KR101599952B1 - Methods of producing polymers and compositions for forming silica insulation films - Google Patents

Abstract

A process for producing a polysilazane polymer having a Si-N linkage in its main chain, which comprises reacting an aminosilane monomer represented by the following formula (1) in the presence of a nucleophilic compound capable of coordinating a Si atom of the aminosilane monomer, With a nitrogen-containing compound represented by the following formula (2), and a process for producing a polymer comprising the polymer produced from the process:
[Chemical Formula 1]
NR ₁ R ₂ R ₃
Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, -Si (R ₄ ) ₃ , a C 1 to C 30 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 10 alkoxy group, C6 to aryloxy C20, C1 to being ah alkyl or aryloxycarbonyl group, a C1 to C20 in the C20 group, or acyloxy Kii of C1 to C20, R _1, R _2, and R ₃ one of the more than -Si (R _{4) 3,} wherein R ₄ is the same or different, each independently, hydrogen, C1 to C30 alkyl groups, C6 to C20 aryl group, an alkoxy group of C1 to C10, or C6 to C20 of being odd aryloxy, R ₄ Lt; / RTI > is hydrogen;
(2)
NH ₂ R ₅
In Formula 2, R ₅ is R ₅ is hydrogen, C1 to C30 alkyl groups, C1 to C10 alkoxy group, C6 to C20 aryl oxy group, C1 to C20 alkyl or aryloxycarbonyl group, -NH _2, C1 to An acyl group of C20, an acyloxy group of C1 to C20 , a hydroxyl group, or an amine group.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a polymer and a composition for forming a silica-based insulating film,

A polysilazane polymer producing method, and a composition for forming a silica-based insulating film.

The silica-based coating film is widely used for an insulating film, a planarizing film, and the like in a semiconductor device, a liquid crystal display device, a photomask included in a phase shift, or the like. For example, a silica-based insulating layer is used to provide a low-defect dielectric layer in the capacitor included in the DRAM. Polysilazane polymers such as hydrogenated polysilazanes are included in compositions for forming such a silica-based insulating layer. Polysilazane according to the prior art uses a chlorine-containing silane compound such as chlorosilane and ammonia as a polymerization raw material, and there is a high possibility that chlorine is included in the skeleton of the obtained polysilazane. When a silica-based insulating film is formed using a composition containing polysilazane in which chlorine remains, residual chlorine may be liberated from the polysilazane skeleton at the time of film formation. Such free chlorine reacts with ammonia generated when polysilazane is oxidized to a silica-based coating film to form crystal grains of ammonium chloride. These crystal grains not only lower the compactness of the final silica coating but also cause flatness Can also have a negative impact. Therefore, there is a need to develop a polysilazane polymer having a very low chlorine content or no chlorine.

One embodiment provides a method of making a substantially chlorine-free polysilazane polymer.

Another embodiment provides a composition for forming a silica-based insulating film containing the polysilazane polymer substantially not containing chlorine.

In one embodiment, a method for producing a polysilazane polymer having a Si-N linkage in its main chain comprises reacting an aminosilane monomer represented by the following formula (1) with a nucleophilic group capable of coordinating a Si atom of the aminosilane monomer In the presence of a compound, with a nitrogen-containing compound represented by the following formula (2): < EMI ID =

 [Chemical Formula 1]

NR _One R ₂ R ₃

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, -Si (R ₄ ) ₃ , a C 1 to C 30 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 10 alkoxy group, C6 to aryloxy C20, C1 to being ah alkyl or aryloxycarbonyl group, a C1 to C20 in the C20 group, or acyloxy Kii of C1 to C20, R _1, R _2, and R ₃ one of the more than -Si (R _{4) 3,} wherein R ₄ is the same or different, each independently, hydrogen, C1 to C30 alkyl groups, C6 to C20 aryl group, an alkoxy group of C1 to C10, or C6 to C20 of being odd aryloxy, R ₄ Lt; / RTI > is hydrogen;

(2)

NH ₂ R ₅

In Formula 2, R ₅ is hydrogen, C1 to C30 alkyl groups, C1 to C10 alkoxy group, C6 to C20 aryl oxy group, C1 to C20 alkyl or aryloxycarbonyl group, -NH _2, C1 to C20 of O An acyloxy group of C1 to C20 , a hydroxyl group, or an amine group.

The aminosilane monomer may have at least two -Si (R ₄ ) ₃ groups of R ₁ , R ₂ , and R ₃ in the general formula (1).

The amino silane _{monomers, (H 3 Si) NH 2} , (H 3 Si) 2 NH, (H 3 Si) NMe 2, (H 3 Si) 2 NMe, (H 3 Si) 3 N, (H 2 MeSi _{) NH 2, (H 2 MeSi} ) (H 3 Si) NH, (H 2 MeSi) (H 3 Si) 2 N, (H 2 MeSi) 2 NH, (H 2 MeSi) 3 N, (H 2 PhSi) _{3 N, (H 2 PhSi)} NH 2, (H 2 PhSi) 2 NH, (H 2 (MeO) Si) 3 N, (H 2 (MeO) Si) 2 NH, (H (MeO) 2 Si) 2 _{NH, (H (MeO) 2} Si) 3 N, (H 2 (MeO) Si) NH 2, (H (MeO) 2 Si) NH 2, (H 3 Si) 2 NMe, (H 3 Si) 2 NPh , Derivatives thereof, or combinations thereof. (Wherein Me represents a methyl residue and Ph represents a phenyl residue)

Wherein the nucleophilic compound is selected from the group consisting of linear tertiary amines, heterocyclic nitrogen containing aromatic compounds, thioethers, linear tertiary phosphines, cyclic tertiary phosphines, N-alkylpyrroles, furans, thiophenes, Lt; / RTI >

The nitrogen-containing compound may be NH ₃ , NH ₂ NH ₂ , methylamine, ethylamine, propylamine, phenylamine, hydroxyamine or a combination thereof.

In this reaction, the nucleophilic compound can be used in an equivalent amount of 0.01 mole or more relative to the aminosilane compound.

In the above reaction, the nitrogen-containing compound may be used in an amount of 0.1 to 30 moles relative to 1 mole of the aminosilane monomer.

The reaction is carried out using an organic solvent which does not react with the aminosilane compound, and the organic solvent may be an aliphatic or aromatic hydrocarbon, a halogenated aliphatic or aromatic hydrocarbon, an ester, a ketone, or an ether.

Further, the above reaction can be carried out using the nucleophilic compound which is in a liquid state as a solvent, and can be carried out using a liquid mixture of one or more nucleophilic compounds as a solvent.

The reaction may be carried out in an organic solvent containing 0.01 to 0.5% by weight of water to form a polysiloxane polymer wherein the polysilazane polymer further comprises a Si-O-Si linkage in the main chain.

In another embodiment, the silica-based insulating film composition includes a polysilazane or polysiloxane polymer prepared by the above-mentioned method for producing a polymer, and has a chlorine content of 0.1 ppm or less.

The weight average molecular weight of the polysilazane-based polymer may be 1,000 to 30,000.

In the polysiloxane polymer, the oxygen atom content may be 0.05 to 3 wt%.

A polysilazane or polysiloxane polymer substantially not containing chlorine can be prepared and when used as a component of a composition for forming a silica-based insulating film, an insulating film having a significantly small number of defects can be formed.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, "polysilazane polymer" or "polysiloxane polymer" includes polysilazanes each having a Si-N bond in the main chain or a polysiloxazane containing a Si- But also polysilazane or polysiloxane residues containing some or all of the following cyclic repeating units as well as linear or branched polysilazanes and linear polysiloxazanes, as well as functional group positions and ring sizes of the following examples, silicon, nitrogen, oxygen atoms But is not limited to the position of

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, a C 1 to C 30 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 10 alkoxy group, a C 6 to C 20 aryloxy group a C1 to C30 alkyl or O aryloxycarbonyl group, a C1 to C20 of the group, or a C1 to be acyloxy Kii of C20, R _1, R _2, and R ₃ is one or more of the hydrogen.

In one embodiment, a method for preparing a polysilazane polymer having a Si-N linkage in its main chain comprises reacting an aminosilane monomer represented by the following formula (1) in the presence of a nucleophilic compound capable of coordinating Si atoms of the aminosilane , With a nitrogen-containing compound represented by the following formula (2): < EMI ID =

[Chemical Formula 1]

NR _One R ₂ R ₃

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, -Si (R ₄ ) ₃ , a C 1 to C 30 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 10 alkoxy group, C6 to aryloxy C20, C1 to being ah alkyl or aryloxycarbonyl group, a C1 to C20 in the C20 group, or acyloxy Kii of C1 to C20, R _1, R _2, and R ₃ one of the more than -Si (R _{4) 3,} wherein R ₄ is the same or different, each independently, hydrogen, C1 to C30 alkyl groups, C6 to C20 aryl group, an alkoxy group of C1 to C10, or C6 to C20 of being odd aryloxy, R ₄ Lt; / RTI > is hydrogen;

(2)

NH ₂ R ₅

In Formula 2, R ₅ is hydrogen, C1 to C30 alkyl groups, C1 to C10 alkoxy group, C6 to C20 aryl oxy group, C1 to C20 alkyl or aryloxycarbonyl group, -NH _2, C1 to C20 of O An acyloxy group of C1 to C20, a hydroxyl group, or an amine group.

In the definition of R ₁ , R ₂ , R ₃ and R _{4 in} the above formula (1), specific examples of the alkyl group include methyl, ethyl, propyl, butyl, heptyl, hexyl, pentyl, octyl, decyl, dodecyl, Butenyl, cyclohexyl, and cyclooctyl, but are not limited thereto. Specific examples of the alkoxy group include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, and cyclohexyloxy. Specific examples of the aryloxy group include a phenyloxy group, a naphthol group, a para-toluyl group, a para-methoxyphenyloxy group, and various phenyl and naphthalene derivatives such as meta-, ortho- and the like. Specific examples of the alkyl or aryloxycarbonyl include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, cyclohexylcarbonyl, phenyloxycarbonyl, naphthyloxycarbonyl, and benzyloxycarbonyl. But is not limited thereto. Specific examples of the acyl group include, but are not limited to, an acetyl group and a benzoyl group. Specific examples of the acyloxy group include, but are not limited to, an acetoxy group and a benzoate group.

In one embodiment, the aminosilane monomers may have two or more -Si (R ₄ ) ₃ groups, more specifically three -Si (R ₄ ) ₃ groups, which are the same or different from each other. In the aminosilane monomer, the -Si (R ₄ ) ₃ group may be H ₃ Si-, H ₂ MeSi-, H ₂ EtSi-, H ₂ MeOS-, H ₂ EtOSi-, H (MeO) ₂ Si, or H ₂ PhSi (Where Me is a methyl residue, Et is an ethyl residue, and Ph is a phenyl residue). Examples of such amino-silane _{monomers, (H 3 Si) NH 2} , (H 3 Si) 2 NH, (H 3 Si) NMe 2, (H 3 Si) 2 NMe, (H 3 Si) 3 N, (H _{2 MeSi) NH 2, (H} 2 MeSi) (H 3 Si) NH, (H 2 MeSi) (H 3 Si) 2 N, (H 2 MeSi) 2 NH, (H 2 MeSi) 3 N, (H 2 _{PhSi) 3 N, (H 2} PhSi) NH 2, (H 2 PhSi) 2 NH, (H 2 (MeO) Si) 3 N, (H (MeO) 2 Si) 2 NH, (H 2 (MeO) Si _{) 2 NH, (H (MeO} ) 2 Si) 3 N, (H 2 (MeO) Si) NH 2, (H (MeO) 2 Si) NH 2, (H 3 Si) 2 NMe, (H 3 Si) ₂ NPh, derivatives thereof, and combinations thereof.

When the aminosilane monomer (for example, trisilylamine) is reacted with a nitrogen-containing compound (for example, ammonia) represented by Formula 2 in the presence of a nucleophilic compound capable of coordinating the Si atom of the aminosilane, A polymer in which Si-N bonds are repeated can be prepared. The nucleophilic compound contains a nucleophilic atom having a pair of non-covalent electrons such as nitrogen, phosphorus, oxygen, sulfur, etc. and does not directly form a covalent bond with the aminosilane monomer but activates the aminosilane monomer Thereby causing a disproportionation reaction or a rearrangement reaction between Si and R ₄ or between Si and N in the aminosilane monomer. At the same time, the nitrogen-containing compound represented by Formula 2 Polysilazanes are produced in which Si-N bonds are repeated in the main chain through various reactions such as the existing Si-N bonds are broken and new Si-N bonds are formed due to the nucleophilic attack.

In the prior art, a polysilazane is synthesized from a silane monomer having Si-Cl bonds and ammonia as starting materials, such as dichlorosilane or trichlorosilane. In this case, a large amount of ammonium chloride, which is a byproduct of reaction with ammonia, The 100% reaction is difficult to complete and the resulting polysilazane or polysilazane composition necessarily contains chlorine atoms. When a composition containing a polysilazane polymer containing a large number of chlorine atoms or a polysilazane polymer is used as an insulating film raw material in a semiconductor or a liquid crystal or in the case of forming a silica layer for gap-filling, the denseness or flatness of the insulating film is low In addition, it was confirmed that a large number of defects of 5 탆 or less in width were generated in the insulating film, and the insulating properties and gap-fill characteristics required for the silica layer were deteriorated. In order to clarify the cause of such a problem, polysilazane was analyzed using a particle analyzer and ion chromatography. As a result, polysilazane solutions prepared according to the prior art method had fine particles of 10 nm or less and a chlorine concentration of 1 ppm And these fine particles were found to be ammonium chloride which was produced as a byproduct when the polysiloxazane was synthesized from chlorine-containing silane monomers and ammonia as starting materials. In the above method according to one embodiment of the present invention, chlorine is not contained in the aminosilane monomer as a polymerization raw material, so that the incorporation of chlorine into the polymer can be fundamentally blocked. In the conventional polysilazane synthesis, a multistage fine filter is applied to remove the ammonium chloride salt, which is a by-product, and a complicated and costly process such as multi-stage solvent exchange is carried out in order to lower the solubility of the ammonium chloride salt and precipitate However, in this case, ammonium chloride salt by-product is not originally generated. Therefore, the number of process steps for applying the fine filter can be reduced, and the amount of solvent required for solvent exchange used can be reduced. Is possible.

Specific examples of the nucleophilic compound include a linear tertiary amine, a heterocyclic nitrogen-containing aromatic compound, a thioether, a linear tertiary phosphine, a cyclic tertiary phosphine, N-alkylpyrrole, furan, thiophene, Derivatives, and combinations thereof. As the linear tertiary amine, trimethylamine, triethylamine, tripropylamine, or a combination thereof may be used, but it is not limited thereto. The aromatic cyclic nitrogen-containing aromatic compound may be pyridine, pyridazine, pyrimidine, pyrazine, quinoline, acridine, lutidine, or a combination thereof, but is not limited thereto.

The nucleophilic compound may be used in an equivalent amount of 0.01 mole or more relative to 1 mole of the aminosilane monomer, and in one embodiment may be used in an equivalent amount of 0.1 mole or more. Depending on the kind of the aminosilane monomer, it is effective to use at least 1 mol equivalent in order to obtain a sufficient reaction rate. When used in the above-mentioned amounts, the nucleophilic compound can efficiently synthesize a polysilazane polymer through disproportionation or rearrangement reaction by coordinating and activating Si atoms of the aminosilane monomer.

In the above reaction, the nitrogen-containing compound represented by Formula 2 may be used in an amount of 0.1 to 30 moles, specifically 1 to 5 moles, per 1 mole of the aminosilane monomer. While not wishing to be bound by any particular theory, it is believed that the nitrogen containing compound is responsible for generating Si-N bonds not derived from aminosilanes through nucleophilic attack.

The reaction may be carried out in an organic solvent which does not react with the aminosilane compound, and the organic solvent may be an aliphatic or aromatic hydrocarbon, a halogenated aliphatic or aromatic hydrocarbon, an ester, a ketone, or an ether. The organic solvent may be used alone or in combination of two or more. Specific examples of the organic solvent include organic solvents such as xylene, toluene, benzene, pentane, pentene, hexane, hexene, heptane, heptene, octane, octene, nonane, nonene, decane, decene, dichloromethane, tetrahydrofuran, diethylether, But are not limited to, hexane, cyclohexene, methylcyclohexane, ethylcyclohexane, limonene, p-menthane, and decalin.

The reaction can be carried out using the nucleophilic compound in liquid phase as a solvent, for example, a mixture of a liquid tertiary amine, a liquid phase heterogeneous nitrogen-containing aromatic compound, and at least one liquid nucleophilic compound Or as a solvent. When a liquid linear tertiary amine or a liquid heterogeneous cyclic nitrogen-containing aromatic compound is used as an organic solvent, the organic solvent may also function as the nucleophilic compound. In this case, there is no need to use an organic solvent, and it is further advantageous in that the reaction rate is maximized by activating the aminosilane by using a large amount of nucleophilic compound.

The reaction may include a first step of adding the nitrogen-containing compound to a mixture of the nucleophilic compound and the aminosilane monomer and stirring the mixture; And a second step of raising the molecular weight of the polymer by the reaction. The first step may be performed at a temperature of 100 DEG C or lower, specifically, a temperature of -50 DEG C to 50 DEG C. The second step may be performed at a temperature in the range of 0 ° C to 150 ° C. The reaction time in each step is not particularly limited and can be appropriately selected. For example, the first step may be performed for 10 hours or less, specifically 5 hours or less, more specifically 3 hours or less, more specifically 30 minutes or more and 2 hours or less, but the present invention is not limited thereto. The second step may be carried out for a period of not more than 4 days, specifically not more than 24 hours, more specifically not more than 12 hours, more specifically not less than 30 minutes and not more than 8 hours.

When the reaction is carried out in an organic solvent, a small amount of water may be added to the organic solvent to form a polysiloxazane polymer further comprising a Si-O-Si linkage with the Si-N linkage in the main chain. In this case, the organic solvent may be an organic solvent which is miscible with water, and the amount of the water may be 0.5% by weight or less, specifically 0.01 to 0.2% by weight based on the weight of the organic solvent . The polysiloxane polymer further comprising a Si-O-Si linkage by such a method may have an oxygen atom content of 0.05 wt% to 3 wt%, specifically 0.1 wt% to 3 wt%.

In the above method according to one embodiment of the present invention, since the aminosilane monomer containing no chlorine is used as the polymerization raw material, a polysilazane polymer substantially containing no chlorine can be produced. The polysilazane polymer may include a repeating unit represented by the following formula (3)

(3)

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, a C1 to C30 alkyl group, a C6 to C20 aryl group, a C1 to C10 alkoxy group, a C6 to C20 An aryloxy group, an alkyl or aryloxycarbonyl group of C1 to C30, an acyl group of C1 to C20, or an acyloxy group of C1 to C20, provided that at least one of R ₁ , R ₂ and R ₃ is hydrogen. In the above formula (2), the details of the alkyl group, aryl group, alkoxy group, alkyl- or aryloxycarbonyl group, acyl group and acyloxy group are as described in relation to the above formula (1).

When the polysilazane polymer further contains a repeating unit represented by the following formula (4), it is referred to as a polysiloxane residual polymer:

[Chemical Formula 4]

Wherein R ₄ , R ₅ , R ₆ and R ₇ are the same or different and each independently represents hydrogen, a C 1 to C 30 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 10 alkoxy group, An aryloxy group of C6 to C20, an alkyl or aryloxycarbonyl group of C1 to C30, an acyl group of C1 to C20 or an acyloxy group of C1 to C20, and at least one of R ₄ , R ₅ , R ₆ and R ₇ Is hydrogen. In the above formula (3), the details of the alkyl group, aryl group, alkoxy group, alkyl or aryloxycarbonyl group, acyl group and acyloxy group are as described in relation to the above formula (1).

The polysiloxane residual polymer further comprising the repeating unit represented by the formula (4) may have an oxygen atom content of about 0.05 to 3% by weight in the polymer.

The polysilazane based or polysiloxane residual polymer may comprise a SiH moiety, a SiH ₂ moiety and a SiH ₃ moiety in the polymer, wherein the total amount of SiH _x (X is an integer from 1 to 3) (SiH + SiH ₂ + SiH quantity ratio of the SiH ₃ to the amount of ₃₎ may range from 0.15 to 0.35. When these ratios are included, the oxidation reaction sufficiently occurs during the heat treatment, thereby suppressing the shrinkage phenomenon during the heat treatment, thereby preventing cracking of the insulating film pattern.

The polysilazane or polysiloxane residual polymer may have a weight average molecular weight of 1,000 to 30,000, specifically 1,500 to 15,000, more specifically 2,000 to 10,000, but is not limited thereto. In the case of the above range, when the surface having irregularities having a line width of 1 탆 or less is coated with a composition for forming an insulating film containing the polysilazane polymer, a fine gap can be finely charged without generating voids.

The polysilazane or polysiloxane polymer may be used as a component of a composition for forming a silica insulating film. The polysilazane or polysiloxane polymer may be contained in the silica insulating film forming composition in an amount of about 0.1 to 50 wt% based on the total weight of the composition. When it is contained in the above range, it is possible to maintain an appropriate viscosity, and when a surface having fine irregularities is coated with a composition for forming a silica layer containing the polysilazane or the polysiloxane polymer, .

The composition for forming a silica layer may further include a thermal acid generator (TAG). The thermal acid generator is an additive for improving the developability of the polysilazane polymer so that the polysilazane polymer can be developed at a relatively low temperature. The thermal acid generator is not particularly limited as long as it is a compound capable of generating an acid (H ⁺ ) by heat, but it can be activated at about 90 캜 or higher to generate sufficient acid and have low volatility. Such thermal acid generators can be selected from, for example, nitrobenzyl tosylate, nitrobenzyl benzene sulfonate, phenol sulfonate, and combinations thereof. The thermal acid generator may be included in an amount of about 0.01 to 25% by weight based on the total amount of the composition for forming a silica layer, and if it is included in the above range, the polysiloxane polymer can be developed at a relatively low temperature and the coating property can be improved .

The composition for forming a silica layer may further include a thermal base generator (TBG) protected by a protecting group capable of being decomposed by heat. The thermal base generators may be selected from the group consisting of (3-tert-butoxycarbonylamino-propyl) -carbamic acid tert-butyl ester, (6-tert-butoxycarbonylamino-hexyl) -carbamic acid tert- And mixtures thereof. However, the present invention is not limited thereto.

The composition for forming a silica layer may further comprise a surfactant. The surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene nonylphenol ether And polyoxyethylene alkyl allyl ethers such as polyoxyethylene alkyl allyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbitol Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan fatty acid ester, Manufactured by Dainippon Ink and Chemicals, Inc.), Megafac F171 and F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Prorad FC430 and FC431 (manufactured by Sumitomo 3M Ltd.) Fluorine surfactants such as Asahi Guard AG710, SHAPRON S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Kasei Corporation), organosiloxane polymer KP341 (Shinetsu Kagaku Kogyo Co., Ltd.) and other silicone surfactants. The surfactant may be included in an amount of about 0.001 to 10% by weight based on the total amount of the composition for forming a silica layer. When the surfactant is included in the range, the dispersibility of the solution is improved and the uniformity of film thickness and the packing property .

The composition for forming an insulating film may be in the form of a polysilazane polymer and a solution in which the above-mentioned components are dissolved in an organic solvent. The organic solvent is not particularly limited as long as it is a compound capable of dissolving the above-mentioned components, and examples thereof include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; And ketone acid esters such as ethyl pyruvate. In addition, there are compounds such as N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, A high boiling solvent such as ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate may be added. Of these, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate , Propylene glycol dimethyl ether acetate, 1-methoxy-2-propanol, ethyl lactate, cyclopentanone, and ethyl hydroxyacetate.

At least one of the solvents may comprise a solvent having a high boiling point. In this case, it is possible to prevent voids from being generated in the gap when filling the gap, and the solvent is slowly volatilized, so that the flatness of the film can be increased. The solvent may be included as the remainder excluding the above-mentioned components with respect to the total content of the composition for forming a silica layer.

The formation of the insulating film from the composition for forming a silica-based insulating film can be carried out according to a known method. For example, a silica-based insulating film can be formed by applying the above composition for forming a silica-based insulating film to a predetermined substrate, drying and then curing in an atmosphere containing water vapor at 200 ° C or higher. The composition for forming an insulating film has a chlorine content of less than 0.1 ppm, specifically less than 0.05 ppm, and substantially does not contain chlorine. Therefore, when the insulating film forming composition is used to form an insulating film, formation of ammonium chloride crystal grains formed by the reaction of free chlorine and ammonia can be prevented originally. In addition, a silica film excellent in flatness and compactness can be formed, and the number of defects present in the produced film can be controlled to a very low level, thereby improving the insulating property and the gap-fill property.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples and comparative examples are for illustrative purposes only and are not intended to limit the present invention.

Example  One

The interior of the reactor having a capacity of 2 L equipped with a stirring and temperature control device was replaced with dry nitrogen. 10 g of trisilylamine was added to 1,000 g of dry pyridine and mixed thoroughly. The reactor was then put into the reactor and the temperature of the reactor was kept at -15 캜. 3 g of ammonia gas was slowly bubbled into the reactor at -15 ° C for 1 hour, and then the reactor was stirred for 1 hour. Then, the reactor was slowly bubbled with dry nitrogen to gradually warm to room temperature over 2 hours, The mixture was heated and stirred for 4 hours. 1,000 g of dry xylene was added to the obtained colorless transparent liquid, and the operation of replacing the solvent with xylene in pyridine using a rotary evaporator was repeated three times in total to obtain a solution having a solid content concentration adjusted to 20%. Analysis of the obtained solution by FT-IR revealed that hydrogenated polysilazane was formed, and as a result of NMR analysis - SiH ₃ / - SiH _x (X is an integer of 1 to 3) 0.25, GPC analysis confirmed a weight average molecular weight was 4,800 coming, in the IC analysis chlorine was not detected.

Comparative Example  One

The interior of the reactor equipped with a stirrer, a temperature controller, and a capacity of 2 L was replaced with dry nitrogen, and 1,500 g of dry pyridine was introduced. 100 g of dichlorosilane was gradually injected over 1 hour while maintaining the temperature at 5 캜. Thereto, 70 g of ammonia was gradually introduced over 3 hours under stirring, and then dried nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry product was filtered through a 1-μm Teflon filter in a dry nitrogen atmosphere, 1,000 g of dry xylene was added thereto, and the solvent was replaced with xylene in pyridine using a rotary evaporator The operation was repeated three times in total, and the solid concentration was adjusted to 20%, followed by filtration through a Teflon filter having a pore size of 0.03 탆. It was confirmed that the obtained colorless transparent solution, the resulting hydrogenated polysilazane was analyzed by FT-IR is formed, NMR analysis _{- SiH 3 / - SiH x (} x is 1, 2, and 3) 0.20, GPC analysis a weight average The molecular weight was 2,000 and the chlorine content by IC analysis was 3.0 ppm.

In the case of the hydrogenated polysilazane synthesized from Example 1, the chlorine content in the polymer was substantially below the detection limit and was not detected. On the other hand, in the case of Comparative Example 1 using chlorosilane and ammonia as polymerization starting materials, the chlorine content in the polymer was 3.0 ppm .

Example  2

The hydrogenated polysilazane solution prepared in Example 1 was applied to an 8 inch N type bare silicon wafer with a spin coater and dried on a hot plate at 100 占 폚. This was cured in an oxygen atmosphere containing 500 캜 and 5 kPa of steam partial pressure for 1 hour to form a silica film. The number of defects in the obtained film was measured, and the results are shown in Table 1 below.

Comparative Example  2

A silacar coating film was formed in the same manner as in Example 2, except that the hydrogenated polysilazane solution prepared in Comparative Example 1 was used. The number of defects in the obtained coating film was measured, and the results are shown in Table 1. < tb > < TABLE >

The analysis / evaluation device is as follows.

_{- SiH 3 / SiH x (total} ): Bruker Corporation of manufacture ¹ H-NMR (400MHz of the polysilazane polymer has NMR -SiH _1, -SiH _2, -SiH ₃ peaks for the presence of, -SiH ₃ peak Calculating the ratio between the area and the area of all-SiH _x peaks)

Weight average molecular weight: GPC (HPLC Pump 1515, RI Detector 2414, manufactured by Waters Corporation), Column (KF801, 802, 803,

- Chlorine content: Chlorine analyzer manufactured by Mitsubishi Chemical Corporation (TOX-2100H)

- Functional analysis: FT-IR from Perkin-Elmer

- Defect number evaluation: Surfscan SP1 manufactured by KLA-Tencor Co.

Number of defects / 8 inch wafer Defect size (nm) 0.150-0.403 um 0.403-1.085 μm 1.085-2.917 [mu] m Bare wafer 4 0 0 Example 2 107 43 One Comparative Example 2 3803 530 40

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (14)

A process for producing a polysilazane polymer having a Si-N linkage in its main chain, which comprises reacting an aminosilane monomer represented by the following formula (1) in the presence of a nucleophilic compound capable of coordinating a Si atom of the aminosilane monomer, With a nitrogen-containing compound represented by the following formula (2): < EMI ID =
[Chemical Formula 1]
NR ₁ R ₂ R ₃
Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents hydrogen, -Si (R ₄ ) ₃ , a C 1 to C 30 alkyl group, a C 6 to C 20 aryl group, a C 1 to C 10 alkoxy group, C6 to aryloxy C20, C1 to being ah alkyl or aryloxycarbonyl group, a C1 to C20 in the C20 group, or acyloxy Kii of C1 to C20, R _1, R _2, and R ₃ one of the more than -Si (R _{4) 3,} wherein R ₄ is the same or different, each independently, hydrogen, C1 to C30 alkyl groups, C6 to C20 aryl group, an alkoxy group of C1 to C10, or C6 to C20 Of at least one of R < ₄ > is hydrogen;
(2)
NH ₂ R ₅
In Formula 2, R ₅ is hydrogen, C1 to C30 alkyl groups, C1 to C10 alkoxy group, C6 to C20 aryl oxy group, C1 to C20 alkyl or aryloxycarbonyl group, -NH _2, C1 to C20 of O An acyloxy group of C1 to C20 , a hydroxyl group, or an amine group,
Wherein the aminosilane monomer has at least two of R ₁ , R ₂ , and R ₃ in the formula (1) having -Si (R ₄ ) ₃ group,
Wherein the nucleophilic compound is selected from the group consisting of a linear tertiary amine, a heterocyclic nitrogen containing aromatic compound, a thioether, a linear tertiary phosphine, a cyclic tertiary phosphine, an N-alkylpyrrole, a furan, a thiophene, Or a combination thereof. delete The method according to claim 1,
The amino silane _{monomers, (H 3 Si) 2 NH} , (H 3 Si) 2 NMe, (H 3 Si) 3 N, (H 2 MeSi) (H 3 Si) NH, (H 2 MeSi) (H 3 _{Si) 2 N, (H 2} MeSi) 2 NH, (H 2 MeSi) 3 N, (H 2 PhSi) 3 N, (H 2 PhSi) 2 NH, (H 2 (MeO) Si) 3 N, (H _{2 (MeO) Si) 2 NH} , (H (MeO) 2 Si) 2 NH, (H (MeO) 2 Si) 3 N, (H 3 Si) 2 NMe, (H 3 Si) 2 NPh, derivatives thereof , Or a combination thereof. delete The method according to claim 1,
Wherein the linear tertiary amine is at least one selected from the group consisting of trimethylamine, triethylamine, tripropylamine, or a combination thereof, and the heterogeneous cyclic nitrogen-containing aromatic compound is selected from the group consisting of pyridine, pyridazine, pyrimidine, pyrazine, quinoline, Lutidine, or a combination thereof. The method according to claim 1,
Wherein the nitrogen-containing compound is NH ₃ , NH ₂ NH ₂ , methylamine, ethylamine, propylamine, phenylamine, hydroxyamine or a combination thereof. The method according to claim 1,
In the above reaction, the nucleophilic compound is used in an amount of 0.01 mol or more relative to 1 mol of the aminosilane monomer. The method according to claim 1,
In the above reaction, the nitrogen-containing compound is used in an amount of 0.1 to 30 moles per 1 mole of the aminosilane monomer. The method according to claim 1,
The reaction is carried out using a non-reactive organic solvent that does not react with the aminosilane monomer and the nitrogen-containing compound, or a mixture of the nucleophilic compound and the non-reactive organic solvent, or one or more nucleophilic compounds as a solvent ≪ / RTI > 10. The method of claim 9,
Wherein the non-reactive organic solvent is an aliphatic or aromatic hydrocarbon, a halogenated aliphatic or aromatic hydrocarbon, an ester, a ketone, or an ether. 10. The method of claim 9,
Wherein the non-reactive organic solvent or the nucleophilic compound comprises not more than 0.5 wt% water based on the total weight of the solvent. 11. A composition for forming a silica-based insulating film, which comprises a polymer produced by the method according to any one of claims 1, 3, and 5 to 11, wherein the chlorine content is 0.1 ppm or less, And an atomic content of 0.05 to 3% by weight. 13. The method of claim 12,
The weight average molecular weight of the polymer is 1000 to 30,000. delete