KR101443758B1 - Composition for forming silica based layer, method for manufacturing the same, silica based layer using the same, and method for manufacturing silica based layer - Google Patents

Abstract

There is provided a composition for forming a silica layer comprising a hydrogenated polysilazane, a hydrogenated polysiloxazane, and a combination selected from the group consisting of hydrogenated polysilazane having a weight average molecular weight of 50,000 or more in terms of polystyrene and hydrogenated polysiloxazane of 0.1% or less .

Description

Technical Field The present invention relates to a composition for forming a silica layer, a method for producing the same, a silica layer using the same, and a method for producing the silica layer using the same.

A composition for forming the silica layer, a method for producing the same, a silica layer using the same, and a method for producing the silica layer.

As the semiconductor technology continues to develop, researches on highly integrated and high-speed semiconductor memory cells with improved integration and higher performance in smaller-sized semiconductor chips are continuing. Particularly, a dynamic random access memory (DRAM) is widely used, which can input and output information in a semiconductor memory cell and can be implemented in a large capacity.

The DRAM comprises a plurality of unit cells including one MOS transistor and one capacitor. Among them, the capacitor includes two electrodes and a dielectric layer disposed therebetween, and the capacity of the capacitor can be determined according to the dielectric constant, the thickness of the dielectric layer, the area of the electrode forming the capacitor, and the like.

On the other hand, as the size of the semiconductor chip is getting smaller, the size of the capacitor becomes smaller, and accordingly, a capacitor capable of securing a sufficient storage capacity is required. In order to realize such a capacitor, there is a method of increasing the overall effective area of the capacitor by increasing the vertical area instead of reducing the horizontal area of the capacitor. When a capacitor is formed by such a method, a silica layer formed by filling a mold and a gap formed in the mold with a composition for forming a silica layer may be used to effectively form electrodes having a relatively high height compared to a narrow horizontal area .

One embodiment of the present invention is to provide a composition for forming a silica layer comprising a hydrogenated polysiloxazane in which fine particles are reduced.

Another embodiment of the present invention is to provide a method for producing a composition for forming a silica layer comprising a hydrogenated polysiloxazane in which fine particles are reduced.

Another embodiment of the present invention is to provide a silica layer with a reduced number of defects.

Another embodiment of the present invention is to provide a method of producing a silica layer with a reduced number of defects.

An embodiment of the present invention is a fuel cell comprising a hydrogenated polysilazane, a hydrogenated polysiloxazane, and a combination selected from the group consisting of hydrogenated polysilazane having a weight average molecular weight of 50,000 or more in terms of polystyrene and hydrogenated polysiloxazane in a concentration of 0.1% By mass or less.

The concentration of the hydrogenated polysilazane having a weight average molecular weight of 50,000 or more in terms of polystyrene and hydrogenated polysiloxazane may be 0.05% or less.
The term "concentration of the sum of the contents of the hydrogenated polysilazane and the hydrogenated polysiloxazane having a weight average molecular weight of 50,000 or more in terms of polystyrene" refers to the concentration of the hydrogenated polysilazane, hydrogenated polysiloxazane, and one of GPC (Gel Permeation Chromatography ) Means the ratio of peaks observed in the region of the polystyrene reduced weight average molecular weight of 50,000 or more.

The composition for forming a silica layer may be in a solution state and the number of fine particles in the solution may be 100 / cc or less.

The hydrogenated polysilazane or the hydrogenated polysiloxazane may include a moiety represented by the following general formula (1).

≪ Formula 1 >

　　　　　　　　　　

In Formula 1,

R ₁ to R ₃ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C 1 to C 30 arylalkyl group, a substituted or unsubstituted C 1 to C 30 heteroalkyl group, a substituted or unsubstituted C 2 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof.

The hydrogenated polysiloxazane may further include a moiety represented by the following formula (2).

(2)

In Formula 2,

R ₄ to R ₇ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C 1 to C 30 arylalkyl group, a substituted or unsubstituted C 1 to C 30 heteroalkyl group, a substituted or unsubstituted C 2 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof.

The hydrogenated polysiloxazane has an oxygen content of 0.2 to 3% by weight and a moiety represented by the following general formula (3) in an amount of 15 to 35% based on the total amount of Si-H bonds in the structure, Lt; / RTI >

(3)

The hydrogenated polysilazane or the hydrogenated polysiloxazane may have a weight average molecular weight of 1,000 to 10,000.

The sum of the hydrogenated polysilazane and the hydrogenated polysiloxazane may be 0.1 to 50 wt%.

According to another aspect of the present invention, there is provided a method for preparing a hydrogenated polysilazane or a hydrogenated polysiloxazane, comprising the steps of: preparing a solution formed by mixing a halosilane compound with a solvent followed by coammonolysis to synthesize hydrogenated polysilazane or hydrogenated polysiloxazane; As the additional solvent to the prepared solution, a solvent such as a C4 to C10 alkane, a C4 to C10 cycloalkane, a C4 to C10 alkene, a C4 to C10 cycloalkene, a decalin, a tetralin, a p-cymene, p-menthane, alpha-pinene, or a combination of at least one thereof to precipitate an insoluble precipitate; And removing the precipitated insoluble precipitate, wherein the hydrogenated polysilazane or the hydrogenated polysiloxazane is a catalyst for forming a silica layer.

The weight ratio of the solvent to the additional solvent in the solution prior to the addition of the additional solvent may be from 1: 1 to 1:30.

And removing the precipitated insoluble precipitate and removing the additional solvent.

The step of removing the precipitated insoluble precipitate may be to remove the insoluble precipitate precipitated with a filter having a pore size of 0.01 to 0.2 μm by filtration.

Another aspect of the present invention provides a silica layer produced using the composition for forming a silica layer and having a defect size of less than 5 um and a defect size of less than 1,000 / 8 inch wafer.

Yet another embodiment of the present invention is a method of forming a silica-based film, comprising: applying the composition for forming silica to a substrate; Drying the substrate coated with the composition for forming silica; And a step of curing in an atmosphere containing water vapor at 200 DEG C or higher.

Other details of the embodiments of the present invention are included in the following detailed description.

When a silica layer is formed using the composition for forming a silica layer containing a hydrogenated polysiloxazane according to the present invention, it is possible to significantly reduce defects and improve the insulation and gap-fill characteristics required of the silica layer .

FIG. 1 is a graph showing the results of high sensitivity GPC (Gel Permeation Chromatography) measurements on the polysilazane and siloxane solutions prepared according to Example 3 and Comparative Example 4 below.

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.

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an alkyl group, an alkenyl group of C2 to C16, a C2 to C16 alkenyl group, An aryl group, C7 to C13 arylalkyl, C1 to C4 oxyalkyl, C1 to C20 heteroalkyl, C3 to C20 heteroarylalkyl, cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 Substituted by a substituent selected from a cycloalkynyl group, a heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.

In one embodiment of the present invention, there is provided a composition for forming a silica layer comprising a hydrogenated polysilazane, a hydrogenated polysiloxazane, and one selected from a combination thereof, wherein the composition for forming a silica layer has a high molecular weight The sum of the hydrogenated polysilazane having a weight average molecular weight of 50,000 or more and the hydrogenated polysiloxane content is 0.1% or less.

Hydrogenated polysilazane or hydrogenated polysiloxazane can be used as an insulating film, a separation membrane, a hard coating or the like in that it has characteristics of converting into a dense silica glass material by heating and oxidation reaction. When the composition for forming a silica layer is used Since voids and defects in the film are controlled and reduced, they are particularly useful for manufacturing devices requiring high electrical characteristics such as semiconductors and liquid crystals.

Particularly, the fine particles having the fluidity contained in the composition for forming a silica layer may cause a defect or a defect in the silica layer produced from the composition for forming a silica layer, The fine particles may have been removed, which can be analyzed using a high sensitivity GPC (Gel Permeation Chromatography).

The removal of high molecular weight particles from the composition for forming a silica layer can be carried out by the following method. The composition for forming a silica layer from which high molecular weight fine particles have been removed in this way has a number of fine particles in the solution of 0 to 100 / cc .

The high molecular weight particles mean one selected from the group consisting of hydrogenated polysilazanes having a weight average molecular weight of 50,000 or more in terms of polystyrene, hydrogenated polysiloxazanes, and combinations thereof, and more specifically, hydrogenated polysilazanes having a weight average molecular weight of 50,000 to 5,000,000 in terms of polystyrene, ≪ / RTI > and combinations thereof.

The high molecular weight fine particles containing one selected from the above-mentioned high molecular weight hydrogenated polysilazane, hydrogenated polysiloxazane, and combinations thereof may be used in an amount of from 0% to 10%, based on the sum of the contents of hydrogenated polysilazane and hydrogenated polysiloxazane in terms of defect. The concentration is preferably in the range of 0% to 0.07%, and most preferably the concentration is in the range of 0% to 0.05%. The concentration of the hydrogenated polysilazane or hydrogenated polysiloxane fine particles having a high molecular weight can be adjusted to fall within the above range since the above range can be effectively used for manufacturing devices requiring high electrical characteristics such as the above-mentioned semiconductor and liquid crystal.

The hydrogenated polysilazane or the hydrogenated polysiloxazane may include a moiety represented by the following general formula (1).

≪ Formula 1 >

　　　　　　　　　　

In Formula 1,

R ₁ to R ₃ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C 1 to C 30 arylalkyl group, a substituted or unsubstituted C 1 to C 30 heteroalkyl group, a substituted or unsubstituted C 2 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof.

The hydrogenated polysiloxazane further comprises a moiety represented by the following formula (2).

(2)

In Formula 2,

R ₄ to R ₇ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C 1 to C 30 arylalkyl group, a substituted or unsubstituted C 1 to C 30 heteroalkyl group, a substituted or unsubstituted C 2 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof.

Thus, the hydrogenated polysiloxazane contains a silicon-oxygen-silicon (Si-O-Si) bond moiety in addition to the silicon-nitrogen (Si-N) bond moiety in the structure. This silicon-oxygen-silicon (Si-O-Si) bond moiety can reduce shrinkage by relaxing stress during curing by heat treatment.

The oxygen content in the hydrogenated polysiloxazane may be about 0.2 to 3% by weight from the viewpoint of suppressing the structural shrinkage in the heating (hot) process. When it is contained in the above range, the stress relaxation due to the silicon-oxygen-silicon (Si-O-Si) bond in the structure is sufficient to prevent shrinkage during heat treatment and to prevent cracks from being generated in the formed filling pattern Do.

From this viewpoint, it is more preferable that the content is about 0.4 to 2% by weight within the above range.

The hydrogenated polysiloxazane may have a moiety represented by the following formula (3) at the terminal.

(3)

The portion represented by Formula 3 is a structure in which the terminal portion is capped with hydrogen and may be included in an amount of about 15 to 35% by weight based on the total amount of Si-H bonds in the hydrogenated polysiloxazane structure. When it is included in the above range, the SiH ₃ portion is prevented from being scattered due to SiH ₄ during the heat treatment while the oxidation reaction sufficiently occurs during the heat treatment, thereby preventing shrinkage and preventing cracks from being formed in the filling pattern formed therefrom.

In one embodiment of the present invention, the weight average molecular weight (Mw) of the hydrogenated polysilazane and / or the hydrogenated polysiloxazane is not particularly limited. However, considering the solubility in an organic solvent and the application characteristics to a substrate, Average molecular weight of about 1,000 to 10,000.

In another embodiment of the present invention, the hydrogenated polysilazane and / or the hydrogenated polysiloxazane may be included in the total amount of the composition for forming a silica layer in an amount of about 0.1 to 50% by weight. When it is included in the above range, it can maintain an appropriate viscosity and can be formed as a composition for forming a silica layer containing the hydrogenated polysilazane and / or the hydrogenated polysiloxazane, and can be formed evenly and without voids in the gap.

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 hydrogenated polysilazane and / or the hydrogenated polysiloxazane so that the hydrogenated polysilazane and / or the hydrogenated polysiloxazane 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 range, the hydrogenated polysiloxazane can be developed at a relatively low temperature, have.

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 a silica layer may be in the form of a solution in which the hydrogenated polysilazane and / or the hydrogenated polysiloxazane and the components are dissolved in a solvent.

The solvent is not particularly limited as long as it is a compound capable of dissolving the above-mentioned components, and for example, it may be an aromatic hydrocarbon such as xylene or an ether such as dibutyl ether.

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.

A method for preparing a composition for forming a silica layer comprising hydrogenated polysilazane and / or hydrogenated polysiloxazane from which the high molecular weight fine particles have been removed comprises: mixing a halosilane compound with a solvent followed by coammonolysis to form a hydrogenated poly Preparing a solution formed by synthesizing silazane or hydrogenated polysiloxazane; As the additional solvent to the prepared solution, a solvent such as a C4 to C10 alkane, a C4 to C10 cycloalkane, a C4 to C10 alkene, a C4 to C10 cycloalkene, a decalin, a tetralin, a p-cymene, p-menthane, alpha-pinene, or a combination of at least one thereof to precipitate an insoluble precipitate; And removing the precipitated insoluble precipitate.

Since the solution of the composition for forming a silica layer prepared according to the above method removes the hydrogenated polysilazane and / or the hydrogenated polysiloxazane having a high molecular weight, the number of particles in the solution in the solution for forming a silica layer is 0 to 100 / cc .

The additional solvent added later in the composition solution for forming a silica layer as described above is used to precipitate a hydrogenated polysilazane and / or a hydrogenated polysiloxazane having a high molecular weight and can be adversely affected in forming a silica layer thereafter It can be removed by evaporation.

The additional solvent may be selected from more specific examples such as n-octane, cyclohexane, n-hexane, p-menthane, a-pinene, n-pentane, n-heptane or combinations thereof.

The additional solvent may selectively precipitate a hydrogenated polysilazane and / or hydrogenated polysiloxazane having a high molecular weight, and may be filtered with a filter or the like to remove high molecular weight fine particles. When the high-molecular-weight fine particles are thus removed, a silica layer with reduced defects can be produced.

The additional solvent may control the range of the molecular weight of the hydrogenated polysilazane and / or the hydrogenated polysiloxazane of high molecular weight to be precipitated by changing the addition amount. Preferably, the weight ratio of the solvent contained in the solution before addition to the additional solvent may be from 1: 1 to 1:30. For example, they can be mixed at a mixing ratio of 1: 5, 1: 8, 1:15, and the like. In the above case, the higher molecular weight hydrogenated polysilazane to be precipitated and / As the precipitation amount of Sazan increases, the weight average molecular weight of the hydrogenated polysilazane and / or the hydrogenated polysiloxazane can be reduced.

The pore size of the filter may be adjusted to remove the precipitated insoluble particulate matter to a particularly large size or more. For example, fine particles larger than the pore size of the filter can be filtered out by using a filter having a pore size of 0.01 to 0.2 um.

The defect-reduced silica layer can be produced using the composition for forming a silica layer of any one of the above-described embodiments of the present invention, and the silica layer thus produced has defects of 5 um or less in number of 1,000 / 8 inches Wafers or less.

The silica layer is not particularly limited, and can be produced by a known production method.

For example, a silica layer can be formed by applying the above-described composition for silica formation onto a device substrate such as a semiconductor or a liquid crystal, followed by drying, and then curing in an atmosphere containing water vapor at 200 DEG C or higher.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

[Example]

The number of particles in the liquid, the oxygen content, the weight average molecular weight and the high molecular weight component of the polysilazane solution or polysiloxane solution prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were measured and are shown in Table 1 below. The equipment used for the measurement is as follows.

- liquid fine particles: manufactured by Rion; Underfloor Particle Sensor / Counter KS-42BF

Oxygen content: manufactured by Thermo Fisher Scientific Inc; FlashEA 1112

- Weight average molecular weight and high molecular weight component:

GPC manufactured by Waters; HPLC Pump 1515, RI Detector 2414

Column manufactured by Shodex; KF801, 802, 803

Example  One

A reactor having a capacity of 2 L and equipped with a temperature control device was replaced with dry nitrogen. Then 1,500 g of dry pyridine was charged into the reactor and the reactor was kept at 5 캜. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, 70 g of ammonia was gradually added thereto over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry-like product was filtered using a 1-μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with xylene in pyridine using a rotary evaporator was repeated three times in total to adjust the solid concentration to 20% by weight, and a pore size of 0.1 μm And filtered through a Teflon filter to obtain a hydrogenated polysilazane solution.

The interior of the reactor with a capacity of 1 L equipped with a stirrer was replaced with dry nitrogen. 100 g of the hydrogenated polysilazane solution obtained above was introduced into the reactor, and 800 g of dry n-octane was slowly injected over 30 minutes while stirring at room temperature. The agitation was stopped and maintained for 3 hours. The filtrate was then filtered through a Teflon filter having a pore size of 0.1 um. Subsequently, the operation of replacing xylene with xylene while removing n-octane by using a rotary evaporator was repeated three times in total, and the solid content concentration was adjusted to 20 wt% and filtered with a pore size 0.02um Teflon filter. The hydrogenated polysilazane solution thus obtained had a polystyrene reduced weight average molecular weight of 1,700 and a peak of 0.02% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution of this solution was 5.2 pieces / cc.

Example  2

The interior of the reactor with a capacity of 1 L equipped with a stirrer was replaced with dry nitrogen. 100 g of the hydrogenated polysilazane solution obtained in Example 1 was injected into the reactor, and 600 g of dry cyclohexane was slowly injected over 30 minutes while stirring at room temperature. The agitation was stopped and maintained for 3 hours. The filtrate was then filtered through a Teflon filter having a pore size of 0.1 um. Subsequently, the operation of replacing cyclohexane with xylene using a rotary evaporator was repeated three times in total, and the solid content concentration was adjusted to 20 wt%, followed by filtration with a pore size 0.02 um Teflon filter. The hydrogenated polysilazane solution thus obtained had a polystyrene reduced weight average molecular weight of 1,700 and a peak of 0.02% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution of this solution was 3.8 / cc.

Example  3

A reactor having a capacity of 2 L and equipped with a temperature control device was replaced with dry nitrogen. Then 1,500 g of dry pyridine was charged into the reactor and the reactor was kept at 5 캜. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, 70 g of ammonia was gradually added thereto over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry-like product was filtered using a 1-μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with xylene in pyridine using a rotary evaporator was repeated three times in total to adjust the solid concentration to 20% by weight, and a pore size of 0.1 μm Filtered through a Teflon filter.

The obtained hydrogenated polysilazane solution was maintained at 40 占 폚 for 240 hours while stirring. The precipitate of ammonium chloride forming a cloudy white turbid in the solution was then filtered with a pore size 0.02 um Teflon filter.

The interior of the reactor with a capacity of 1 L equipped with a stirrer was replaced with dry nitrogen. 100 g of the hydrogenated polysilazane solution obtained above was charged into the reactor, and 700 g of dry n-hexane was slowly injected over 30 minutes while stirring at room temperature. The agitation was stopped and maintained for 3 hours. Thereafter, the mixture was filtered through a Teflon filter having a pore size of 0.1 um. Subsequently, the operation of replacing n-hexane with dibutyl ether by using a rotary evaporator was repeated three times in total, and the solid concentration was adjusted to 20% by weight and filtered through a 0.04-μm pore size filter made of Teflon. The hydrogenated polysilazane solution thus obtained had a polystyrene reduced weight average molecular weight of 2,100 and a peak of 0.02% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution of this solution was 3.2 pieces / cc.

Example  4

A reactor having a capacity of 2 L and equipped with a temperature control device was replaced with dry nitrogen. Then, 0.6 g of pure water was poured into 1,500 g of dry pyridine, and the mixture was thoroughly mixed. Then, the mixture was placed in a reactor and kept at 20 ° C. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, 70 g of ammonia was gradually added thereto over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry-like product was filtered using a 1-μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with dibutyl ether in pyridine using a rotary evaporator was repeated three times in total to adjust the solid concentration to 20% by weight, and pore size 0.1um Of a Teflon filter. The obtained hydrogenated polysiloxane solution had an oxygen content of 0.2% and a weight average molecular weight of 4,300, and a peak was observed in a high molecular weight region of 50,000 or more

The obtained hydrogenated polysiloxane solution was placed in a stainless steel canister having a capacity of 5 L, the inside thereof was sufficiently replaced with dry nitrogen, and the pressure was increased to 1 kg / cm ² G. The mixture was aged in a freezer at -10 DEG C for 10 hours, and then filtered through a Teflon filter having a pore size of 0.02 mu. The hydrogenated polysiloxazane solution had a weight average molecular weight of 4,400 and a peak in a high molecular weight region of 50,000 or more.

The interior of the reactor with a capacity of 1 L equipped with a stirrer was replaced with dry nitrogen. 100 g of the obtained hydrogenated polysiloxane solution was introduced into the reactor, and 1,000 g of dry p-menthane was gradually injected over 30 minutes while stirring at room temperature. The agitation was stopped and maintained for 3 hours. Thereafter, the mixture was filtered through a Teflon filter having a pore size of 0.1 um. Subsequently, the procedure of replacing p-menthane with dibutyl ether by using a rotary evaporator was repeated three times in total, and the solid concentration was adjusted to 20% by weight and filtered with a pore size 0.02 μm Teflon filter. The weight average molecular weight of the obtained hydrogenated polysiloxane solution in terms of polystyrene was 4,200, and a peak was observed at 0.04% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution of this solution was 2.1 pcs / cc.

Example  5

A reactor having a capacity of 2 L and equipped with a temperature control device was replaced with dry nitrogen. Then, 0.6 g of pure water was poured into 1,500 g of dry pyridine, and the mixture was thoroughly mixed. Then, the mixture was placed in a reactor and kept at 20 ° C. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, 70 g of ammonia was gradually added thereto over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry-like product was filtered using a 1-μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with dibutyl ether in pyridine using a rotary evaporator was repeated three times in total to adjust the solid concentration to 20%, and a pore size of 0.1 mu m Filtered through a Teflon filter. The obtained hydrogenated polysiloxane solution had an oxygen content of 0.2% and a weight average molecular weight of 4,300, and a peak was observed in a high molecular weight region of 50,000 or more.

The obtained hydrogenated polysiloxane solution was placed in a stainless steel canister having a capacity of 5 L, the inside thereof was sufficiently replaced with dry nitrogen, and the pressure was increased to 1 kg / cm ² G. The mixture was aged in a freezer at -10 DEG C for 10 hours, and then filtered through a Teflon filter having a pore size of 0.02 mu. The hydrogenated polysiloxazane solution had a weight average molecular weight of 4,400 and a peak in a high molecular weight region of 50,000 or more.

The interior of the reactor with a capacity of 1 L equipped with a stirrer was replaced with dry nitrogen. 100 g of the obtained hydrogenated polysiloxane solution was introduced into the reactor, and 900 g of dry? -Pinene was slowly injected over 30 minutes while stirring at room temperature. The agitation was stopped and maintained for 3 hours. Thereafter, the mixture was filtered through a Teflon filter having a pore size of 0.1 um. Subsequently, the procedure of replacing? -Pinene with dibutyl ether by using a rotary evaporator was repeated three times in total, and the solid content concentration was adjusted to 20%, followed by filtering with a pore size 0.02um Teflon filter. The weight average molecular weight of the obtained hydrogenated polysiloxane solution in terms of polystyrene was 4,500, and a peak was observed at 0.04% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution of this solution was 4.1 pieces / cc.

Comparative Example  One

A reactor having a capacity of 2 L and equipped with a temperature control device was replaced with dry nitrogen. Then 1,500 g of dry pyridine was charged into the reactor and the reactor was kept at 5 캜. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, 70 g of ammonia was gradually added thereto over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry-like product was filtered using a 1-μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with xylene in pyridine using a rotary evaporator was repeated three times in total to adjust the solid concentration to 20% by weight, and a pore size of 0.1 μm Filtered through a Teflon filter. The hydrogenated polysilazane solution thus obtained had a polystyrene reduced weight average molecular weight of 1,600 and a peak of 0.21% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution was 1,220 particles / cc.

Comparative Example  2

The hydrogenated polysilazane solution obtained in Comparative Example 1 was maintained at 40 DEG C for 240 hours while stirring under the conditions described in Example 1, and then filtered through a Teflon filter having a pore size of 0.1 mu m. The hydrogenated polysilazane solution thus obtained had a weight average molecular weight in terms of polystyrene of 1,800 and a peak of 0.28% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution was 1,460 particles / cc.

Comparative Example  3

The hydrogenated polysilazane solution obtained in Comparative Example 1 was filtered with a pore size 0.02 um Teflon filter. The hydrogenated polysilazane solution thus obtained had a weight average molecular weight in terms of polystyrene of 1,800 and a peak of 0.13% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution of this solution was 960 / cc.

Comparative Example  4

A reactor having a capacity of 2 L and equipped with a temperature control device was replaced with dry nitrogen. Then, 2.0 g of pure water was poured into 1,500 g of dry pyridine, and the mixture was thoroughly mixed. Then, the mixture was placed in a reactor and kept at 5 캜. Subsequently, 100 g of dichlorosilane was slowly added over 1 hour. Then, 70 g of ammonia was gradually added thereto over 3 hours while stirring. Next, dry nitrogen was injected for 30 minutes to remove ammonia remaining in the reactor. The resulting white slurry-like product was filtered using a 1-μm Teflon filter in a dry nitrogen atmosphere to obtain 1,000 g of a filtrate. 1,000 g of dry xylene was added thereto, and the operation of replacing the solvent with dibutyl ether in pyridine using a rotary evaporator was repeated three times in total to adjust the solid concentration to 20% by weight, and pore size 0.1um Of a Teflon filter. The obtained hydrogenated polysiloxane solution had an oxygen content of 0.5% and a weight average molecular weight of 2,200, and a peak of 0.35% was observed in a high molecular weight region of 50,000 or more. The oxygen content was 3.5 ppm. The number of fine particles of 0.2um or more in the solution of this solution was 690 / cc.

Comparative Example  5

The hydrogenated polysilazane solution obtained in Comparative Example 1 was maintained at 40 占 폚 for 240 hours while stirring. The precipitate of ammonium chloride forming a cloudy white turbid in the solution was then filtered with a pore size 0.02 um Teflon filter. The hydrogenated polysiloxazane solution had a weight average molecular weight of 2,200 and a peak of 0.25% in a high molecular weight region of 50,000 or more. The number of fine particles of 0.2um or more in the solution was 740 / cc.

Weight average molecular weight Content of high molecular weight components above 50,000 Number of liquid particles
(Dogs / cc) Comparative Example 1 1,600 0.21% 1,220 Comparative Example 2 1,800 0.28% 1,460 Comparative Example 3 1,800 0.13% 960 Example 1 1,700 0.02% 5.2 Example 2 1,700 0.02% 3.8 Comparative Example 4 2,200 0.35% 690 Comparative Example 5 2,200 0.25% 740 Example 3 2,100 0.02% 3.2 Example 4 4,200 0.04% 2.1 Example 5 4,500 0.04% 4.1

FIG. 1 is a graph showing a result of a high sensitivity GPC (Gel Permeation Chromatography) measurement of the polysilazane and polysiloxane solution. The solid line is the result of the polysiloxane solution obtained in Comparative Example 4, and the dotted line is the polysiloxane solution obtained in Example 3 This is the result for the residual solution. In Example 3, it can be confirmed that the weight average molecular weight in terms of polystyrene decreased to 50,000 or more.

From the results of Table 1, it was confirmed that the high molecular weight components of 50,000 or more were removed in Examples 1 to 5. Particularly, in Comparative Example 2, the high molecular weight component was not removed, whereas in Example 1 in which n-octane was used to precipitate the insoluble matter, it was confirmed that the high molecular weight component was removed. Further, in Example 2, insoluble matter was precipitated by using cyclohexane to the hydrogenated polysilazane prepared in the same manner as in Comparative Example 1, whereby the high molecular weight component could be lowered. In Examples 3 to 5, it was confirmed that high molecular weight components were effectively removed by precipitating an insoluble substance using n-hexane, p-menthane, and? -Pinene in the polysiloxane solution.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (14)

Hydrogenated polysiloxane, hydrogenated polysiloxane, and hydrogenated polysiloxazane, and combinations thereof,
Wherein the sum of the contents of hydrogenated polysilazane and hydrogenated polysiloxazane having a weight average molecular weight of 50,000 or more in terms of polystyrene is 0.1% or less.
The term "concentration of the sum of the contents of the hydrogenated polysilazane and the hydrogenated polysiloxazane having a weight average molecular weight of 50,000 or more in terms of polystyrene" refers to the concentration of the hydrogenated polysilazane, hydrogenated polysiloxazane, and one of GPC (Gel Permeation Chromatography ) Means the ratio of peaks observed in the region of the polystyrene reduced weight average molecular weight of 50,000 or more. The method according to claim 1,
Wherein the sum of the contents of hydrogenated polysilazane and hydrogenated polysiloxazane having a weight average molecular weight of 50,000 or more in terms of polystyrene is 0.05% or less.
The term "concentration of the sum of the contents of the hydrogenated polysilazane and the hydrogenated polysiloxazane having a weight average molecular weight of 50,000 or more in terms of polystyrene" refers to the concentration of the hydrogenated polysilazane, hydrogenated polysiloxazane, and one of GPC (Gel Permeation Chromatography ) Means the ratio of peaks observed in the region of the polystyrene reduced weight average molecular weight of 50,000 or more. The method according to claim 1,
Wherein the composition for forming a silica layer is in a solution state and the number of fine particles in the solution is 0 to 100 / cc. The method according to claim 1,
Wherein the hydrogenated polysilazane or the hydrogenated polysiloxazane comprises a moiety represented by the following formula (1):
≪ Formula 1 >

In Formula 1,
R ₁ to R ₃ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C 1 to C 30 arylalkyl group, a substituted or unsubstituted C 1 to C 30 heteroalkyl group, a substituted or unsubstituted C 2 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof. 5. The method of claim 4,
Wherein the hydrogenated polysiloxazane further comprises a moiety represented by the following formula (2): < EMI ID =
(2)

In Formula 2,
R ₄ to R ₇ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C 1 to C 30 arylalkyl group, a substituted or unsubstituted C 1 to C 30 heteroalkyl group, a substituted or unsubstituted C 2 to C 30 heterocycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted An alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof. 6. The method of claim 5,
The hydrogenated polysiloxazane has an oxygen content of 0.2 to 3% by weight and a moiety represented by the following general formula (3) in an amount of 15 to 35% based on the total amount of Si-H bonds in the structure, Composition for forming a silica layer:
(3)

The method according to claim 1,
Wherein the hydrogenated polysilazane or the hydrogenated polysiloxazane has a weight average molecular weight of 1,000 to 10,000. The method according to claim 1,
Wherein the sum of the hydrogenated polysilazane and the hydrogenated polysiloxazane is 0.1 to 50 wt%. Preparing a solution formed by mixing a halosilane compound with a solvent, followed by coammonolysis to synthesize hydrogenated polysilazane or hydrogenated polysiloxazane;
As the additional solvent to the prepared solution, a solvent such as a C4 to C10 alkane, a C4 to C10 cycloalkane, a C4 to C10 alkene, a C4 to C10 cycloalkene, a decalin, a tetralin, a p-cymene, p-menthane, alpha-pinene, or a combination of at least one thereof to precipitate an insoluble precipitate; And
Removing the precipitated insoluble precipitate;
A hydrogenated polysilazane or a hydrogenated polysiloxazane. 10. The method of claim 9,
Wherein the weight ratio of the solvent contained in the solution prior to the addition of the additional solvent to the additional solvent is in the range of 1: 1 to 1:30. 10. The method of claim 9,
Removing the precipitated insoluble precipitate and removing the additional solvent. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt; 10. The method of claim 9,
Wherein the step of removing the precipitated insoluble precipitate comprises filtering and removing insoluble precipitates precipitated with a filter having a pore size of 0.01 to 0.2 mu m. A silica layer produced using the composition for forming a silica layer according to any one of claims 1 to 8, wherein the defect of 5 m or less is 1,000 / 8 inch wafer or less. Applying the composition for forming a silica according to any one of claims 1 to 8 to a substrate;
Drying the substrate coated with the composition for forming silica; And
Curing in an atmosphere containing water vapor at 200 DEG C or higher
&Lt; / RTI &gt;

Images