JP6989525B2 - Method for producing polysilane compound, composition, membrane, and substrate - Google Patents

Description

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, optoelectronic materials (eg, photoelectron photographic materials such as photoresists and organic photoconductors, optical transmission materials such as optical waveguides, optical recording materials such as optical memory, materials for electroluminescence elements), and various elements. Used in applications such as interlayer insulating films, encapsulation materials for light emitting elements such as LED elements and organic EL elements, coating films for spreading impurities on semiconductor substrates, and gap fill materials for semiconductor processes. In the material field, there are high demands for the removal of metal components from raw materials. Further, in a manufacturing process including microfabrication and a multi-layer process, gap fill characteristics for filling irregularities on a substrate are required, and chemical resistance and ease of processability are required.

As a method for producing such a polysilane compound, for example, Patent Document 1 discloses a method for producing polysilane by reacting a halosilane compound with metallic magnesium in the presence of a metal halide such as zinc chloride.
In the production method using 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. The problem is that the remaining metal may impair the performance as a photoelectronic material such as a film containing polysilane.
In addition, there is a dilemma that the gap fill characteristics deteriorate when the molecular weight of polysilane produced for the purpose of reducing residual metal is increased.

Further, Patent Document 2 describes a purification method for removing residual metal using a metal compound such as copper chloride after producing polysilane.
However, in purification using a metal compound such as copper chloride, there is a problem that the terminal in polysilane is hydrolyzed to silanol (Si-OH) and polysilane is converted to siloxane. Further, it has been known that silanolization in polysilane may cause deterioration in performance (for example, generation of cracks) of the film containing polysilane.

Japanese Patent No. 5571992 Japanese Patent No. 5658608

In view of the above-mentioned problems of the prior art, an object of the present invention is to provide a method for producing a polysilane compound having a small amount of residual metal (for example, Zn, Cu, Fe), a composition containing the polysilane compound, a film, and a substrate.

By using a specific organic metal complex in the method for producing a polysilane compound, the present inventors can suppress siloxane formation of the produced polysilane compound, achieve a mass average molecular weight of 5000 or less, and reduce residual metal. This has led to the completion of the present invention.

The first aspect of the present invention is
It is a method for producing a polysilane compound having a mass average molecular weight of 5000 or less, which comprises reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium.
M ^p L _{p / q} (A1)

(In the above general formula (A1), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represent an integer of 1 or more.)

The second aspect of the present invention is
The area of the peaks (1X) and (2X) below obtained by peak separation of the spectrum having the maximum detection 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, which is 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 mass average molecular weight is 5000 or less. It is a compound.

(1X) ... Area of a peak having a maximum detected peak height in the range where the binding energy is 99.0 eV or more and 99.5 eV or less (2X) ... The maximum detected peak height in the range where the binding energy is 100 eV or more and 104 eV or less. Area of peak with energy (3X) ... (2X) / [(1X) + (2X)]

A third aspect of the present invention is a composition containing the polysilane compound of the second aspect.
A fourth aspect of the present invention is a membrane 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.

According to the present invention, it is possible to provide a method for producing a polysilane compound having a small amount of residual metal (for example, Zn, Cu, Fe), a composition containing the polysilane compound, a film, and a substrate.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention. ..
Further, in the present specification, "~" means the following from the above unless otherwise specified.

<Manufacturing method of polysilane compound>
The method for producing a polysilane compound according to the first aspect is a method for producing a polysilane compound, which comprises reacting the halosilane compound in the presence of the organometallic complex represented by the above general formula (A1) and magnesium.
According to the method for producing a polysilane compound according to the first aspect, the residual metal can be reduced by using the organometallic complex represented by the above general formula (A1).
Further, the mass average molecular weight of the produced polysilane compound can be achieved to be 5000 or less, and the gap fill characteristics can be improved.

(Organometallic complex)
In the method for producing a polysilane compound according to the first aspect, the reaction of the halosilane compound is carried out in the presence of an organometallic complex represented by the following general formula (A1).

M ^p L _{p / q} (A1)

(In the above general formula (A1), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represent an integer of 1 or more.)

The metal atoms constituting the p-valent metal cation M ^p, 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, renium, rhodium, ruthenium, samarium, scandium, tin, terbium, titanium, thulium, vanadium, chromium, tantalum, ytterbium, gold, mercury tungsten, Examples include metals selected from the group consisting of ytterbium, zinc and zirconium.
The p is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.
The q is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
Examples of the q-valent organic ligand L include β-diketonato ligands such as acetylacetonato, olefins, conjugated ketones, nitriles, amines, carboxylat ligands, carbon monoxide, phosphine, phosphinite, phosphonite, and phosphite. Organic ligands such as. The q-valent organic ligand L may be a chelate ligand.

（上記一般式（Ａ２）中、Ｍは、鉄、銀、アルミニウム、ビスマス、セリウム、コバルト、銅、ジスプロシウム、エルビウム、ユーロピウム、ガリウム、ガドリニウム、ハフニウム、ホルミウム、インジウム、イリジウム、ランタン、ルテチウム、マンガン、モリブデン、ネオジム、ニッケル、オスミウム、パラジウム、プロメチウム、プラセオジム、白金、レニウム、ロジウム、ルテニウム、サマリウム、スカンジウム、スズ、テルビウム、チタン、ツリウム、バナジウム、クロム、タンタル、イッテルビウム、金、水銀タングステン、イットリウム、亜鉛及びジルコニウムよりなる群から選択される金属を表し、Ｒ^ａ１は、各々独立して、飽和炭化水素基、不飽和炭化水素基、芳香族炭化水素基、アラルキル基、アルコキシ基、アリールオキシ基、アラルキルオキシ基又はアリールオキシアルキル基を表し、Ｒ^ａ２は、水素原子、飽和炭化水素基、不飽和炭化水素基、芳香族炭化水素基又はアラルキル基を表わす。ｐは１以上の整数を表す。）The organometallic complex is preferably an organometallic complex represented by the following general formula (A2).

(In the above general formula (A2), M is iron, silver, aluminum, bismuth, cerium, cobalt, copper, disprosium, erbium, europium, gallium, gadrinium, hafnium, formium, indium, iridium, lanthanum, lutetium, manganese, Molybdenum, Neodim, Nickel, Osmium, Palladium, Promethium, Placeodim, Platinum, Renium, Rodium, Luthenium, Samalium, Scandium, Tin, Terbium, Titanium, Thurium, Vanadium, Chromium, Tantal, Itterbium, Gold, Mercury Tungsten, Ittrium, Zinc and represents a metal selected from the group consisting of zirconium, R ^a1 are each independently a saturated hydrocarbon group, unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyl Represents an oxy group or an aryloxyalkyl group, ^Ra2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group. P represents an integer of 1 or more.)

Saturated hydrocarbon groups 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 and heptyl. Carbons such as groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tetradecyl groups, hexadecyl groups, octadecyl groups, icosyl groups, docosyl groups, 2-dodecyl hexadecyl groups, triacontyl groups, dotriacontyl groups and tetracontyl groups. Linear or branched alkyl groups of number 1-40, which are halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy groups (such as those described below), silyl groups (described below). Alkyl groups substituted with one or more of the substituents such as those described), such as 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- (heptafluoroiso) Propoxy) propyl group, trimethylsilylmethyl group, etc .; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, bicycloheptyl group, cyclooctyl group, adamantyl group, etc. Cyclic-saturated hydrocarbon groups, and those in which these cyclic-saturated hydrocarbon groups are substituted with one or more of substituents such as alkyl groups (such as those described above) and aryl groups (such as those described above), for example. , 4-t-Butylcyclohexyl group, 4-phenylcyclohexyl group and the like; or the above-mentioned alkyl group having a cyclic saturated hydrocarbon group (such as those mentioned above), for example, cyclohexylmethyl group, adamantylethyl group and the like.

The ^{unsaturated hydrocarbon group represented by R a1} and R ^a2 includes a vinyl group, an ethynyl group, an allyl group, a 1-propenyl group, a propargyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, a decanyl group and a dodecanyl group. , Octadecanyl groups and other linear or branched alkenyl groups having 2 to 18 carbon atoms, alkynyl groups, and these unsaturated hydrocarbon groups are halogen atoms (such as those mentioned above) and alkoxy groups (described below). , Etc.), Cyril groups (such as those described below), aryl groups (such as those described below) substituted with one or more substituents, eg 2-trifluoromethylethenyl. Group, 2-trifluoromethylethynyl group, 3-methoxy-1-propenyl group, 3-methoxy-1-propynyl group, 2-trimethylsilylethenyl 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; Alkyl group having the cyclic unsaturated hydrocarbon group (such as those mentioned above), for example, cyclo. Examples include a hexenylethyl group.

The ^{aromatic hydrocarbon group represented by R a1} and R ^a2 may be one or more of a phenyl group, an alkyl group such as a trill group, a butylphenyl group and a butoxyphenyl group, an alkoxy group and an amino group. Examples include substituted 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, and examples of the heteroaralkyl group include a pyridylmethyl group and the like. Examples thereof include a pyridyl ethyl group.

^Examples of the alkoxy group represented by R a1 include an alkoxy group 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 examples of the aryloxy group include phenoxy. Examples thereof include a substituted phenoxy group substituted with a substituent such as a group and a substituent such as an alkyl group such as a triloxy 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.

Preferred as R ^a1 are saturated hydrocarbon groups and aromatic hydrocarbon groups having 1 to 30 carbon atoms, and more preferable ones are alkyl groups and phenyl groups having 1 to 15 carbon atoms, particularly. Preferred are methyl groups.

Preferred as R ^a2 are hydrogen atoms, saturated hydrocarbon groups having 1 to 18 carbon atoms, aromatic hydrocarbon groups and the like, and more preferable ones are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms and phenyl. Groups, phenylethyl groups and the like, particularly preferred are hydrogen atoms.
It is preferable that R ^a1 represents a methyl group and R a ^{2 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 above metal M and Ra1} and Ra2. Specific examples include acetylacetonato silver (I), tris (acetylacetonato) aluminum (III), tris (2,2,6,6-tetramethyl-3,5-heptandionat) aluminum (III), and tris. (2,2,6,6-tetramethyl-3,5-heptandionat) Bismus (III), Tris (Acetylacetonato) Serium (III), Bis (Acetylacetonato) Cobalt (II), Tris (Acetylacetonato) ) Cobalt (III), Tris (1,3-diphenyl-1,3-propanedionat) Cobalt (III), Tris (3-methyl-2,4-pentandionato) Cobalt (III), Tris (3-) Phenyl-2,4-pentandionato) cobalt (III), tris (3- (1-phenylethyl) -2,4-pentandionato) cobalt (III), bis (benzoylacetone) cobalt (II) bis ( Hexafluoroacetylacetonato) cobalt (II), tris (2,2,6,6-tetramethyl-3,5-heptandionat) cobalt (III), bis (acetylacetonato) copper (II), bis (2, 2,6,6-Tetramethyl-3,5-heptadionat) Copper (II), Tris (2,2,4,6,6-pentamethyl-3,5-Heptandionato) Cobalt (III), Tris (2,2) , 6,6-Tetramethyl-4- (1-phenylethyl) -3,5-heptandionato) Cobalt (III), Tris (2,2,6,6-tetramethyl-4-phenyl-3,5-heptandionato) ) Cobalt (III), Bis (Hexafluoroacetylacetonato) Copper (II), Bis (Trifluoroacetylacetonato) Copper (II), Tris (Acetylacetonato) Disprosium (III), Tris (Acetylacetonato) Elbium (III), Tris (2,2,6,6,-Tetramethyl-3,5-Heptandionato) Elbium (III), Tris (Acetylacetonato) Europium (III), Bis (Acetylacetonato) Iron (II) , Tris (acetylacetonato) iron (III), Tris (1,3-diphenyl-1,3-propanedionat) iron (III), Tris (3-methyl-2,4-pentandionato) iron (III) ), Tris (3-phenyl-2,4-pentandionato) iron (III), Tris (3- (1-phenylethyl) -2,4-pentandionato) iron (III), Tris (2,2) , 6,6-Tetramethyl-3,5-Heptandionato) Iron (III), Tris (2,2,4,6,6-Pentamethyl-3,5-Heptandionato) Iron (III), Tris (2,2) 6,6-Tetramethyl-4- (1-phenylethyl) -3,5-heptandionato) Iron (III), Tris (2,2,6,6-tetramethyl-4-phenyl-3,5-heptandionato) Iron (III), Tetrakiss (Acetylacetonato) Hafnium (IV), Tris (Acetylacetonato) Gallium (III), Tris (Acetylacetonato) Gadrinium (III), Tris (Acetylacetonato) Holmium (III), Tris (Acetylacetonato) Indium (III), Tris (Acetylacetonato) Iridium (III), Tris (Acetylacetonato) Lantern (III), Tris (Acetylacetonato) Lutetium (III), Bis (Acetylacetonato) Manganese (II), Tris (Acetylacetonato) Manganese (III), Bis (Hexafluoroacetylacetonato) Manganese (II), Bis (Acetylacetonato) Dioxomolybdenum (IV), Tris (Acetylacetonato) Neodim (III) ), Tris (2,2,6,6-tetramethyl-3,5-heptadionat) Neodim (III), Bis (acetylacetonato) Nickel (II), Bis (2,2,6,6-tetramethyl-) 3,5-Heptazionato) Nickel (II), Bis (hexafluoroacetylacetonato) Nickel (II), Bis (1,3-diphenyl-1,3-Propanozionato) Nickel (II), Bis (3-Methyl) -2,4-Pentandionato) Nickel (II), Bis (3-phenyl-2,4-Pentandionato) Nickel (II), Bis (3- (1-phenylethyl) -2,4-Pentandio Nato) Nickel (II), Bis (2,2,4,6,6-pentamethyl-3,5-heptandionat) Nickel (II), Bis (2,2,6,6-Tetramethyl-4- (1-) Phenylethyl) -3,5-heptandionato) Nickel (II), Bis (2,2,6,6-tetramethyl-4-phenyl-3,5-heptandionato) Nickel (II), Bis (acetylacetonato) Palladium (II), bis (hexafluoroacetylacetonato) palladium (II), bis (1,3-diphenyl-1,3-propanedionat) palladium (II), bis (3-Methyl-2,4-pentandionato) palladium (II), bis (3-phenyl-2,4-pentandionato) palladium (II), bis (3- (1-phenylethyl) -2, 4-Pentandionato) Palladium (II), Bis (2,2,4,6,6-pentamethyl-3,5-Heptandionato) Palladium (II), Bis (2,2,6,6-Tetramethyl-4) -(1-Phenylethyl) -3,5-heptandionato) palladium (II), bis (2,2,6,6-tetramethyl-4-phenyl-3,5-heptandionato) palladium (II), tris (acetyl) Acetnato) Promethium (III), Tris (Acetylacetonato) Placeodim (III), Tris (Hexafluoroacetylacetonato) Placeodim (III), Bis (Acetylacetonato) Platinum (II), Tris (Acetylacetonato) Rodium (III), Tris (Acetylacetonato) Luthenium (III), Tris (Acetylacetonato) Scandium (III), Tris (Hexafluoroacetylacetonato) Scandium (III), Tris (2,2,6,6-Tetra) Methyl-3,5-Heptazineato) Scandium (III), Tris (Acetylacetonato) Samalium (III), Tris (2,2,6,6-Tetramethyl-3,5-Heptandionato) Samalium (III), Bis ( Acetylacetonato tin (II), tris (acetylacetonato) terbium (III), tris (2,2,6,6-tetramethyl-3,5-heptandionat) terbium (III), tris (2,2) 6,6-Tetramethyl-3,5-heptandionat) Thurium (III), Tris (acetylacetonato) vanadium (III), Tris (acetylacetonato) ittrium (III), Tris (hexafluoroacetylacetonato) ittrium ( III), Tris (2,2,6,6-tetramethyl-3,5-heptandionat) ittrium (III), bis (acetylacetonato) zinc (II), bis (hexafluoroacetylacetonato) zinc (II) , Bis (2,2,6,6-tetramethyl-3,5-heptandionat) zinc (II), tetrakis (acetylacetonato) zirconium (IV), tetrakis (2,2,6,6-tetramethyl-3) , 5-Heptandionato) Zyrosine (IV), Tetrakiss (Trifluoro) Acetylacetonato) Zirconium (IV) and the like can be mentioned.
These organometallic complexes can be used alone or in combination of two or more. As the organometallic complex, a pre-synthesized metal complex may be used, or one produced in the system may be used.

The amount of the organometallic complex used is preferably in the range of 0.0001 to 10 mol times, more preferably 0.0005 to 1 mol times, and particularly preferably 0.001 to 0.1 times the halosilane compound. It is in the range of molar times.

(magnesium)
In the method for producing a polysilane compound according to the first aspect, the reaction of the halosilane compound is carried out in the presence of magnesium.
Magnesium can function as a reducing agent for dehalogenating and polycondensing a halosilane compound ("magnesium reduction method", WO98 / 29476, the method described in JP-A-2003-277507, etc.).
The magnesium may be in the form of metallic magnesium (elemental magnesium), in the form of a magnesium alloy, or a mixture thereof (hereinafter, also simply referred to as “magnesium component”).
The type of the magnesium alloy is not particularly limited, and examples thereof include conventional magnesium alloys, for example, magnesium alloys containing components such as aluminum, zinc, and rare earth elements (scandium, ittrium, etc.).
The shape of the magnesium component is not particularly limited as long as the reaction of the halosilane compound is not impaired, but powder granules (powder, granules, etc.), ribbon-like bodies, cut pieces, lumps, rods, plates ( (Flat plate shape, etc.) are exemplified, and in particular, powder, granular material, ribbon-like body, cut piece-like body, etc. are preferable. The average particle size of magnesium (for example, powdered magnesium) may be, for example, 1 to 10000 μm, preferably 10 to 7000 μm, and more preferably 15 to 5000 μm (for example, 20 to 3000 μm).
The magnesium component may be used alone or in combination of two or more.

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 with respect to the halogen atom of the halosilane compound. It is more preferably present, and it is particularly preferable that the amount is 1.2 to 5 equivalents.
The amount of magnesium used is preferably 1 to 20 times, more preferably 1.1 to 14 times, and 1.2 to 10 times the number of moles of the halosilane compound. Is more preferable, and 1.2 to 5 times is particularly preferable.

(Halosilane compound)
In the method for producing a polysilane compound according to the first aspect, the halosilane compound is preferably a compound represented by the following formula (1).

X _n SiR _4-n (1)

(In the equation, n is an integer of 2 to 4, n Xs are independently halogen atoms, and (4-n) Rs are each independently a hydrogen atom, an organic group or a silyl. Is the basis.)

Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable.

The organic group represented by R includes an alkyl group [an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl and a t-butyl group (preferably an alkyl group having 1 to 6 carbon atoms). , Especially alkyl groups with 1 to 4 carbon atoms)], cycloalkyl groups (cycloalkyl groups with 5 to 8 carbon atoms such as cyclohexyl groups, especially cycloalkyl groups with 5 to 6 carbon atoms), alkenyl groups [ethenyl An alkenyl group having 2 to 10 carbon atoms such as a group, a propenyl group and a butenyl group (preferably an alkenyl group having 2 to 6 carbon atoms, particularly an alkenyl group having 2 to 4 carbon atoms)], a cycloalkenyl group [1- Cycloalkenyl groups having 5 to 10 carbon atoms such as cyclopentenyl group and 1-cyclohexenyl group (preferably cycloalkenyl groups having 5 to 8 carbon atoms, especially cycloalkenyl groups having 5 to 7 carbon atoms)], aryl Group (aryl group with 6 to 10 carbon atoms such as phenyl and naphthyl groups), aralkyl group [C _6-10 aryl-C _1-6 alkyl group such as benzyl and phenethyl groups (C _6-10 aryl-C _{1) -4} Alkyl group, etc.)], amino group, N-substituted amino group (N-mono or di-substituted amino group substituted with the above alkyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, etc.), etc. Can be mentioned. The above-mentioned alkyl group, cycloalkyl group, aryl group, aryl group constituting an aralkyl group and the like may have one or a plurality of substituents. Examples of such a substituent include the above-exemplified alkyl groups (particularly, alkyl groups having 1 to 6 carbon atoms) and the like. _{Examples of the organic group having such a substituent include C 1-6} alkyl-C such as a trill group (methylphenyl group), a xylenyl group (2,6-dimethylphenyl group), an ethylphenyl group and a methylnaphthyl group. _Examples thereof include 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, etc.).

Examples of the silyl group include substituted silyl groups substituted with the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, aralkyl group, alkoxy group and the like.

When n is 2 (dihalosilane compound), as R, a hydrocarbon group such as an alkyl group or an aryl group is preferable.

Typical dihalosilane compounds include, for example, dialkyldihalosilane (diC _1-10 alkyldihalosilane such as dimethyldichlorosilane, preferably diC _1-6 alkyldihalosilane, more preferably diC _1-4. alkyl dihalo silanes, etc.), mono _{C 1-10} alkyl _{mono-C 6-12} aryl dihalo silane such as monoalkyl monoaryl dihalo silane (methyl phenyl dichlorosilane, preferably mono _{C 1-6} alkyl mono- C6-10 aryl dihalosilane, more preferably such mono _{C 1-4} alkyl mono- _{C 6-8} aryl dihalo silane), diaryl dihalo silane (di _{C 6-12} aryl dihalo silane such as diphenyl dichlorosilane, preferably di _{C 6 -10} aryldihalosilane, more preferably diC _6-8 aryldihalosilane, etc.) and the like. As the dihalosilane compound, dialkyldihalosilane or monoalkylmonoaryldihalosilane is preferable. The dihalosilane compound can be used alone or in combination of two or more.

When n is 3 (trihalosilane compound), as R, a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group which may have a substituent, and an aralkyl group is preferable, and an alkyl group or an aryl is particularly preferable. Groups are preferred.

_{Typical trihalosilane compounds include C 1-10} alkyl trihalosilanes such as alkyl trihalosilanes (methyltrichlorosilanes, butyltrichlorosilanes, t-butyltrichlorosilanes, hexyltrichlorosilanes, etc., preferably C _1-6 alkyltrihalosilanes, etc. More preferably, C _1-4 alkyl trihalosilanes, etc.), cycloalkyl trihalosilanes (mono C _6-10 cycloalkyl trihalosilanes such as cyclohexyltrihalosilanes, etc.), aryltrihalosilanes (phenyltrichlorosilanes, trilltrichlorosilanes, xylyltrichlorosilanes, etc.) Such as C _6-12 aryl trihalosilane, preferably C _6-10 aryl trihalosilane, more preferably C _6-8 aryl trihalosilane) and the like. As the trihalosilane compound, alkyltrihalosilane or aryltrihalosilane is preferable.
The trihalosilane compound can be used alone or in combination of two or more.

Specific examples of the case where n is 4 (tetrahalosilane compound) include tetrachlorosilane, dibromodichlorosilane, tetrabromosilane, and the like. The tetrahalosilane compound 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.

Further, the halosilane compound may be a monohalosilane compound. Typical monohalosilanes include, for example, trialkyl monohalosilanes (tri-C _1-10 alkyl monohalosilanes such as trimethylchlorosilane, preferably tri-C _1-6 alkyl monohalosilanes, more preferably tri-C _1-4 alkyl. Monohalosilane, etc.), Dialkyl monoaryl monohalosilane (diC _1-10 alkyl mono C _6-12 aryl monohalosilane, preferably di C _1-6 alkyl mono C _6-10 aryl monohalo, such as dimethylphenylchlorosilane) Silanes, more preferably diC _1-4 alkyl mono C _6-8 aryl monohalosilanes _{), monoalkyl diaryl monohalosilanes (mono C 1-10} alkyl di _{C 6-12} aryl monohalosilanes such as methyldiphenyl chlorosilanes, etc.), Preferred are mono C _1-6 alkyl di C _6-10 aryl monohalosilanes, more preferably mono C _1-4 alkyl di C _6-8 aryl monohalosilanes), triaryl monohalosilanes (triphenyl chlorosilanes and the like tri C). _6-12 aryl monohalosilanes, preferably tri-C _6-10 aryl monohalosilanes, more preferably tri-C _6-8 aryl monohalosilanes, etc.) and the like. The monohalosilane compound can be used alone or in combination of two or more.

These halosilane compounds can be used alone or in combination of two or more.

The halosilane compound preferably contains at least one selected from the dihalosilane compound and the trihalosilane compound.

When the halosilane compound contains a trihalosilane compound and / or a tetrahalosilane compound, a network-like (mesh-like or branched-chain) polysilane compound can be produced. In the case of obtaining a network-shaped polysilane compound, typical halosilanes (or combinations thereof) include (a) alkyltrihalosilanes alone (for example, alkyltrihalosilanes alone, methyltrihalosilanes and C _2-10 alkyltrihalosilanes). C _2-10 alkyltrihalosilanes, etc.), (b) aryltrihalosilanes (eg, aryltrihalosilanes alone), (c) combinations of aryltrihalosilanes and dihalosilanes (eg, monoalkylmonoaryldihalosilanes, etc.) Can be mentioned.

In the halosilane compound, the ratio (use ratio) of at least one selected from the dihalosilane compound and the trihalosilane compound is 50 mol% or more (for example, 60 mol% or more), preferably 70 mol% or more, based on the whole halosilane. It may be (for example, 80 mol% or more), more preferably 90 mol% or more (for example, 95 mol% or more).

In the case of obtaining a network-shaped polysilane, the proportion (usage ratio) of the trihalosilane compound is 30 mol% or more (for example, 40 mol% or more), preferably 50 mol% or more (for example, 60) of the whole halosilane compound. It may be mol% or more), more preferably 70 mol% or more (for example, 75 mol% or more), and particularly 80 mol% or more.

When the dihalosilane compound and the trihalosilane compound are combined, the ratio thereof is the former / the latter (molar ratio) = 99/1 to 1/99, preferably 90/10 to 2/98 (for example, 85/15 to 85/15 to). 2/98), even more preferably 80/20 to 3/97 (eg, 70/30 to 4/96), especially 60/40 to 5/95 (eg, 50/50 to 7/93). It may be usually 50/50 to 5/95 (for example, 45/55 to 7/93, preferably 40/60 to 10/90, and more preferably 30/70 to 88/12).

The halosilane compound is preferably as pure as possible. For example, it is preferable to dry the liquid halosilane compound with a drying agent such as calcium hydride and distill it for use, and for the solid halosilane compound, purify it by a recrystallization method or the like before use. Is preferable.

The concentration (substrate concentration) of the halosilane compound 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, and more preferably 0.2 to 5 mol. It may be about / l.

(Metal halide)
In the method for producing a polysilane compound according to the first aspect, the halosilane compound may be further reacted with the organometallic complex and magnesium in the presence of a metal halide.
Examples of the metal halide include polyvalent metal halides, for example, transition metals (for example, Group 3A elements of the Periodic Table such as samarium, Group 4A elements of the Periodic Table such as titanium, Group 5A elements of the Periodic Table such as vanadium, iron, nickel, and the like. 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 (aluminum, etc.), Periodic Table Group 4B metals (tin, etc.) Examples thereof include halides of metals such as chlorides, bromides or iodides. The valence of the metal constituting the metal halide is not particularly limited, but is preferably 2 to 4 valences, particularly 2 or 3 valences. These metal halides can be used alone or in combination of two or more.

As the metal halide, chloride or bromide of at least one metal selected from iron, aluminum, zinc, copper, tin, nickel, cobalt, vanadium, titanium, palladium, samarium and the like is preferable.

Examples of such metal halides include chlorides (iron chloride such as _{FeCl 2} , FeCl _{3 ; AlCl 3} , ZnCl ₂ , SnCl ₂ , CoCl ₂ , VCl ₂ , TiCl ₄ , PdCl ₂ , SmCl _2, etc.). Examples thereof include bromide (such as iron bromide such as _{FeBr 2} and FeBr ₃ ) and iodide (such as _{SmI 2).} Of these metal halides, chlorides (eg, iron chloride such as iron (II) chloride and iron (III) chloride, zinc chloride, etc.) and bromides are preferable. Usually, 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 mol times, more preferably 0.001 to 1 mol times, and particularly preferably 0.001 to 0.1 times the halosilane compound. It is in the range of molar 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, and more preferably about 0.01 to 3 mol / L. May be.

(Protic solvent)
The reaction of the halosilane compound in the method for producing a polysilane compound according to the first aspect is preferably carried out in a solvent (reaction solvent), more preferably in an aprotic solvent.
Examples of the aprotic solvent as a solvent (reaction solvent) include ethers (1,4-dioxane, tetrahydrofuran, tetrahydropyran, diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl)). Cyclic or chain C _4-6 ether such as ether), carbonates (propylene carbonate, etc.), nitriles (acetoyl, benzonitrile, etc.), amides (dimethylformamide, dimethylacetamide, etc.), sulfoxides (dimethylsulfoxide, etc.) , Aromatic hydrocarbons (benzene, toluene, xylene, etc.), aliphatic hydrocarbons (eg, chain or cyclic hydrocarbons such as hexane, cyclohexane, octane, cyclooctane) and the like.

These aprotic solvents can be used alone or in combination of two or more as a mixed solvent. Among these solvents, at least polar solvents [eg, ethers [eg, tetrahydrofuran, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,4-dioxane and the like (particularly tetrahydrofuran, 1,2-). It is preferable to use dimethoxyethane)]]. The polar solvent may be used alone or in combination of two or more, or a polar solvent and a non-polar solvent may be combined.

In the method for producing a polysilane compound according to the first aspect, the above-mentioned solution is purified by contacting the solution (reaction solution) after the reaction with an aqueous solution containing at least one selected from the group consisting of a base and an acid. It is preferable to further include obtaining a polysilane compound.
By contacting the polysilane compound with a base or an acid for purification treatment, impurities such as halogen atoms (for example, halogen ions (chloride ions and the like) and Si-Cl remaining in the polysilane compound) can be removed. In addition, it is possible to promote the reduction of the molecular weight of the polysilane compound, and it is possible to improve the solvent solubility of the polysilane compound.
The acid can also function as a quencher for the reaction of the halosilane compound.
Further, by contacting the polysilane compound with the following metal halide for purification treatment, metal atoms (for example, Mg, Zn, Cu, Fe, etc.) remaining in the polysilane compound can be removed.
The treatment temperature is preferably about −50 ° C. to the boiling point of the solvent, and more preferably room temperature to 100 ° C.

As the base to be used, various compounds exhibiting basicity can be used. For example, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, sodium hydrogencarbonate can be used. , 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 halides composed of ions), alkoxides such as sodium methoxydo, sodium ethoxydo, potassium t-butoxide, triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, 4-dimethylaminopyridine, diazabicyclo Organic bases such as undecene (DBU) can be used. The reaction temperature is preferably about −50 ° C. to the boiling point of the solvent, and more preferably room temperature to 100 ° C.
Various acids can be used, but inorganic acids such as hydrogen chloride can be used.

Here, various solvents can be used as the solvent used for the above-mentioned base or acid treatment, and for example, a hydrocarbon solvent such as benzene, toluene and xylene, a glycol solvent such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, and the like. 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.

（式（Ｓ１）中、Ｒ^ｓ１は、それぞれ独立に、アルキル基であり、ｐは１〜６の整数であり、ｑは０〜（ｐ＋１）の整数である。）
Ｒ^ｓ１で表されるアルキル基としては炭素原子数１〜３のアルキル基が挙げられ、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基が挙げられる。Further, the cyclic skeleton-containing acetate compound can also be preferably used as the solvent used for the above-mentioned base or acid treatment.
The cyclic skeleton-containing acetate compound is not particularly limited as long as it is an acetate-based solvent having a cyclic skeleton that does not impair the effects of the present invention, but cycloalkyl acetate represented by the following formula (S1) is preferable.

(In the formula (S1), R ^s1 is an alkyl group independently, p is an integer of 1 to 6, and q is an integer of 0 to (p + 1).)
^Examples of the alkyl group represented by R s1 include an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an i-propyl group.

Specific examples of the cycloalkyl acetate represented by the formula (S1) include cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate, and cyclooctyl acetate.
Among these, cyclohexyl acetate is preferable from the viewpoint of availability and the like.

According to the method for producing a polysilane compound according to the first aspect, the polysilane compound can be obtained in a yield of 50% or more, preferably 70% or more.

<Polysilane compound>
According to the method for producing a polysilane compound according to the first aspect, a polysilane compound having a mass average molecular weight (Mw) of 5000 or less can be produced.
In the present specification, the mass average molecular weight (Mw) is a measurement value obtained 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 further preferably 2500 or less, from the viewpoint of gap fill property.
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, still more preferably 500 or more. It is particularly preferably 600 or more, and most preferably 700 or more.

（上記一般式（Ｔ−２）中、Ｒ^ｔ１６及びＲ^ｔ１７は、それぞれ独立に、水素原子、水酸基又は有機基を表す。Ｕは３〜２０の整数を表す。）、
Ｒ^ｔ１０〜Ｒ^ｔ１７で表される有機基としては、Ｒで表される有機基として前述した具体例及び好ましい例と同様のものが挙げられる。
Ｒ^ｔ１０〜Ｒ^ｔ１７で表される有機基としては、例えば、特開２００３−２６１６８１号公報段落００３１に記載の方法により任意の有機基を導入することもできる。According to the method for producing a polysilane compound according to the first aspect, at least one polysilane compound selected from the group consisting of linear polysilane, branched polysilane, and cyclic polysilane can be produced. In particular, cyclic polysilane compounds can also be selectively produced.
The cyclic polysilane compound can be preferably a polysilane compound having Mw 5000 or less in terms 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 the polysilane compounds represented by the following general formulas (T-1) and (T-2).

(R ^t10 R ^t11 R ^t12 Si) _t1 (R ^t13 R ^t14 Si) _t2 (R ^t15 Si) _t3 (Si) _t4 (T-1)
(In the above general formula, R ^t10 , R ^t11 , R ^t12 , R ^t13 , R ^t14 and R ^t15 are independently hydrogen atoms, hydroxyl groups or organic groups. T1, t2, t3 and t4 are independent, respectively. In addition, it is a mole fraction, and t1 + t2 + t3 + t4 = 1, 0 ≦ t1 ≦ 1, 0 ≦ t2 ≦ 1, 0 ≦ t3 ≦ 1, and 0 ≦ t4 ≦ 1.)

(In the above general formula (T-2), R ^t16 and R ^t17 each independently represent 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 above-mentioned specific examples and preferred examples as the organic group represented by R.
As the ^{organic group represented by R t10 to} R ^t17 , for example, any organic group can be introduced by the method described in paragraph 0031 of JP-A-2003-261681.

In the polysilane compound according to the second aspect, the ratio of the siloxane bond (Si—O) measured by X-ray photoelectron spectroscopy in the polysilane compound is preferably 0.5 or less.

According to the method for producing a polysilane compound according to the first aspect, a spectrum having a maximum detection peak height in a binding energy range of 99 eV or more and 104 eV or less 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 peak areas of the following (1X) and (2X), can be 0.4 or less. It is preferably 35 or less, more preferably 0.3 or less, further preferably 0.2 or less, particularly preferably 0.1 or less, and most preferably 0.05 or less.

(1X) ... Area of the peak having the maximum peak height in the range where the binding energy is 99.0 eV or more and 99.5 eV or less (2X) ... The maximum peak height is set in the range where the binding energy is 100 eV or more and 104 eV or less. Area of peak (3X) ... (2X) / [(1X) + (2X)]

The peak area obtained by measuring the peak intensity and separating the peaks in each of the above (1X) and (2X) binding energy ranges is the maximum in the range where the binding energy of (2X) is 100 eV or more and 104 eV or less. From the area of the peak having the peak height, the content ratio of Si—O and Si—C can be known. Further, the Si—Si content ratio can be found from the area of the peak having the maximum peak height in the range where the binding energy of (1X) is 99.0 eV or more and 99.5 eV or less.

When the polysilane compound contains not only Si—C but also Si—O, peaks having two maximum peak heights appear overlapping in the range of 100 eV or more and 104 eV or less after peak separation, but the second aspect is concerned. In the polysilane compound, it is preferable that only one 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. Therefore, substantially Si- It is considered that O-bonds are not included.
Further, when the conventional polysilane compound contains not only Si-C but also Si-O, two peaks having the maximum peak height appear in the range of 100 eV or more and 104 eV or less after peak separation, so that the area ratio is high. Since it becomes large, the ratio expressed by the above formula exceeds 0.4.

According to the method for producing a polysilane compound according to the first aspect, since the organic metal complex does not contain a halogen atom, it is possible to suppress the formation of side reactants such as a siloxane bond and a silanol group, and polysilane. The abundance of siloxane bonds (Si—O) in the compound can be reduced, and the performance of the film such as suppression of microcrack generation can be improved.

According to the method for producing a polysilane compound according to the first aspect, 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. It is preferably 100 ppb or less, more preferably 50 ppb or less, and particularly preferably 10 ppb or less.
By setting the content within the above range, it is possible to prevent deterioration of the performance of the photoelectronic material such as a film containing the polysilane compound.

<Composition>
The composition according to the third aspect is a composition containing the polysilane compound of the second aspect.
Further, the composition according to the third aspect may be a thermosetting composition or may not be a thermosetting composition.
Further, the composition according to the third aspect may be a radiation-sensitive composition or not a radiation-sensitive composition, and is a positive radiation-sensitive composition that is solubilized in a developing solution by exposure. It may be a material, or it may be a negative type radiation-sensitive composition that is insoluble in a developing solution by exposure.
Examples of the light source of the radiation include active energy rays such as ultraviolet rays and excima laser light, and light sources that emit ultraviolet rays such as high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, and carbon arc lamps.

(solvent)
The composition according to the third aspect preferably contains a solvent. As the solvent, the above cyclic skeleton-containing acetate 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;
Lactone ring-containing organic solvent such as γ-butyrolactone;
Compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ethers, monoethyl ethers, monopropyls of the polyhydric alcohols or compounds having the ester bonds. Derivatives of polyhydric alcohols such as monoalkyl ethers such as ethers and monobutyl ethers or compounds having an ether bond such as monophenyl ethers;
Cyclic ethers such as dioxane and esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate;
Aromatic organic solvents such as anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, amylbenzene, isopropylbenzene, toluene, xylene, simen, mesityrene;
N, N, N', N'-tetramethylurea, N, N, 2-trimethylpropionamide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylacetamide, N, N-diethyl Nitrogen-containing organic solvents such as formamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone;
Can be mentioned.

Of these, the cyclic skeleton-containing acetate compound, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), N, N, N', N'-tetramethylurea (TMU), and butanol are preferable.
These solvents may be used in combination of two or more.

The water content of the composition according to the third aspect is 0.5% by mass or less because the composition according to the third aspect suppresses microcracks or easily forms a silica-based film having a low dielectric constant. It is preferably 0.3% by mass or less, and particularly preferably less than 0.3% by mass.
The water content of the composition according to the third aspect is often derived from the solvent. Therefore, it is preferable that the solvent is dehydrated so that the water content of the composition according to the third aspect is the above amount.

The amount of the solvent used is not particularly limited as long as it does not impair the object of the present invention. 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.

(Other ingredients)
The composition according to the third aspect may contain polysilane other than the polysilane compound according to the first aspect. For example, a polysilane compound having a high Mw (hereinafter, also simply referred to as “high molecular weight polysilane”) may be mentioned in terms of improving chemical resistance, and the Mw of the high molecular weight polysilane is, for example, more than 5,000 and less than 100,000, preferably more than 5,000. 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. Examples of 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 10000, and even more preferably 2000 to 8000.
In the polysilane-polysiloxane resin, for example, the polysilane compound according to the first aspect is treated with the above-mentioned basic conditions in a solvent, and then the following general formulas (A-1-1) to (A-) are used. With at least one silicon compound selected from the group consisting of the silicon compounds represented by 1-4) and at least one selected from the group consisting of hydrolysates, condensates and hydrolyzed condensates of the above silicon compounds. Can be produced by hydrolyzing and condensing the reaction.
R ¹ R ² R ³ SiX ¹ (A-1-1)
R ⁴ R ⁵ SiX ² ₂ (A-1-2)
R ⁶ SiX ³ ₃ (A-1-3)
SiX ⁴ ₄ (A-1-4)
(In the ^formula, 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 It is an organic group, and the 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, an isocyanate group (NCO) and the like, and an alkoxy group is preferable.
Examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms, and specifically, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, and the like. Examples include a pentoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and 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. Alkyl groups with 1 to 10 carbon atoms (preferably alkyl groups with 1 to 6 carbon atoms, particularly alkyl groups with 1 to 4 carbon atoms)], cycloalkyl groups (5-carbon atoms such as cyclohexyl groups) 8 cycloalkyl groups, especially cycloalkyl groups with 5 to 6 carbon atoms), alkenyl groups [alkenyl groups with 2 to 10 carbon atoms such as ethenyl groups, propenyl groups, butenyl groups (preferably 2 to 6 carbon atoms) Alkenyl groups, particularly alkenyl groups having 2 to 4 carbon atoms, etc.)], cycloalkenyl groups [1-cyclopentenyl groups, 1-cyclohexenyl groups, and other cycloalkenyl groups having 5 to 10 carbon atoms (preferably having 5 to 10 carbon atoms). 5-8 cycloalkenyl groups, especially cycloalkenyl groups with 5-7 carbon atoms)], aryl groups (aryl groups with 6-10 carbon atoms such as phenyl and naphthyl groups), aralkyl groups [benzyl, phenethyl groups] C _6-10 aryl-C _1-6 alkyl group (C _6-10 aryl-C _1-4 alkyl group, etc.)], amino group, N-substituted amino group (the above alkyl group, cycloalkyl group, aryl group, etc.) , N-mono or di-substituted amino group substituted with an aralkyl group, an acyl group, etc.) and the like. The above-mentioned alkyl group, cycloalkyl group, aryl group, aryl group constituting an aralkyl group and the like may have one or a plurality of substituents. Examples of such a substituent include the above-exemplified alkyl group (particularly, an alkyl group having 1 to 6 carbon atoms), the above-exemplified alkoxy group, and the like. _{Examples of the organic group having such a substituent include a C 1-6} alkyl-C _6-10 aryl group (preferably mono, di or tri C _1-4) such as tolyl, xylenyl, ethylphenyl, methylnaphthyl group and the like. Alkyl-C _6-10 aryl groups, especially mono or diC _{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) and the like.

Further, the silicon compound represented by the general formula (A-1-3) may be a silicon compound represented by the following formula (A-3).

HOOC-U-Z-Y-Si (OR ^a ) ₃ (A-3)

(In the above general formula (A-3), U is a divalent group or a branched chain generated by removing one hydrogen atom of each of the two ring carbon atoms from the aromatic ring group or the alicyclic group. and / or represents an alkylene group which may have a double bond, Z is represents -NHCO- or -CONH-, Y is a single bond, an alkylene group, an arylene group or a ^-R Y1 ^{-NH-R Y2} -. (. ^{wherein, R Y1} and ^{R Y2} is to represent each independently an alkylene group) represents, ^{R a} each independently represents a hydrocarbon group, however, U and / or Y, (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 an aromatic ring having 6 to 10 carbon atoms which may have a substituent having 1 to 2 carbon atoms (for example, a benzene ring, a naphthalene ring, a tolyl group, a xylyl group, etc.). be able to.
Examples of the alicyclic in U include an alicyclic having 5 to 10 carbon atoms (for example, a monocyclic cycloalkyl group, a monocyclic cycloalkenyl group, a bicyclic alkyl group, a cage-type alkyl group, and the like, and specific examples thereof. For example, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, dicyclopentadiene ring, norbornene ring, norbornene ring, cuban ring, basketane ring, etc.) can be mentioned.
Examples of the alkylene group which may have a branched chain and / or a double bond in U include an alkylene group having 1 to 4 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group and a vinylene group. 2-octenyl) ethylene group, (2,4,6-trimethyl-2-nonenyl) alkylene group such as ethylene group, alkylene group having a double bond or alkylene group having a branched chain having 1 to 9 carbon atoms. Can be done.

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 in Y is preferably one having 6 to 10 carbon atoms. Examples of such a group include a phenylene group (ortho, meta, para, etc.), a naphthylene group (1,4-, 1,5-, 2,6-, etc.) and the like. Specific examples ^{of −R Y1} −NH ^{−R Y2} − in the above Y _{include −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 -etc. be able to.

The polysiloxane resin is a hydrolyzate or condensate of at least one silicon compound selected from the group consisting of silicon compounds represented by the above general formulas (A-1-1) to (A-1--4). And at least one selected from the group consisting of hydrolyzed condensates.

The resin other than the polysilane compound according to the first aspect (hereinafter, other Si resin) may be used alone or in combination of two or more.
When the other Si resin is contained, the compounding ratio (mass ratio) of the polysilane compound according to the first aspect to the other Si resin in the composition according to the third aspect may be appropriately changed depending on the intended use. For example, it is 1:99 to 99: 1, preferably 10:90 to 90:10.

The composition according to the third aspect may contain an organic compound having two or more hydroxyl groups or carboxyl groups in one molecule as a dissolution accelerator in an alkaline aqueous solution or solution. Examples of such an organic compound include the compounds shown below.

Incidentally, E in the above formula is a hydrogen atom, a methyl group, or a hydroxymethyl group, R ¹⁵ is methylene group, a carbonyl group, or a phenylene group, n is an integer of 3 or more and less than 100. na indicates a natural number of 1 to 3, nb indicates a natural number of 1 or more, nc indicates a natural number of 2 to 4, and nd indicates a natural number of 2 or more.
Although enantiomers and diastereomers may exist in the above structural formulas, each structural formula represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

The organic compounds may be used alone or in combination of two or more. The amount used is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total amount of the solid content of the composition according to the third aspect excluding the solvent.
By adding such an organic compound, the disintegration of the film formed by using the above composition is accelerated and peeling becomes easy.

The composition according to the third aspect may contain a monovalent or divalent or higher organic acid having 1 to 30 carbon atoms in order to improve stability. The acids added at this time include malonic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, hexane acid, hepatic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, and 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, methyl succinic acid, glutaric acid, adipic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, citric acid and the like. Of these, oxalic acid, maleic acid, formic acid, acetic acid, propionic acid, citric acid and the like are particularly preferable. Further, in order to maintain stability, two or more kinds of acids may be mixed and used. The above organic acid is converted into the pH of the composition and blended so that 0 ≦ pH ≦ 7, more preferably 0.3 ≦ pH ≦ 6.5, and further preferably 0.5 ≦ pH ≦ 6. That's good.

Further, the composition according to the third aspect may contain a monohydric or divalent or higher alcohol having a cyclic ether as a substituent as a stabilizer, or an ether compound. Specific examples of the stabilizer that can be used include the stabilizers described in paragraphs (0180) to (0184) of JP-A-2009-126940.

The composition according to the third aspect may contain water. The addition of water improves lithography performance. The content of water in the solvent component of the composition according to the third aspect is preferably more than 0% by mass and less than 50% by mass, more preferably 0.3 to 30% by mass, still more preferably 0.5 to 20% by mass. Is.

The composition according to the third aspect may contain a photoacid generator. Specific examples of the photoacid generator that can be used include the photoacid generators described in paragraphs (0160) to (0179) of JP-A-2009-126940.

The composition according to the third aspect may contain a surfactant, if necessary. Specific examples of the surfactant that can be used include the surfactant described in paragraph 2009-126940 (0185).

The composition according to the third aspect may contain a thermal cross-linking accelerator. Specific examples of the heat-crosslinking accelerator that can be used include the heat-crosslinking accelerator described in JP-A-2007-302873. Examples of the thermal cross-linking accelerator include phosphate compounds and borate compounds. Examples of such a phosphate compound include ammonium salts such as ammonium phosphate, tetramethylammonium phosphate and tetrabutylammonium phosphate, and sulfonium salts such as triphenylsulfonium phosphate. Examples of such borate compounds include ammonium salts such as ammonium borate, tetramethylammonium borate, and tetrabutylammonium borate, and sulfonium salts such as triphenylsulfonium borate.
The thermal cross-linking accelerator may be used alone or in combination of two or more. The amount of the thermal cross-linking accelerator added 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 of the composition excluding the solvent.

The composition according to the third aspect may contain various other curing agents.
Examples of the curing agent include Bronsted acid; imidazoles; organic amines; organic phosphorus compounds and their complexes; organic amine complexes of Lewis acid; amidines; curing agents that generate basic components by light or heat. Be done.

(Use)
Since the composition according to the third aspect contains a polysilane compound in which the amount of residual metal is small and siloxane formation is suppressed (controlled), it can be suitably used as a material for a manufacturing process such as a semiconductor, a display or a solar cell. .. For example, it can be used for forming a protective film or an interlayer film that protects 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), electrophoresis displays (electronic paper), touch panels, color filters, backlights, and other display material substrates (metal oxide-containing films, various metal-containing substrates). Includes membranes), solar cell substrates (including metal oxide-containing films and various metal-containing films), substrates for photoelectric conversion elements such as optical sensors (including metal oxide-containing films and various metal-containing films). , Substrate of photoelectric element (including metal oxide-containing film and various metal-containing films).
Further, when the substrate component (resin component) in the composition according to the third aspect is substantially composed of only the polysilane compound according to the first aspect, the gap fill characteristics are particularly excellent, so that the semiconductor substrate is used. A trench isolation structure is included in which a fine groove is formed on the surface, the inside of the groove is filled with the composition according to the third aspect, and the elements formed on both sides of the groove are electrically separated from each other. It can be used for forming an insulating film, a passivation film, a flattening film, a protective film, and the like.

<Membrane and substrate provided with the above film>
The membrane according to the fourth aspect is a membrane containing the polysilane compound of the second aspect.
The substrate according to the fifth aspect is a substrate provided with a film containing the polysilane compound of the second aspect.
As described above, the film according to the fourth aspect is preferably an insulating film, a passivation film, a flattening 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 effect of the present invention is not impaired, but a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, etc. is applied on an arbitrary substrate as needed. A method of coating using a non-contact coating device such as a spinner (rotary coating device) or a curtain flow coater can be mentioned.
The substrate is not particularly limited, but for example, a substrate (containing metal oxide) of a display material such as a semiconductor substrate, a liquid crystal display, an organic light emitting display (OLED), an electrophoresis display (electronic paper), a touch panel, a color filter, and a backlight. Films, including various metal-containing films), solar cell substrates (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) Including films), photoelectric element substrates (including metal oxide-containing films and various metal-containing films), glass substrates, quartz substrates, transparent or translucent resin substrates (eg, polycarbonate, polyethylene terephthalate, poly). Heat-resistant materials such as ether sulfone, polyimide, and polyamideimide), metals, silicon substrates, and the like.
The thickness of the substrate is not particularly limited, and can be appropriately selected depending on the usage mode of the pattern forming body.

The coating film after the coating is preferably dried (prebaked). The drying method is not particularly limited, and 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 method of drying at room temperature for several hours to Examples thereof include a method of leaving it for several days, and (3) a method of putting it in a hot air heater or an infrared heater for several tens of minutes to several hours to remove the solvent.

The dried coating film may or may not be exposed by irradiating it 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. The exposure step may be performed in place of the firing step described later or in combination with the firing step. Further, in the step of exposure, for example, the formed coating film may be selectively exposed, and when the selective exposure step is included, the step of developing may be included. Further, for example, imprint lithography may be performed on the formed coating film. When performing imprint lithography, for example;
A step of applying the composition of the third aspect on a substrate to form a coating film, and
The process of pressing the mold on which the uneven structure of a predetermined pattern is formed against the coating film, and
Examples thereof include a method including an exposure step.
The step of exposure is performed on the coating film made of the composition of the third aspect while the mold is pressed against the coating film. By peeling off the mold after curing by exposure, a film according to the fourth aspect patterned according to the shape of the mold can be obtained.

The coating film after drying, exposure, or development is preferably fired (post-baked) in order to improve the physical characteristics of the film. The firing temperature depends on the lower substrate and the intended use, but is, for example, in the range of 200 to 1000 ° C, preferably 200 ° C to 500 ° C, and more preferably 200 to 250 ° C. The firing atmosphere is not particularly limited, and may be under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, under vacuum, or under reduced pressure. It may be in the atmosphere, or the oxygen concentration may be appropriately controlled. The firing time may be appropriately changed, for example, about 10 minutes to 120 minutes.

The film thickness in the fourth and fifth aspects is preferably 10 to 3000 nm, more preferably 50 to 1500 nm, and even more preferably 100 to 1000 nm.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Example 1]
In a round flask having an internal volume of 1000 ml equipped with a three-way cock, 25 g of granular (particle size 20 to 1000 μm) magnesium and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst were charged, and 1 mmHg (1 mmHg) at 50 ° C. After heating and reducing the pressure to 133 kPa) to dry the inside of the reactor (flask), dry argon gas is introduced into the reactor, 500 ml of tetrahydrofuran (THF) previously dried with sodium-benzophenone ketyl is added, and the temperature is 25 ° C. The mixture was stirred for about 60 minutes. To this reaction mixture, 63.5 g (0.3 mol) of methylphenyldichlorosilane purified in advance by distillation was added with a syringe, and the mixture was stirred at 25 ° C. for about 24 hours. After completion of the reaction, 1000 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, and the mixture was further extracted with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then the toluene was distilled off to obtain 28.4 g of a linear methylphenylsilane polymer (mass average molecular weight 2000). Obtained (yield 63%).

[Example 2]
In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 25 g of granular magnesium (particle size 20 to 1000 μm) and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst are charged 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 THF previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at 25 ° C. for about 60 minutes. To this reaction mixture, 63.5 g (0.3 mol) of methylphenyldichlorosilane purified in advance by distillation was added with a syringe, and the mixture was stirred at 25 ° C. for about 24 hours.
The obtained linear methylphenylsilane polymer is dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and _{200 g of a copper chloride aqueous solution containing copper (II) chloride (CuCl 2} ) in a proportion of 10% by mass is further mixed. After stirring for 60 minutes, the organic phase containing a linear methylphenylsilane polymer and the aqueous phase containing copper chloride were separated. Then, the organic phase containing the linear methylphenylsilane polymer was washed 3 times with 200 ml of pure water, and then the solvent component was distilled off to obtain a linear methylphenylsilane polymer (mass average molecular weight 2000). 32.4 g was obtained (yield 72.6%).

[Example 3]
In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 25 g of granular magnesium (particle size 20 to 1000 μm) and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst are charged 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. To this reaction mixture, 105.8 g (0.50 mol) of phenyltrichlorosilane purified in advance by distillation was added, and the mixture was stirred at 20 ° C. for about 18 hours. After completion of the reaction, 300 ml of toluene was added, and then magnesium chloride and excess magnesium produced by the reaction were removed by vacuum filtration. The filtrate was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.
After completion of the reaction, 1000 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, and the mixture was further extracted with 500 ml of toluene. 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 38.2 g of branched polyphenylsilane (mass average molecular weight 2000) (mass average molecular weight 2000). Yield 72%).

[Example 4]
In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 25 g of granular (particle size 20 to 1000 μm) magnesium and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst are charged 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. To this reaction mixture, 105.8 g (0.50 mol) of phenyltrichlorosilane purified in advance by distillation was added, and the mixture was stirred at 20 ° C. for about 18 hours. After completion of the reaction, 300 ml of toluene was added, and then magnesium chloride and excess magnesium produced by the reaction were removed by vacuum filtration. The filtrate was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.
The obtained branched polyphenylsilane is dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and _{200 g of a copper chloride aqueous solution containing copper (II) chloride (CuCl 2} ) in a proportion of 10% by mass is further mixed and 60. After stirring for 1 minute, the organic phase containing branched polyphenylsilane and the aqueous phase containing copper chloride were separated. Then, the organic phase containing the branched polyphenylsilane was washed 3 times with 200 ml of pure water, and then the solvent component was distilled off to obtain 41.9 g of the branched polyphenylsilane (mass average molecular weight 2000) (mass average molecular weight 2000). Yield 79%).

[Example 5]
In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 25 g of granular magnesium (particle size 20 to 1000 μm) and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst are charged 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 THF previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at 25 ° C. for about 60 minutes. To this reaction mixture, 63.5 g (0.3 mol) of phenyltrichlorosilane purified in advance by distillation and 34.5 g (0.3 mol) of dimethyldichlorosilane were added with a syringe, and the mixture was stirred at 25 ° C. for about 24 hours. After completion of the reaction, 1000 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, and the mixture was further extracted with 500 ml of toluene. The toluene phase was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then the toluene was distilled off to obtain a branched phenylsilane-methylsilane copolymer (former / latter (molar ratio) =). 1/1) was obtained (mass average molecular weight 3000).
The obtained branched phenylsilane-dimethylsilane copolymer is dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and _{200 g of a copper chloride aqueous solution containing copper (II) chloride (CuCl 2} ) in a proportion of 10% by mass. Was mixed and stirred for 60 minutes, and then the organic phase containing the branched phenylsilane-dimethylsilane copolymer and the aqueous phase containing copper chloride were separated. Then, the organic phase containing the branched phenylsilane-dimethylsilane copolymer was washed 3 times with 200 ml of pure water, and then the solvent component was distilled off to obtain a phenylsilane-methylsilane copolymer (mass average molecular weight 2000). 36.6 g was obtained (yield 74%).

[Example 6]
In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 25 g of granular magnesium (particle size 20 to 1000 μm) and 2.1 g of tris (acetylacetonato) iron (III) as a catalyst are charged 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 for about 30 minutes. To this reaction mixture, 63.5 g (0.3 mol) of methylphenyldichlorosilane purified in advance by distillation was added, and the mixture was stirred at 20 ° C. for about 6 hours. After completion of the reaction, 300 ml of toluene was added, and then magnesium chloride and excess magnesium produced by the reaction were removed by vacuum filtration. The filtrate was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of a cyclic methylphenylsilane polymer.
After completion of the reaction, 1000 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, and the mixture was further extracted with 500 ml of toluene. 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 31 g of a cyclic methylphenylsilane polymer (mass average molecular weight 700) (collection). Rate 86%).

[Comparative Example 1]
_{25.0 g of granular magnesium (particle size 20 to 1000 μm) and 16.2 g of anhydrous zinc chloride (ZnCl 2} ) are charged in a round flask having an internal volume of 1000 ml equipped with a three-way cock, and heated and depressurized to 1 mmHg at 50 ° C. After drying 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. To this reaction mixture, 63.5 g (0.3 mol) of methylphenyldichlorosilane purified in advance by distillation was added with a syringe, and the mixture was stirred at 25 ° C. for about 24 hours. After completion of the reaction, 1000 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, and the mixture was further extracted with 500 ml of toluene. 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 a methylphenylsilane polymer (mass average molecular weight 6000) (collection). Rate 60%).

[Comparative Example 2]
_{25.0 g of granular (particle size 20 to 1000 μm) magnesium and 16.2 g of anhydrous zinc chloride (ZnCl 2} ) are charged in a round flask having an internal volume of 1000 ml equipped with a three-way cock, and heated and depressurized to 1 mmHg at 50 ° C. After drying the inside of the reactor, dry argon gas was introduced into the reactor, 500 ml of tetrahydrofuran (THF) previously dried with sodium-benzophenone ketyl was added, and the mixture was stirred at 25 ° C. for about 60 minutes. To this reaction mixture, 63.5 g (0.3 mol) of methylphenyldichlorosilane purified in advance by distillation was added with a syringe, and the mixture was stirred at 25 ° C. for about 24 hours.
The obtained linear phenylsilane-dimethylsilane copolymer is dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and a copper _{chloride aqueous solution containing copper (II) chloride (CuCl 2} ) in a proportion of 10% by mass. After mixing 200 g and stirring for 60 minutes, the organic phase containing a linear phenylsilane-dimethylsilane copolymer and the aqueous phase containing copper chloride were separated. Then, the organic phase containing the linear phenylsilane-dimethylsilane copolymer was washed three times with 200 ml of pure water, and then the solvent component was distilled off to obtain a linear phenylsilane-dimethylsilane copolymer (a linear phenylsilane-dimethylsilane copolymer). 21.6 g (mass average molecular weight 3000) was obtained (yield 60%).

[Comparative Example 3]
In a round flask with an internal volume of 1000 ml equipped with a three-way cock, 25.0 g of granular magnesium (particle size 20 to 1000 μm), 21.4 g of anhydrous lithium chloride, and 4.1 g of second iron chloride are charged and adjusted to 1 mmHg at 50 ° C. After heating and reducing the pressure to dry the reaction mixture, 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. To this reaction mixture, 105.8 g (0.50 mol) of methylphenyldichlorosilane purified in advance by distillation was added, and the mixture was stirred at 20 ° C. for about 18 hours. After completion of the reaction, 300 ml of toluene was added, and then magnesium chloride and excess magnesium produced by the reaction were removed by vacuum filtration. The filtrate was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of a linear methylphenylsilane polymer.
The obtained linear methylphenylsilane polymer is dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and _{200 g of a copper chloride aqueous solution containing copper (II) chloride (CuCl 2} ) in a proportion of 10% by mass is further mixed. After stirring for 60 minutes, the organic phase containing a linear methylphenylsilane polymer and the aqueous phase containing copper chloride were separated. Then, the organic phase containing the linear methylphenylsilane polymer was washed 3 times with 200 ml of pure water, and then the solvent component was distilled off to obtain 36 g of the linear methylphenylsilane polymer (mass average molecular weight 2000). Was obtained (yield 60%).

[Comparative Example 4]
In a round flask having an internal volume of 1000 ml equipped with a three-way cock, 25.0 g of granular magnesium (particle size 20 to 1000 μm) and _{16.2 g of anhydrous zinc chloride (ZnCl 2} ) are charged, and the mixture is heated and depressurized to 1 mmHg at 50 ° C. After drying the reaction mixture, 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. To this reaction mixture, 105.8 g (0.50 mol) of phenyltrichlorosilane purified in advance by distillation was added, and the mixture was stirred at 20 ° C. for about 18 hours. After completion of the reaction, 300 ml of toluene was added, and then magnesium chloride and excess magnesium produced by the reaction were removed by vacuum filtration. The filtrate was washed 10 times with 200 ml of pure water, the toluene phase was dried over anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.
After completion of the reaction, 1000 ml of 1N (= 1 mol / L) hydrochloric acid was added to the reaction mixture, and the mixture was further extracted with 500 ml of toluene. 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 38.2 g of a branched polyphenylsilane polymer (mass average molecular weight 2000). (Yield 60%).

[Comparative Example 5]
In a round flask having an internal volume of 1000 ml equipped with a three-way cock, 25.0 g of granular magnesium (particle size 20 to 1000 μm) and _{16.2 g of anhydrous zinc chloride (ZnCl 2} ) are charged, and the mixture is heated and depressurized to 1 mmHg at 50 ° C. After drying the reaction mixture, 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. To this reaction mixture, 105.8 g (0.50 mol) of phenyltrichlorosilane purified in advance by distillation was added, and the mixture was stirred at 20 ° C. for about 18 hours. After completion of the reaction, 300 ml of toluene was added, and then magnesium chloride and excess magnesium produced by the reaction were removed by vacuum filtration. The filtrate was washed 10 times with 200 ml of pure water, the toluene layer was dried over anhydrous magnesium sulfate, and then toluene and tetrahydrofuran were distilled off to obtain 50 g of branched polyphenylsilane.
The obtained branched polyphenylsilane is dissolved in a mixed solution of 150 g of toluene and 150 g of tetrahydrofuran, and _{200 g of a copper chloride aqueous solution containing copper (II) chloride (CuCl 2} ) in a proportion of 10% by mass is further mixed and 60. After stirring for 1 minute, the organic phase containing branched polyphenylsilane and the aqueous phase containing copper chloride were separated. Then, the organic phase containing the branched polyphenylsilane was washed 3 times with 200 ml of pure water, and then the solvent component was distilled off to obtain 31.8 g of the branched polyphenylsilane polymer (mass average molecular weight 2000). (Yield 60%).

Examples 1 to 6 and Comparative Examples 1 to 5 are summarized in Table 1 below.

The polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated for the contents of each of Zn, Cu, and Fe, the gap fill characteristics, and the siloxane bond (Si—O) ratio according to the following methods.

<Evaluation of the content of each of Zn, Cu, and Fe>
The contents of Zn, Cu, and Fe in the polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were measured using ICP-MS (Inductively coupled plasma mass spectroscopic). The results are shown in Table 2.
(Evaluation criteria)
〇: Content of Zn, Cu, Fe is 500 ppb or less ×: Content of Zn, Cu, Fe is more than 500 ppb

<Gap fill characterization>
The polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5 were dissolved in cyclohexylacetate 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 using the composition) according to the following evaluation method.
(Evaluation criteria)
A silicon wafer having a line width of 40 nm and a space width of 15 nm and a height (space depth) of 85 nm is formed in a repeating trench pattern. The pattern was applied so that the height from the bottom surface was about 185 nm), prebaked 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 by SEM. Evaluation was made according to the following criteria.
〇: The polysilane compound film is uniformly embedded in the trench pattern portion.
X: Poor embedding of the polysilane compound film is observed in the trench pattern portion.

<Evaluation of ratio of siloxane bond (Si—O) and Si—C bond>
XPS analysis was performed on the polysilane compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 5, and a spectrum having a maximum detected peak height was separated into peaks in the binding energy range of 99 eV or more and 104 eV or less, and the binding energy was 100 eV or more. The area of the peak having the maximum peak height in the range of 104 eV or less (2X) (the peak area derived from the siloxane bond (Si—O) and the Si—C bond) and the binding energy of 99.0 eV or more and 99.5 eV or less. The peak area (1X) (peak area derived from Si—Si), which is a range, was calculated, and the ratio represented by the following formula (3X) was calculated and evaluated according to the following criteria.

(1X) ... Area of the peak having the maximum peak height in the range where the binding energy is 99.0 eV or more and 99.5 eV or less (2X) ... The maximum peak height is set in the range where the binding energy is 100 eV or more and 104 eV or less. Area of peak (3X) ... (2X) / [(1X) + (2X)]

(Evaluation criteria)
⊚: 15% or less 〇: More than 15% 40% or less ×: More than 40% The results are shown in Table 2.
In Table 2, the absence of "Si-O peak" means that there is only one peak attributed in the range of 100 eV or more and 104 eV or less. The presence of "Si-O peak" means that there are two peaks attributed in the range of 100 eV or more and 102 eV or less.

As is clear from the results shown in Table 2, in Comparative Examples 1, 2, 4 and 5 in which zinc chloride was used without using the organometallic complex in the production of the polysilane compound, Zn remained in the polysilane compound. ..
Further, in Comparative Examples 2, 3 and 5 in which purification treatment was performed with copper chloride without using an organic metal complex in the production of the polysilane compound, Cu remained in the polysilane compound, and the siloxane bond in the polysilane compound was obtained. The ratio of (Si—O) and Si—C bonds exceeded 40%.
Further, in Comparative Examples 2 and 3 in which iron chloride was used without using the organometallic complex in the production of the polysilane compound, Fe remained in the polysilane compound.
On the other hand, in Examples 1 to 6 in which the polysilane compound was produced using the organic metal complex, the Mw of the polysilane compound was 5000 or less, the residual amount of Zn, Cu and Fe in the polysilane compound was low, and the siloxane bond (siloxane bond () The content ratios of Si—O) and Si—C bonds were also 15% or less. In addition, all of Examples 1 to 6 were excellent in gap fill characteristics.

Claims (21)

A method for producing a polysilane compound having a mass average molecular weight of 300 or more and 2500 or less, which comprises reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium , wherein the polysilane compound is a semiconductor process. A method, which is a polysilane compound for gapfill materials in .

M ^p L _{p / q} (A1)

(In the above general formula (A), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represent an integer of 1 or more.) The manufacturing method according to claim 1, wherein the gap fill material is a gap fill material for filling a groove on the surface of a semiconductor substrate. The production method according to claim 1 or 2, excluding the method for producing polysilanes, which comprises allowing magnesium to act in the presence of an alkali metal salt in a solvent. Reacting the halosilane compound in the presence of the organometallic complex represented by the following general formula (A1) and magnesium , and
A method for producing a polysilane compound having a mass average molecular weight of 5000 or less, which comprises contacting a polysilane compound obtained after the reaction with a metal halide or a base for purification , wherein the metal halide is Cr, Ga, Fe ( At least one selected from the group consisting of Fe (II) or Fe (III)), Cd, Co, Ni, Sn, Pb, Cu (Cu (II) or Cu (I)), Ag, Pd, Pt and Au. A metal halide containing one metal or metal ion,
At least one alkyl metal whose base is selected from the group consisting of methyllithium, n-butyllithium, methylmagnesium chloride, and ethylmagnesium bromide.
At least one alkoxide selected from the group consisting of sodium methoxide, sodium ethoxide, and potassium t-butoxide, or
A method which is at least one organic base selected from the group consisting of triethylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, 4-dimethylaminopyridine, and diazabicycloundecene (DBU) .

M ^p L _{p / q} (A1)

(In the above general formula (A), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represent an integer of 1 or more.) The metal halide or base is Cr, Ga, Fe (Fe (II) or Fe (III)), Cd, Co, Ni, Sn, Pb, Cu (Cu (II) or Cu (I)), Ag. The production method according to claim 4, wherein the metal halide contains at least one metal or metal ion selected from the group consisting of Pd, Pt and Au. A method for producing a polysilane compound having a mass average molecular weight of 5000 or less, which comprises reacting a halosilane compound in the presence of an organometallic complex represented by the following general formula (A1) and magnesium, wherein the produced polysilane compound is cyclic. A manufacturing method that is polysilane .

M ^p L _{p / q} (A1)

(In the above general formula (A), M ^p represents a p-valent metal cation, L represents a q-valent organic ligand, and p and q each independently represent an integer of 1 or more.) The production method according to any one of claims 1 to 6, wherein the organometallic complex is an organometallic complex represented by the following general formula (A2).

(In the above general formula (A2), M is iron, silver, aluminum, bismuth, cerium, cobalt, copper, disprosium, erbium, europium, gallium, gadrinium, hafnium, formium, indium, iridium, lanthanum, lutetium, manganese, Molybdenum, Neodim, Nickel, Osmium, Palladium, Promethium, Placeodim, Platinum, Renium, Rodium, Luthenium, Samalium, Scandium, Tin, Terbium, Titanium, Thurium, Vanadium, Chromium, Tantal, Itterbium, Gold, Mercury , Tungsten, Itterium, represents a metal selected from zinc and the group consisting of zirconium, R ^a1 are each independently a saturated hydrocarbon group, unsaturated hydrocarbon group, an aromatic hydrocarbon group, an aralkyl group, an alkoxy group, an aryloxy group, Represents an aralkyloxy group or an aryloxyalkyl group, ^Ra2 represents a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or an aralkyl group. P represents an integer of 1 or more.) In formula ^{(A2), R a1} represents a methyl ^{group, R a2} represents a hydrogen atom, a manufacturing method of claim 7. The production method according to any one of claims 1 to 5 , wherein the polysilane compound to be produced is at least one polysilane selected from the group consisting of linear polysilane, branched polysilane, and cyclic polysilane. The polysilane compound is a cyclic polysilane production process according to claim 9. Areas of the peaks (1X) and (2X) below obtained by peak separation of spectra having the maximum detection 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 production method according to any one of claims 1 to 10 , wherein the ratio represented by the following formula (3X), which is the ratio of the following (2X) to the sum of the above, is 0.4 or less.

(1X) ... Area of the peak having the maximum peak height in the range where the binding energy is 99.0 eV or more and 99.5 eV or less (2X) ... The maximum peak height is set in the range where the binding energy is 100 eV or more and 104 eV or less. Area of peak (3X) ... (2X) / [(1X) + (2X)]
The production method according to any one of claims 1 to 11 , wherein the content of each of the metals , Zn, Cu or Fe, in the polysilane compound is 500 ppb or less. An aqueous solution containing at least one selected from metal halides and the group consisting of bases, further comprising obtaining the polysilane compound by purification by contacting the liquid after the reaction, any claim 1-3 The manufacturing method according to item 1. The production method according to any one of claims 1 to 13 , wherein the halosilane compound is a compound represented by the following formula (1).

X _n SiR _4-n (1)

(In the equation, n is an integer of 2 to 4, n Xs are independently halogen atoms, and (4-n) Rs are each independently a hydrogen atom, an organic group or a silyl. Is the basis.) The area of the peaks (1X) and (2X) below obtained by peak separation of the spectrum having the maximum detected peak height in the bond energy range of 99 eV or more and 104 eV or less measured by X-ray photoelectron spectroscopy in the polysilane compound. The ratio represented by the following formula (3X), which is the ratio of the following (2X) to the sum, is 0.4 or less, and the content of each of the Zn, Cu, or Fe metals in the polysilane compound is 500 ppb or less. A polysilane compound having a mass average molecular weight of 300 or more and 2500 or less, which is used as a gap fill material in a semiconductor process .

(1X) ... Area of the peak having the maximum peak height in the range where the binding energy is 99.0 eV or more and 99.5 eV or less (2X) ... The maximum peak height is set in the range where the binding energy is 100 eV or more and 104 eV or less. Area of peak (3X) ... (2X) / [(1X) + (2X)] The polysilane compound according to claim 15, wherein the gap fill material is a gap fill material for filling a groove on the surface of a semiconductor substrate. The polysilane compound according to claim 15 or 16, wherein the polysilane compound is cyclic polysilane. The area of the peaks (1X) and (2X) below obtained by peak separation of 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, which is represented by the following formula (3X), is 0.4 or less, and the content of each of the Zn, Cu, or Fe metals in the polysilane compound is 500 ppb or less. A cyclic polysilane compound having a mass average molecular weight of 5000 or less. A composition comprising the polysilane compound according to any one of claims 15 to 18. A film containing the polysilane compound according to any one of claims 15 to 18. A substrate comprising a film containing the polysilane compound according to any one of claims 15 to 18.