmium, indium, iridium, lanthanum, lutetium, manganese, Molybdenum, neodymium, nickel, osmium, palladium, promethium, praseodymium, platinum, rhenium, rhodium, ruthenium, samarium, scandium, tin, terbium, titanium, thulium, vanadium, chromium, tantalum, ytterbium, gold, mercury tungsten, yttrium, zinc
  • R a1 each independently represents a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aral
  • R a2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group, and p represents an integer of 1 or more.
  • Examples of the saturated hydrocarbon group represented by R a1 and R a2 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, heptyl Group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, docosyl group, 2-dodecylhexadecyl group, triacontyl group, dotriacontyl group, tetracontyl group, etc.
  • a linear or branched alkyl group having a number of 1 to 40 which further includes a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group (such as those described below), a silyl group (described below) Alkyl groups substituted with one or more substituents, such as those described), for example Chloropropyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, tridecafluoro-1,1,2,2- Tetrahydrooctyl group, heptadecafluoro-1,1,2,2-tetrahydrodecyl group, 3- (heptafluoroisopropoxy) propyl group, trimethylsilylmethyl group, etc .; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group,
  • Examples of the unsaturated hydrocarbon group represented by R a1 and R a2 include vinyl group, ethynyl group, allyl group, 1-propenyl group, propargyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, decanyl group, dodecanyl group
  • a linear or branched alkenyl group having 2 to 18 carbon atoms such as an octadecanyl group, an alkynyl group, and these unsaturated hydrocarbon groups include a halogen atom (such as those described above) and an alkoxy group (described below).
  • Silyl groups such as those described below
  • aryl groups such as those described below
  • substituents such as 2-trifluoromethylethenyl Group, 2-trifluoromethylethynyl group, 3-methoxy-1-propenyl group, 3-methoxy-1-propynyl group, 2-trimethyl Rusilylethenyl group, 2-trimethylsilylethynyl group, 2-phenylethenyl group, 2-phenylethynyl group, etc .
  • cyclic unsaturated hydrocarbon group having 3 to 18 carbon atoms such as cyclopropenyl group, cyclohexenyl group, cyclooctenyl group
  • Examples thereof include an alkyl group having an unsaturated hydrocarbon group (such as those described above), such as a cyclohexenylethyl group.
  • Examples of the aromatic hydrocarbon group represented by R a1 and R a2 include one or more of a phenyl group, an alkyl group such as a tolyl group, a butylphenyl group, and a butoxyphenyl group, an alkoxy group, and an amino group. Examples include substituted phenyl groups.
  • Examples of the aralkyl group represented by R a1 and R a2 include a benzyl group, a phenethyl group, a methylphenethyl group, a butylphenethyl group, a phenylpropyl group, and a methoxyphenylpropyl group.
  • a heteroaralkyl group a pyridylmethyl group, A pyridylethyl group etc. are mentioned.
  • Examples of the alkoxy group represented by R a1 include alkoxy groups having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, and an octyloxy group, and an aryloxy group includes a phenoxy group And a substituted phenoxy group substituted with a substituent such as an alkyl group such as a tolyloxy group and a butylphenoxy group.
  • Examples of the aralkyloxy group represented by R a1 include a benzyloxy group and a phenethyloxy group, and examples of the aryloxyalkyl group include a phenoxypropyl group and a phenoxybutyl group.
  • R a1 is preferably a saturated hydrocarbon group or aromatic hydrocarbon group having 1 to 30 carbon atoms, and more preferably an alkyl group or phenyl group having 1 to 15 carbon atoms. Preferred is a methyl group.
  • R a2 is preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group or the like, and more preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, phenyl, Group, phenylethyl group and the like, and particularly preferred is a hydrogen atom.
  • R a1 represents a methyl group
  • R a2 preferably represents a hydrogen atom. Preferred examples of p are as described above.
  • Examples of the metal complex include various metal complexes depending on the combination of the metal M and R a1 and R a2 . Specific examples include silver acetylacetonate (I), tris (acetylacetonato) aluminum (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) aluminum (III), tris (2,2,6,6-tetramethyl-3,5-heptanedionato) bismuth (III), tris (acetylacetonato) cerium (III), bis (acetylacetonato) cobalt (II), tris (acetylacetonato ) Cobalt (III), Tris (1,3-diphenyl-1,3-propanedionato) cobalt (III), Tris (3-methyl-2,4-pentandionato) cobalt (III), Tris (3- Phenyl-2,4-pentanedionato) cobalt (III), tris (3- (1-
  • the amount of the organometallic complex used is preferably in the range of 0.0001 to 10 mol times, more preferably in the range of 0.0005 to 1 mol times, and particularly preferably in the range of 0.001 to 0.1 mol with respect to the halosilane compound. It is the range of mole times.
  • magnesium In the method for producing a polysilane compound according to the first aspect, the reaction of the halosilane compound is performed in the presence of magnesium.
  • Magnesium can function as a reducing agent for dehalogenating polycondensation of a halosilane compound (“magnesium reduction method”, methods described in WO98 / 29476, JP2003-277507, etc.).
  • Magnesium may be in the form of metallic magnesium (magnesium alone), a magnesium alloy, or a mixture thereof (hereinafter also simply referred to as “magnesium component”).
  • the kind of magnesium alloy is not particularly limited, and examples thereof include conventional magnesium alloys such as magnesium alloys containing components such as aluminum, zinc, rare earth elements (scandium, yttrium, etc.).
  • the shape of the magnesium component is not particularly limited as long as the reaction of the halosilane compound is not impaired. Flat form etc.) etc. are illustrated, and it is preferable that they are a powder, a granular material, a ribbon-like body, a cutting piece-like body etc. especially.
  • the average particle size of magnesium eg, powdered magnesium
  • the said magnesium component may be used independently and may be used in combination of 2 or more type.
  • the amount of the magnesium component used is preferably 1 to 20 equivalents, more preferably 1.1 to 14 equivalents, and 1.2 to 10 equivalents in terms of magnesium with respect to the halogen atom of the halosilane compound. More preferably, it is 1.2 to 5 equivalents. Further, the amount of magnesium used is preferably 1 to 20 times, more preferably 1.1 to 14 times, and more preferably 1.2 to 10 times as magnesium in terms of moles with respect to the halosilane compound. Is more preferable, and 1.2 to 5 times is particularly preferable.
  • the halosilane compound is preferably a compound represented by the following formula (1).
  • X n SiR 4-n (1) Wherein n is an integer of 2 to 4, n Xs are each independently a halogen atom, and (4-n) Rs are each independently a hydrogen atom, an organic group or silyl Group.
  • halogen atom represented by X examples include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.
  • Examples of the organic group represented by R include alkyl groups [alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups (preferably alkyl groups having 1 to 6 carbon atoms).
  • a cycloalkyl group (a cycloalkyl group having 5 to 8 carbon atoms such as a cyclohexyl group, particularly a cycloalkyl group having 5 to 6 carbon atoms), an alkenyl group [ethenyl Group, propenyl group, butenyl group and the like alkenyl group having 2 to 10 carbon atoms (preferably alkenyl group having 2 to 6 carbon atoms, especially alkenyl group having 2 to 4 carbon atoms)], cycloalkenyl group [1- A cycloalkenyl group having 5 to 10 carbon atoms such as a cyclopentenyl group and a 1-cyclohexenyl group (preferably a cycloalkenyl group having 5 to 8 carbon atoms, Such cycloalkenyl group having 5-7 carbon atoms)], the aryl group (phenyl, aryl group having
  • the aryl group constituting the alkyl group, cycloalkyl group, aryl group or aralkyl group may have one or more substituents.
  • substituents include the above-exemplified alkyl groups (particularly alkyl groups having 1 to 6 carbon atoms).
  • organic group having such a substituent include C 1-6 alkyl-C such as tolyl group (methylphenyl group), xylenyl group (2,6-dimethylphenyl group), ethylphenyl group and methylnaphthyl group.
  • a 6-10 aryl group preferably a mono, di or tri C 1-4 alkyl-C 6-10 aryl group, particularly a mono or di C 1-4 alkylphenyl group).
  • silyl group examples include substituted silyl groups substituted with the above alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, aralkyl group, alkoxy group and the like.
  • R is preferably a hydrocarbon group such as an alkyl group or an aryl group.
  • dihalosilane compounds include, for example, dialkyldihalosilanes (diC 1-10 alkyldihalosilanes such as dimethyldichlorosilane, preferably diC 1-6 alkyldihalosilanes, more preferably diC 1-4 Alkyl dihalosilanes), monoalkyl monoaryl dihalosilanes (mono C 1-10 alkyl mono C 6-12 aryl dihalosilanes such as methylphenyldichlorosilane, preferably mono C 1-6 alkyl mono C6-10 aryl) Dihalosilanes, more preferably mono C 1-4 alkyl mono C 6-8 aryl dihalo silanes, etc., diaryl dihalo silanes (diC 6-12 aryl dihalo silanes such as diphenyl dichloro silane, preferably di C 6 -10 aryl dihalo silane, more preferably di C 6-8 A Rujiharoshiran, etc.),
  • R is preferably a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group which may have a substituent, or an aralkyl group, particularly an alkyl group or an aryl group. Groups are preferred.
  • trihalosilane compounds include alkyltrihalosilanes (C 1-10 alkyltrihalosilanes such as methyltrichlorosilane, butyltrichlorosilane, t-butyltrichlorosilane, hexyltrichlorosilane, preferably C 1-6 alkyltrihalosilane, More preferably, C 1-4 alkyltrihalosilane, etc., cycloalkyltrihalosilane (mono C6-10 cycloalkyltrihalosilane, such as cyclohexyltrihalosilane), aryltrihalosilane (phenyltrichlorosilane, tolyltrichlorosilane, xylyltrichlorosilane) C 6-12 aryl trihalosilane, preferably C 6-10 aryl trihalosilane, more preferably C 6-8 aryl trihalosilane, etc.) .
  • tetrahalosilane compound examples include, for example, tetrachlorosilane, dibromodichlorosilane, and tetrabromosilane.
  • the tetrahalosilane compounds may be used alone or in combination of two or more.
  • the tetrahalosilane compound is preferably used in combination with a mono-, di- or trihalosilane compound.
  • the halosilane compound may be a monohalosilane compound.
  • Representative monohalosilanes include, for example, trialkylmonohalosilanes (tri-C 1-10 alkyl monohalosilanes such as trimethylchlorosilane, preferably tri-C 1-6 alkyl monohalosilanes, more preferably tri-C 1-4 alkyls).
  • Monohalosilanes, etc.), dialkyl monoaryl monohalosilanes (diC 1-10 alkyl mono C 6-12 aryl monohalosilanes such as dimethylphenylchlorosilane, preferably diC 1-6 alkyl mono C 6-10 aryl monohalo Silane, more preferably diC 1-4 alkyl mono C 6-8 aryl monohalosilane, etc., monoalkyl diaryl monohalo silane (mono C 1-10 alkyl di C 6-12 aryl monohalo silane, such as methyldiphenylchlorosilane, preferably mono C 1 6 alkyl di C 6-10 aryl monohaloalkyl silane, more preferably such mono C 1-4 alkyl di C 6-8 aryl monohaloalkyl silane), tri C 6-12 aryl monohaloalkyl such triaryl monohaloalkyl silane (triphenyl chlorosilane Silane, preferably tri-C 6-10 aryl
  • halosilane compounds can be used alone or in combination of two or more.
  • the halosilane compound preferably contains at least one selected from a dihalosilane compound and a trihalosilane compound.
  • halosilane compound contains a trihalosilane compound and / or a tetrahalosilane compound
  • a network-like (network-like or branched) polysilane compound can be generated.
  • representative halosilanes include (a) alkyltrihalosilanes (for example, alkyltrihalosilanes alone, methyltrihalosilanes in combination with C2-10 alkyltrihalosilanes, C 2-10 alkyltrihalosilane), (b) aryltrihalosilane (eg, aryltrihalosilane alone), (c) combination of aryltrihalosilane and dihalosilane (eg, monoalkylmonoaryldihalosilane), etc. Can be mentioned.
  • the ratio (use ratio) of at least one selected from dihalosilane compounds and trihalosilane compounds is 50 mol% or more (for example, 60 mol% or more), preferably 70 mol% or more, based on the entire halosilane. (For example, 80 mol% or more), more preferably 90 mol% or more (for example, 95 mol% or more).
  • the proportion (use ratio) of the trihalosilane compound is 30 mol% or more (for example, 40 mol% or more), preferably 50 mol% or more (for example, 60 mol%) of the entire halosilane compound. Mol% or more), more preferably 70 mol% or more (for example, 75 mol% or more), particularly 80 mol% or more.
  • the halosilane compound is preferably as pure as possible.
  • liquid halosilane compounds are preferably dried and dried using a desiccant such as calcium hydride, and solid halosilane compounds are purified and used by recrystallization or the like. Is preferred.
  • the concentration of the halosilane compound (substrate concentration) in the raw material mixture (reaction solution) is, for example, about 0.05 to 20 mol / l, preferably about 0.1 to 15 mol / l, more preferably 0.2 to 5 mol. / L may be sufficient.
  • the halosilane compound may be further reacted with the organometallic complex and magnesium in the presence of a metal halide.
  • the metal halide include polyvalent metal halides such as transition metals (for example, periodic table group 3A elements such as samarium, periodic table group 4A elements such as titanium, periodic table group 5A elements such as vanadium, iron, nickel, Periodic table group 8 elements such as cobalt and palladium, periodic table group 1B elements such as copper, periodic table group 2B elements such as zinc), periodic table group 3B metals (such as aluminum), periodic table group 4B metals (such as tin) Metal halides such as chloride, bromide or iodide.
  • the valence of the metal constituting the metal halide is not particularly limited, but is preferably 2 to 4, more preferably 2 or 3. These metal halides can be used alone or in combination of two or more.
  • the metal halide is preferably a chloride or bromide of at least one metal selected from iron, aluminum, zinc, copper, tin, nickel, cobalt, vanadium, titanium, palladium, samarium and the like.
  • metal halides examples include chlorides (iron chloride such as FeCl 2 and FeCl 3 ; AlCl 3 , ZnCl 2 , SnCl 2 , CoCl 2 , VCl 2 , TiCl 4 , PdCl 2 , and SmCl 2 ).
  • chlorides iron chloride such as FeCl 2 and FeCl 3 ; AlCl 3 , ZnCl 2 , SnCl 2 , CoCl 2 , VCl 2 , TiCl 4 , PdCl 2 , and SmCl 2 ).
  • bromides such as iron bromide such as FeBr 2 and FeBr 3
  • iodides such as SmI 2
  • chlorides for example, iron chlorides such as iron (II) chloride and iron (III), zinc chloride, etc.
  • bromides are preferred.
  • iron chloride and / or zinc chloride, especially zinc chloride and the like are used.
  • the amount of the metal halide used is preferably in the range of 0.001 to 10 mole times, more preferably in the range of 0.001 to 1 mole times, particularly preferably 0.001 to 0.1 moles relative to the halosilane compound. It is the range of mole times.
  • the concentration of the metal halide in the reaction solution is usually about 0.001 to 6 mol / L, preferably about 0.005 to 4 mol / L, more preferably about 0.01 to 3 mol / L. It may be.
  • the reaction of the halosilane compound in the method for producing a polysilane compound according to the first aspect is preferably performed in a solvent (reaction solvent), more preferably in an aprotic solvent.
  • the aprotic solvent as the solvent (reaction solvent) include ethers (1,4-dioxane, tetrahydrofuran, tetrahydropyran, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) Cyclic or linear C 4-6 ethers such as ethers), carbonates (such as propylene carbonate), nitriles (such as acetonitrile and benzonitrile), amides (such as dimethylformamide and dimethylacetamide), sulfoxides (such as dimethyl sulfoxide) Aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons
  • aprotic solvents can be used alone or in combination of two or more as a mixed solvent.
  • at least polar solvents for example, ethers [for example, tetrahydrofuran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,4-dioxane, etc. (especially tetrahydrofuran, 1,2- Dimethoxyethane)]] is preferably used.
  • a polar solvent may be used individually or in combination of 2 or more types, and may combine a polar solvent and a nonpolar solvent.
  • the solution after the reaction is brought into contact with an aqueous solution containing at least one selected from the group consisting of a base and an acid to purify the solution. It is preferable to further include obtaining a polysilane compound.
  • impurities such as halogen atoms (eg, halogen ions (chloride ions, etc.), Si—Cl remaining in the polysilane compound) can be removed.
  • the molecular weight reduction of the polysilane compound can be promoted, and the solvent solubility of the polysilane compound can be improved.
  • the acid can also function as a quencher for the reaction of the halosilane compound.
  • the metal atom for example, Mg, Zn, Cu, Fe, etc.
  • the treatment temperature is preferably from ⁇ 50 ° C. to the boiling point of the solvent, more preferably from room temperature to 100 ° C.
  • bases can be used as long as they are basic compounds.
  • Inorganic bases such as potassium carbonate, lithium hydride, sodium hydride, potassium hydride, calcium hydride, alkyl metals such as methyl lithium, n-butyl lithium, methyl magnesium chloride, ethyl magnesium bromide, Cr, Ga , Fe (Fe (II), Fe (III)), Cd, Co, Ni, Sn, Pb, Cu (Cu (II), Cu (I)), Ag, Pd, Pt, Au, and other metals (or metals) Metal halide composed of ions), sodium methoxide, sodium ethoxide, potassium t- Alkoxides such as Tokishido, triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine,
  • various solvents can be used as the base or acid treatment, for example, hydrocarbon solvents such as benzene, toluene and xylene, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, Ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, ethanol, isopropyl alcohol, One or more selected from alcohol solvents such as butanol can be used.
  • hydrocarbon solvents such as benzene, toluene and xylene
  • glycol solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether
  • a cyclic skeleton acetate-containing compound can also be preferably used as a solvent used in the above base or acid treatment.
  • the acetate compound containing a cyclic skeleton is not particularly limited as long as it is an acetate solvent having a cyclic skeleton that does not impair the effects of the present invention, but is preferably a cycloalkyl acetate represented by the following formula (S1).
  • each R s1 is independently an alkyl group, p is an integer of 1 to 6, and q is an integer of 0 to (p + 1).
  • alkyl group represented by R s1 include alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.
  • cycloalkyl acetate represented by the formula (S1) include cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate, and cyclooctyl acetate.
  • cyclohexyl acetate is preferable from the viewpoint of availability.
  • the polysilane compound can be obtained with a yield of 50% or more, and preferably the yield is 70% or more.
  • a polysilane compound having a mass average molecular weight (Mw) of 5000 or less can be produced.
  • the mass average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) in terms of polystyrene.
  • the Mw of the polysilane compound is preferably 4000 or less, more preferably 3000 or less, and still more preferably 2500 or less from the viewpoint of gap fill properties.
  • the lower limit of Mw of the polysilane compound is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 300 or more, more preferably 400 or more, and further preferably 500 or more, It is particularly preferably 600 or more, and most preferably 700 or more.
  • a polysilane compound selected from the group consisting of linear polysilane, branched polysilane, and cyclic polysilane can be produced.
  • a cyclic polysilane compound can also be selectively produced.
  • the cyclic polysilane compound is preferably a polysilane compound having a Mw of 5000 or less in view of chemical structure and chemical properties. Examples of the polysilane compound include polysilane compounds having 3 to 40 Si atoms, and polysilane compounds having 5 to 30 Si atoms are preferable.
  • the polysilane compound is preferably at least one selected from the group consisting of polysilane compounds represented by the following general formulas (T-1) and (T-2).
  • R t10 , R t11 , R t12 , R t13 , R t14 and R t15 are each independently a hydrogen atom, a hydroxyl group or an organic group.
  • R t16 and R t17 each independently represents a hydrogen atom, a hydroxyl group or an organic group.
  • U represents an integer of 3 to 20).
  • Examples of the organic group represented by R t10 to R t17 include the same as the specific examples and preferred examples described above as the organic group represented by R.
  • any organic group can be introduced by the method described in paragraph 0031 of JP-A No. 2003-261681, for example.
  • the ratio represented by the following formula of the siloxane bond (Si—O) measured by X-ray photoelectron spectroscopy in the polysilane compound is preferably 0.5 or less.
  • the spectrum having the maximum detected peak height in the binding energy range of 99 eV to 104 eV measured by X-ray photoelectron spectroscopy in the polysilane compound is peak-separated.
  • the ratio represented by the following formula (3X), which is the ratio of the following (2X) to the sum of the areas of the following (1X) and (2X) peaks, can be reduced to 0.4 or less. It is preferably 35 or less, more preferably 0.3 or less, still more preferably 0.2 or less, particularly preferably 0.1 or less, and most preferably 0.05 or less.
  • the content ratio of Si—O and Si—C can be seen from the area of the peak having the peak height. Further, the content ratio of Si—Si is found from the area of the peak having the maximum peak height in the range where the bond energy of (1X) is 99.0 eV or more and 99.5 eV or less.
  • the polysilane compound contains not only Si—C but also Si—O, peaks having two maximum peak heights appear in the range of 100 eV or more and 104 eV or less after peak separation, but according to the second aspect In the polysilane compound, it is preferable that only a peak having one maximum peak height appears after peak separation in the range of 100 eV or more and 104 eV or less, and ideally only one peak appears. O-bonds are not considered to be included.
  • the peak ratio in the range of 100 eV or more and 104 eV or less appears as two peaks having the maximum peak height overlapping, so the area ratio is Since it becomes large, the ratio represented by the above formula exceeds 0.4.
  • the organometallic complex does not contain a halogen atom, generation of by-products such as a siloxane bond and a silanol group can be suppressed.
  • the amount of siloxane bonds (Si—O) present in the compound can be reduced, and the film performance such as suppression of microcracking can be improved.
  • the content of the residual metal in the polysilane compound can be reduced, the content of the metal in the polysilane compound can be 500 ppb or less, and 400 ppb or less. Preferably, it is 100 ppb or less, more preferably 50 ppb or less, and particularly preferably 10 ppb or less. By setting it within the above range, it is possible to prevent performance degradation as a photoelectron material such as a film containing the polysilane compound.
  • the composition which concerns on a 3rd aspect is a composition containing the polysilane compound of a 2nd aspect.
  • the composition according to the third aspect may be a thermosetting composition or may not be a thermosetting composition.
  • the composition according to the third aspect may be a radiation-sensitive composition or not a radiation-sensitive composition, and is a positive-type radiation-sensitive composition that is solubilized in a developer upon exposure. Or a negative radiation-sensitive composition that becomes insoluble in a developer upon exposure.
  • the radiation light source include an active energy ray such as ultraviolet light and excimer laser light, a light source that emits ultraviolet light such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a carbon arc lamp.
  • the composition according to the third aspect preferably contains a solvent.
  • the solvent the above-mentioned cyclic skeleton acetate-containing compound, Alcohols such as methanol, ethanol, propanol, n-butanol; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; a lactone ring-containing organic solvent such as ⁇ -butyrolactone; Compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate, monomethyl ether, monoethyl ether, monopropyl of the above polyhydric alcohols or the above compound having an ester bond Derivation of the
  • PGMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • TNU N′-tetramethylurea
  • butanol two or more of these solvents may be used in combination.
  • the water content of the composition according to the third aspect is 0.5% by mass or less in that the composition according to the third aspect is easy to form a silica-based film having a low dielectric constant or suppressing microcracks.
  • 0.3 mass% or less is more preferable, and less than 0.3 mass% is especially preferable.
  • the water content of the composition according to the third aspect is often derived from a solvent. For this reason, it is preferable that the solvent is dehydrated so that the water content of the composition according to the third aspect becomes the above amount.
  • the amount of solvent used is not particularly limited as long as the object of the present invention is not impaired. From the viewpoint of film forming property, the solvent is used so that the solid content concentration of the composition according to the third aspect is preferably 1 to 50% by mass, more preferably 10 to 40% by mass.
  • the composition according to the third aspect may include a polysilane other than the polysilane compound according to the first aspect.
  • a polysilane compound having a high Mw hereinafter also simply referred to as “high molecular weight polysilane” in terms of improving chemical resistance and the like, and the Mw of the high molecular weight polysilane is, for example, more than 5,000 and less than 100,000, preferably It is about 6000 to 60000.
  • the composition according to the third aspect may contain a silicon-containing resin other than the polysilane compound in terms of improving processability.
  • the silicon-containing resin other than the polysilane compound include a polysiloxane resin or a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2).
  • the Mw of the silicon-containing resin other than the polysilane compound is preferably 500 to 20000, more preferably 1000 to 10,000, and still more preferably 2000 to 8000.
  • the polysilane-polysiloxane resin is prepared by, for example, treating the polysilane compound according to the first embodiment in a solvent under the basic conditions described above, and then adding the following general formulas (A-1-1) to (A- 1-4) at least one silicon compound selected from the group consisting of silicon compounds and at least one selected from the group consisting of hydrolysates, condensates and hydrolysis condensates of the above silicon compounds; Can be produced by hydrolytic condensation reaction.
  • X 1 to X 4 are each independently a hydrolyzable group
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or An organic group, and a hydrogen atom in the organic group may be substituted with a halogen atom.
  • Examples of the hydrolyzable group represented by X 1 to X 4 include an alkoxy group, a halogen atom or an isocyanate group (NCO), and an alkoxy group is preferable.
  • Examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, Examples include a pentoxy group.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, A chlorine atom is preferable.
  • Examples of the organic group represented by R 1 to R 6 include an organic group having 1 to 30 carbon atoms, and an alkyl group [methyl, ethyl, n-propyl, i-propyl, n-butyl group and t-butyl group.
  • An alkyl group having 1 to 10 carbon atoms preferably an alkyl group having 1 to 6 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms
  • a cycloalkyl group having 5 to 5 carbon atoms such as a cyclohexyl group).
  • alkenyl groups [alkenyl groups having 2 to 10 carbon atoms such as ethenyl group, propenyl group, butenyl group (preferably 2 to 6 carbon atoms). Alkenyl groups, especially alkenyl groups having 2 to 4 carbon atoms, etc.]], cycloalkenyl groups [cycloalkenyl groups having 5 to 10 carbon atoms such as 1-cyclopentenyl group, 1-cyclohexenyl group, etc.
  • a group (preferably a cycloalkenyl group having 5 to 8 carbon atoms, particularly a cycloalkenyl group having 5 to 7 carbon atoms)], an aryl group (an aryl group having 6 to 10 carbon atoms such as phenyl or naphthyl group), Aralkyl groups [C 6-10 aryl-C 1-6 alkyl groups such as benzyl and phenethyl groups (C 6-10 aryl-C 1-4 alkyl groups etc.)], amino groups, N-substituted amino groups (the above alkyl groups) , N-mono- or di-substituted amino group substituted with a cycloalkyl group, an aryl group, an aralkyl group, an acyl group, and the like.
  • the aryl group constituting the alkyl group, cycloalkyl group, aryl group or aralkyl group may have one or more substituents.
  • substituents include the above-exemplified alkyl groups (particularly alkyl groups having 1 to 6 carbon atoms), the above-exemplified alkoxy groups, and the like.
  • organic group having a substituent include a C 1-6 alkyl-C 6-10 aryl group such as tolyl, xylenyl, ethylphenyl, methylnaphthyl group (preferably mono, di or tri C 1-4).
  • Alkyl-C 6-10 aryl groups especially mono or di C 1-4 alkylphenyl groups); C 1-10 alkoxy C 6-10 aryl groups such as methoxyphenyl, ethoxyphenyl, methoxynaphthyl groups (preferably C 1 -6 alkoxy C 6-10 aryl group, especially C 1-4 alkoxyphenyl group, etc.).
  • the silicon compound represented by the general formula (A-1-3) may be a silicon compound represented by the following formula (A-3).
  • HOOC-UZY-Si (OR a ) 3 (A-3) (In the above general formula (A-3), U represents a divalent group or branched chain formed by removing one hydrogen atom of each of two ring carbon atoms from an aromatic ring group or an alicyclic group.
  • Z represents —NHCO— or —CONH—
  • Y represents a single bond, an alkylene group, an arylene group or —R Y1 —NH—R Y2 -
  • R Y1 and R Y2 each independently represents an alkylene group
  • R a each independently represents a hydrocarbon group, provided that U and / or Y are a (meth) acryl group, (It may have at least one group selected from the group consisting of a vinyl group and an epoxy group as a substituent.)
  • Examples of the aromatic ring in U include aromatic rings having 6 to 10 carbon atoms which may have a substituent having 1 to 2 carbon atoms (for example, benzene ring, naphthalene ring, tolyl group, xylyl group, etc.). be able to.
  • Examples of the alicyclic ring in U include alicyclic rings having 5 to 10 carbon atoms (for example, a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a bicyclic alkyl group, a cage alkyl group, and the like.
  • a cyclopentane ring for example, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a dicyclopentadiene ring, a norbornane ring, a norbornene ring, a cubane ring, and a basuketan ring.
  • Examples of the alkylene group in Y include an alkylene group having 1 to 6 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • the arylene group for Y is preferably one having 6 to 10 carbon atoms. Examples of such include phenylene groups (ortho, meta, para, etc.), naphthylene groups (1,4-, 1,5-, 2,6-, etc.) and the like.
  • —R Y1 —NH—R Y2 — in Y include, for example, —CH 2 —NH—CH 2 —, — (CH 2 ) 2 —NH— (CH 2 ) 2 —, — ( CH 2 ) 3 —NH— (CH 2 ) 3 —, —CH 2 —NH— (CH 2 ) 2 —, — (CH 2 ) 2 —NH—CH 2 —, — (CH 2 ) 2 —NH— ( CH 2 ) 3 —, — (CH 2 ) 3 —NH— (CH 2 ) 2 —, —CH 2 —NH— (CH 2 ) 3 —, — (CH 2 ) 3 —NH—CH 2 — and the like be able to.
  • the polysiloxane resin includes a hydrolyzate or condensate of at least one silicon compound selected from the group consisting of silicon compounds represented by the general formulas (A-1-1) to (A-1-4). And at least one selected from the group consisting of hydrolysis condensates.
  • Resins other than the polysilane compound according to the first aspect may be used singly or in combination.
  • the blending ratio (mass ratio) of the polysilane compound according to the first aspect and the other Si resin in the composition according to the third aspect may be appropriately changed according to the application. For example, it is 1:99 to 99: 1, preferably 10:90 to 90:10.
  • composition which concerns on a 3rd aspect may contain the organic compound which has a 2 or more hydroxyl group or carboxyl group in 1 molecule as a solubility promoter to alkaline aqueous solution or a solution.
  • organic compound which has a 2 or more hydroxyl group or carboxyl group in 1 molecule as a solubility promoter to alkaline aqueous solution or a solution.
  • examples of such an organic compound include the following compounds.
  • E in the above structural formula is a hydrogen atom, a methyl group or a hydroxymethyl group
  • R 15 is a methylene group, a carbonyl group or a phenylene group
  • n is an integer of 3 or more and less than 100.
  • na represents a natural number of 1 to 3
  • nb represents a natural number of 1 or more
  • nc represents a natural number of 2 to 4
  • nd represents a natural number of 2 or more.
  • the structural formula may include enantiomers and diastereoisomers, and each structural formula represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.
  • the said organic compound can be used individually by 1 type or in combination of 2 or more types.
  • the amount used is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total solid content excluding the solvent of the composition according to the third aspect.
  • the composition according to the third embodiment may contain a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms in order to improve stability.
  • Acids added at this time include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid , Phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, dimethylmalonic acid Diethyl malonic acid, succinic acid,
  • oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are particularly preferable.
  • two or more kinds of acids may be mixed and used.
  • the organic acid is blended so that it is preferably 0 ⁇ pH ⁇ 7, more preferably 0.3 ⁇ pH ⁇ 6.5, and even more preferably 0.5 ⁇ pH ⁇ 6, in terms of the pH of the composition. It is good.
  • composition according to the third aspect may contain a monovalent or divalent or higher alcohol having a cyclic ether as a substituent, or an ether compound as a stabilizer.
  • a monovalent or divalent or higher alcohol having a cyclic ether as a substituent or an ether compound as a stabilizer.
  • Specific examples of the stabilizer that can be used include those described in paragraphs (0180) to (0184) of JP2009-126940A.
  • the composition according to the third aspect may contain water. Lithography performance is improved by adding water.
  • the content of water in the solvent component of the composition according to the third aspect is preferably more than 0% and less than 50% by weight, more preferably 0.3 to 30% by weight, still more preferably 0.5 to 20% by weight. It is.
  • composition according to the third aspect may contain a photoacid generator.
  • a photoacid generator that can be used include the photoacid generators described in paragraphs (0160) to (0179) of JP2009-126940A.
  • composition according to the third aspect may contain a surfactant as necessary.
  • a surfactant as necessary.
  • Specific examples of the surfactant that can be used include the surfactants described in paragraph (0185) of JP2009-126940A.
  • the composition according to the third aspect may contain a thermal crosslinking accelerator.
  • thermal crosslinking accelerators that can be used include thermal crosslinking accelerators described in JP-A-2007-302873.
  • the thermal crosslinking accelerator include phosphate compounds and borate compounds.
  • phosphate compounds include ammonium salts such as ammonium phosphate, tetramethylammonium phosphate, and tetrabutylammonium phosphate, and sulfonium salts such as triphenylsulfonium phosphate.
  • borate compounds examples include ammonium salts such as ammonium borate, tetramethylammonium borate, tetrabutylammonium borate, and sulfonium salts such as triphenylsulfonium borate.
  • the said thermal crosslinking accelerator can be used individually by 1 type or in combination of 2 or more types.
  • the addition amount of the thermal crosslinking accelerator is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the total amount of the solid content excluding the solvent of the composition.
  • composition which concerns on a 3rd aspect may contain the other various hardening
  • the curing agent include Bronsted acids; imidazoles; organic amines; organic phosphorus compounds and complexes thereof; organic amine complexes of Lewis acids; amidines; curing agents that generate a base component by light or heat. It is done.
  • the composition which concerns on a 3rd aspect has few residual metals and contains the polysilane compound by which silanization was suppressed (control), it can be used suitably for the material for manufacturing processes, such as a semiconductor, a display, or a solar cell. .
  • the material for manufacturing processes such as a semiconductor, a display, or a solar cell.
  • it can be used as an application for forming a protective film or an interlayer film for protecting various substrates (including metal oxide-containing films and various metal-containing films).
  • the various substrates include semiconductor substrates, liquid crystal displays, organic light emitting displays (OLEDs), electrophoretic displays (electronic paper), touch panels, color filters, backlights, and other display material substrates (metal oxide-containing films, various metal-containing materials).
  • a film Including a film), a substrate for a solar cell (including a metal oxide-containing film and various metal-containing films), a substrate for a photoelectric conversion element such as an optical sensor (including a metal oxide-containing film and various metal-containing films). And substrates of photoelectric devices (including metal oxide-containing films and various metal-containing films).
  • the base material component (resin component) in the composition according to the third aspect is substantially composed only of the polysilane compound according to the first aspect, the gap fill characteristics are particularly excellent.
  • Including a trench isolation structure in which a fine groove is formed on the surface and the inside of the groove is filled with the composition according to the third aspect to electrically isolate elements formed on both sides of the groove. It can be used as an application for forming insulating films, passivation films, planarization films, protective films, and the like.
  • membrane which concerns on a 4th aspect is a film
  • substrate which concerns on a 5th aspect is a board
  • the film according to the fourth aspect is preferably an insulating film, a passivation film, a planarizing film, or a protective film including a trench isolation structure.
  • the method for forming the film according to the fourth aspect is not particularly limited as long as the effects of the present invention are not impaired, but a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, etc., on an arbitrary substrate as necessary. And a method of coating using a non-contact coating apparatus such as a spinner (rotary coating apparatus) or a curtain flow coater.
  • a contact transfer type coating apparatus such as a roll coater, a reverse coater, a bar coater, etc.
  • a non-contact coating apparatus such as a spinner (rotary coating apparatus) or a curtain flow coater.
  • substrate of display materials such as a semiconductor substrate, a liquid crystal display, an organic light emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a color filter, and a backlight (metal oxide containing) Films, including various metal-containing films), substrates for solar cells (including metal oxide-containing films and various metal-containing films), substrates for photoelectric conversion elements such as optical sensors (metal oxide-containing films, various metal-containing films) Glass substrate, quartz substrate, transparent or translucent resin substrate (for example, polycarbonate, polyethylene terephthalate, poly, etc.) in addition to photoelectric device substrates (including metal oxide-containing films and various metal-containing films).
  • display materials such as a semiconductor substrate, a liquid crystal display, an organic light emitting display (OLED), an electrophoretic display (electronic paper), a touch panel, a color filter, and a backlight (metal oxide containing) Films, including various metal-containing films), substrates for solar cells (including metal oxide-
  • Heat-resistant materials such as ether sulfone, polyimide, polyamideimide, etc.), metals, silicon substrates, etc.
  • substrate is not specifically limited, According to the usage condition of a pattern formation body, it can select suitably.
  • the drying method is not particularly limited. For example, (1) a method of drying on a hot plate at a temperature of 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, and (2) a room temperature for several hours to Examples include a method of leaving for several days, and (3) a method of removing the solvent by placing it in a warm air heater or an infrared heater for several tens of minutes to several hours.
  • the dried coating film may or may not be exposed to irradiation with active energy rays such as ultraviolet rays and excimer laser light.
  • the energy dose to be irradiated is not particularly limited, and for example, about 30 to 2000 mJ / cm 2 can be mentioned. You may perform the process to expose with the process of baking instead of the process of baking mentioned later.
  • the exposure step for example, the formed coating film may be selectively exposed, and in the case of including a selective exposure step, a developing step may be included. Further, for example, imprint lithography may be performed on the formed coating film.
  • the dried, exposed or developed coating film is preferably baked (post-baked) from the viewpoint of improving film properties.
  • the firing temperature depends on the lower substrate and the intended use, it is, for example, in the range of 200 to 1000 ° C., preferably 200 ° C. to 500 ° C., more preferably 200 to 250 ° C.
  • the firing atmosphere is not particularly limited, and may be an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, a vacuum, or a reduced pressure. It may be under air or the oxygen concentration may be controlled appropriately.
  • the firing time may be appropriately changed, and is, for example, about 10 minutes to 120 minutes.
  • the film thickness in the fourth and fifth embodiments is preferably 10 to 3000 nm, more preferably 50 to 1500 nm, and still more preferably 100 to 1000 nm.
  • THF tetrahydrofuran
  • Example 2 A round flask with an internal volume of 1000 ml equipped with a three-way cock is charged with 25 g of granular (particle size 20 to 1000 ⁇ m) magnesium and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst, and adjusted to 1 mmHg at 50 ° C. After heating and reducing pressure to dry the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of THF previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at 25 ° C. for about 60 minutes.
  • Example 3 A round flask with an internal volume of 1000 ml equipped with a three-way cock is charged with 25 g of granular (particle size 20 to 1000 ⁇ m) magnesium and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst, and adjusted to 1 mmHg at 50 ° C. After heating and reducing the pressure to dry the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at room temperature (25 ° C.) for about 30 minutes.
  • Example 4 A round flask with an internal volume of 1000 ml equipped with a three-way cock is charged with 25 g of granular (particle size 20 to 1000 ⁇ m) magnesium and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst, and adjusted to 1 mmHg at 50 ° C. After heating and reducing the pressure to dry the inside of the reactor (flask), dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at room temperature for about 30 minutes.
  • the obtained branched polyphenylsilane was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and further mixed with 200 g of an aqueous copper chloride solution containing copper chloride (II) (CuCl 2 ) at a ratio of 10% by mass. After stirring for a minute, the organic phase containing branched polyphenylsilane and the aqueous phase containing copper chloride were separated.
  • Example 5 A round flask with an internal volume of 1000 ml equipped with a three-way cock is charged with 25 g of granular (particle size 20 to 1000 ⁇ m) magnesium and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst, and adjusted to 1 mmHg at 50 ° C. After heating and reducing pressure to dry the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of THF previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at 25 ° C. for about 60 minutes.
  • the obtained branched phenylsilane-dimethylsilane copolymer is dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and further 200 g of an aqueous copper chloride solution containing copper (II) (CuCl 2 ) in a proportion of 10% by mass. And the mixture was stirred for 60 minutes, and then the organic phase containing the branched phenylsilane-dimethylsilane copolymer and the aqueous phase containing copper chloride were separated.
  • the organic phase containing the branched phenylsilane-dimethylsilane copolymer was washed with 200 ml of pure water three times, and then the solvent component was distilled off to obtain a phenylsilane-methylsilane copolymer (mass average molecular weight 2000). 36.6 g was obtained (74% yield).
  • Example 6 A round flask with an internal volume of 1000 ml equipped with a three-way cock is charged with 25 g of granular (particle size 20 to 1000 ⁇ m) magnesium and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst, and adjusted to 1 mmHg at 50 ° C. After heating and reducing pressure to dry the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at room temperature for about 30 minutes.
  • the toluene phase was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then toluene was distilled off to obtain 21.6 g of methylphenylsilane polymer (mass average molecular weight 6000) (recovery). Rate 60%).
  • the organic phase containing the linear phenylsilane-dimethylsilane copolymer was washed with 200 ml of pure water three times, the solvent component was distilled off, and the linear phenylsilane-dimethylsilane copolymer ( 21.6 g (mass average molecular weight 3000) was obtained (yield 60%).
  • the obtained linear methylphenylsilane polymer was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and further 200 g of an aqueous copper chloride solution containing 10% by mass of copper (II) chloride (CuCl 2 ) was mixed. After stirring for 60 minutes, the organic phase containing the linear methylphenylsilane polymer and the aqueous phase containing copper chloride were separated. And after wash
  • the obtained branched polyphenylsilane was dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and further mixed with 200 g of an aqueous copper chloride solution containing copper chloride (II) (CuCl 2 ) at a ratio of 10% by mass. After stirring for a minute, the organic phase containing branched polyphenylsilane and the aqueous phase containing copper chloride were separated. And after wash
  • ⁇ Gap fill characteristic evaluation> The polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were dissolved in cyclohexyl acetate so that the concentration of the polysilane compound was 5% by mass, and each of the obtained polysilane compound solutions (including the polysilane compound) was dissolved.
  • the gap fill characteristics were evaluated according to the following evaluation method using the composition. (Evaluation criteria) Each polysilane compound solution is applied to a silicon wafer on which a repeated trench pattern having a line width of 40 nm, a space width of 15 nm, and a height (space depth) of 85 nm is formed.
  • the pattern was applied so that the height from the bottom of the pattern was about 185 nm), pre-baked at 100 ° C. for 100 seconds, and then baked (post-baked) at 350 ° C. for 30 minutes to obtain a polysilane compound film.
  • the cross-sectional portion was immersed in a 0.4% hydrofluoric acid aqueous solution for 1 minute, and then the cross-sectional shape was observed with an SEM. Evaluation was made according to the following criteria. A: The polysilane compound film is uniformly embedded in the trench pattern portion. X: Poor filling of the polysilane compound film is observed in the trench pattern portion.
  • Peak area (2X) having a maximum peak height in the range of 104 eV or less peak area derived from siloxane bond (Si—O) and Si—C bond), and bond energy of 99.0 eV or more and 99.5 eV or less
  • the range peak area (1X) (peak area derived from Si—Si) was calculated, the ratio represented by the following formula (3X) was calculated, and evaluated according to the following criteria.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de production d'un composé polysilane comprenant peu d'un métal résiduel (tel que Zn, Cu et Fe), une composition contenant le composé polysilane, un film et un substrat. Elle porte sur un procédé de production d'un composé polysilane ayant une masse moléculaire moyenne en masse de 5000 ou moins, le procédé comprenant la réaction d'un composé halogénosilane en présence d'un complexe organométallique représenté par la formule générale (A1) et de magnésium. (A1) MpLp/q (Dans la formule générale (A1), Mp représente un cation métallique de valence p, L représente un ligand organique de valence q, et p et q représentent chacun d'une manière indépendante un entier valant 1 ou plus).
PCT/JP2017/045124 2016-12-28 2017-12-15 Procédé de production d'un composé polysilane, composition, film et substrat WO2018123658A1 (fr)

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US10763491B2 (en) 2014-04-01 2020-09-01 The Research Foundation For The State University Of New York Low-temperature synthesis process of making MgzMxOy, where M is Mn, V or Fe, for manufacture of electrode materials for group II cation-based batteries

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JPH01198631A (ja) * 1987-10-09 1989-08-10 Mitsui Petrochem Ind Ltd ポリシラン化合物の製造方法
JPH04288334A (ja) * 1991-03-15 1992-10-13 Shin Etsu Chem Co Ltd ポリシランの製造方法
JP2002097414A (ja) * 2000-09-25 2002-04-02 Jsr Corp 膜形成用組成物および絶縁膜形成用材料
JP2003277507A (ja) * 2002-03-20 2003-10-02 Osaka Gas Co Ltd ポリシラン系コポリマーの製造方法
JP2006316197A (ja) * 2005-05-13 2006-11-24 Nitto Kasei Co Ltd ポリシラン類の製造方法
JP2007106894A (ja) * 2005-10-13 2007-04-26 Nippon Soda Co Ltd ポリシランの製造方法

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KR101308790B1 (ko) * 2005-12-07 2013-09-17 오사까 가스 가부시키가이샤 폴리실란 및 폴리실란을 함유하는 수지 조성물

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01198631A (ja) * 1987-10-09 1989-08-10 Mitsui Petrochem Ind Ltd ポリシラン化合物の製造方法
JPH04288334A (ja) * 1991-03-15 1992-10-13 Shin Etsu Chem Co Ltd ポリシランの製造方法
JP2002097414A (ja) * 2000-09-25 2002-04-02 Jsr Corp 膜形成用組成物および絶縁膜形成用材料
JP2003277507A (ja) * 2002-03-20 2003-10-02 Osaka Gas Co Ltd ポリシラン系コポリマーの製造方法
JP2006316197A (ja) * 2005-05-13 2006-11-24 Nitto Kasei Co Ltd ポリシラン類の製造方法
JP2007106894A (ja) * 2005-10-13 2007-04-26 Nippon Soda Co Ltd ポリシランの製造方法

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