TWI564355B - Composition for forming silica layer, method for manufacturing the same, silica layer using the same, and method for manufacturing silica layer - Google Patents

Description

Composition for forming a ruthenium oxide layer, method for producing the composition, ruthenium oxide layer using the composition, and method for producing a ruthenium oxide layer Field of invention

The present invention relates to a composition for forming a silicon oxide layer, a method of making the composition, a silicon oxide layer using the composition, and a method of producing a silicon oxide layer.

Background of the invention

As semiconductor technology continues to evolve, there is ongoing research into the formation of highly integrated and faster semiconductor memory components with improved performance and integration of smaller semiconductor wafers. Among these semiconductor memory elements, for example, a DRAM (Dynamic Random Access Memory) can be used. DRAM is free to input and output information and can achieve large capacity.

The DRAM may include, for example, a plurality of unit cells including one MOS transistor (MOS transistor) and one capacitor. The capacitor can include two electrodes and a dielectric layer disposed therebetween. The capacitor may have various capacities depending on, for example, a dielectric constant, a thickness of the dielectric layer, an area of the electrode, and the like.

As semiconductor wafers are reduced in size, the size of the capacitors within them will also decrease. However, smaller capacitors require sufficient storage capacity. A larger capacity of the capacitor can be achieved by, for example, increasing the vertical area rather than reducing the horizontal area to increase the overall active area. When the capacitor is formed in this manner, the composition for forming the tantalum layer can be used to fill the mold and the gap thereon, and to effectively form a relatively high electrode compared to a smaller horizontal area.

Summary of invention

One embodiment of the present invention provides a composition for forming a ruthenium oxide layer comprising a hydrogenated polysiloxazane having reduced particulates.

Another embodiment of the present invention provides a method of making a composition for forming a ruthenium oxide layer, the composition comprising a hydrogenated polyxaazepine having reduced particulates.

Yet another embodiment of the present invention provides a silicon oxide layer having a small number of defects.

Yet another embodiment of the present invention provides a method of fabricating a silicon oxide layer having a small number of defects.

According to an embodiment of the present invention, there is provided a composition for forming a ruthenium oxide layer comprising one selected from the group consisting of hydrogenated polysilazane, hydrogenated polyoxazane, and the like. , wherein, based on the total amount of the hydrogenated polyazide and the hydrogenated polyoxazane, the hydrogenated polyazane and the hydrogenated polyoxynium having a weight average molecular weight greater than or equal to about 50,000 when converted to polystyrene are converted The concentration of the sum of the decazane ranges from less than or equal to about 0.1% by weight.

Based on the total amount of hydrogenated polyazane and hydrogenated polyoxazane, the sum of the hydrogenated polyazoxide and the hydrogenated polyoxazane having a weight average molecular weight (converted to polystyrene) of greater than or equal to about 50,000 The concentration may range from less than or equal to about 0.05% by weight.

The amount of in-liquid particulate of the composition used to form the siloxane layer is less than or equal to about 100/cc.

The hydrogenated polyazane or hydrogenated polyoxazane may include a moiety represented by the following Chemical Formula 1.

In Chemical 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, Substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxyl group, or a combination thereof.

The hydrogenated polyoxazane may further include a moiety represented by the following Chemical Formula 2.

In Chemical 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, Substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxyl group, or a combination thereof.

The hydrogenated polyoxazane may include a moiety represented by the following Chemical Formula 3 at its end, and has an oxygen content of from about 0.2 wt% to about 3 wt%, and may be about 15 based on the total amount of Si-H bonds. The amount of wt% to about 35 wt% includes the moiety represented by the following Chemical Formula 3.

<Chemical Formula 3>

*-SiH ₃ .

The hydrogenated polyazane or hydrogenated polyoxazane may have a weight average molecular weight of from about 1,000 to about 10,000.

The sum of the hydrogenated polyazane and the hydrogenated polyoxazane may range from about 0.1 wt% to about 50 wt%.

According to another embodiment of the present invention, there is provided a process for the manufacture of a composition for forming a ruthenium oxide layer comprising a hydrogenated polyazane or a hydrogenated polyxaazepine, the process comprising reacting a halogenated decane compound with a solvent Mixing and coammonolyze to synthesize hydrogenated polyazane or hydrogenated polyoxazane, thereby forming a product solution comprising hydrogenated polyazane or hydrogenated polyoxazane (resultant) Solution); adding C4 to C10 alkane, C4 to C10 cycloalkane, C4 to C10 olefin, C4 to C10 cyclic olefin, decalin, tetralin, p-isopropyl toluene to the product solution (p-cymene), an additional solvent for the combination of at least one of p-menthane, alpha-pinene or the like to precipitate insoluble precipitates; and to remove precipitated Insoluble precipitate.

The weight ratio of the solvent contained in the solution to the additional solvent before the addition of the additional solvent may range from about 1:1 to about 1:30.

The method can further include removing the additional solvent after removing the precipitated insoluble precipitate.

The removal of the precipitated insoluble precipitate may include filtering the precipitated insoluble precipitate by a filter having a pore diameter of from about 0.01 to about 0.2 μm to remove it.

According to another embodiment of the present invention, there is provided a silicon oxide layer fabricated by using a composition for forming a germanium oxide layer, and having 1000 or less dimensions per 8 inch wafer less than or equal to about 5μm defect.

According to still another embodiment of the present invention, there is provided a method of manufacturing a defect-reduced tantalum layer, the method comprising coating a composition for forming a tantalum layer on a substrate; drying coating for forming The substrate of the composition of the ruthenium layer; is cured in an atmosphere comprising water vapor at a temperature of about 200 ° C or higher.

Other embodiments of the invention are described in detail below.

When the composition for forming a tantalum layer comprising a hydrogenated polyxaazepine according to the present invention is used to form the tantalum layer, the defects are remarkably reduced, thereby improving the insulating properties and gap filling properties required for the tantalum layer.

Simple illustration

Fig. 1 is a graph showing the results of measurement of a polyoxazane and a siloxazane solution obtained from Example 3 and Comparative Example 4 on a high sensitivity GPC (gel permeation chromatography).

Detailed description

Exemplary embodiments of the present invention will be described in detail below. However, these embodiments are merely exemplary and do not limit the invention.

As used herein, the term "substituted", when not otherwise defined, refers to a compound substituted with at least one substituent selected from halo (F, Br, Cl or I), hydroxy, alkoxy. Base, nitro, cyano, amine, azide, amidino group, hydrazino, hydrazono group, carbonyl, amine mercapto, thiol, ester, carboxyl or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, an alkyl group, a C2 to C16 alkenyl group, a C2 to C16 alkynyl group, an aryl group, a C7 to C13 aralkyl group, a C1 to C4 oxyalkyl group, C1 to C20 heteroalkyl, C3 to C20 heteroarylalkyl, C3 to C16 cycloalkyl, C3 to C15 cycloalkenyl, C6 to C15 cycloalkynyl, C1 to C16 heterocycloalkyl, and combinations thereof.

As used herein, when a definition is not otherwise provided, the prefix "hetero" may refer to a compound including 1 to 3 hetero atoms selected from N, O, S, and P.

According to an embodiment of the present invention, the composition for forming the ruthenium oxide layer comprises one selected from the group consisting of hydrogenated polyazane, hydrogenated polyoxazane, and combinations thereof, and the composition for forming the ruthenium oxide layer is removed. Polymer microparticles, and based on the total amount of hydrogenated polyazide and hydrogenated polyoxazane, a weight average molecular weight (converted to polystyrene) of greater than or equal to about 50,000 hydrogenated polyazane and hydrogenated polyoxonium The concentration of the sum of the alkane ranges from less than or equal to about 0.1% by weight.

When a hydrogenated polyazide or a hydrogenated polyoxazepine is converted into a condensed silica glass material by heating and oxidation reaction, it can be used for an insulating layer, a separator, a hard coating (hard coating) )Wait. When the composition is used to form a silicon oxide layer, voids or defects in the layer can be controlled and reduced, so that it can be used to manufacture devices requiring high quality electrical characteristics such as semiconductors, liquid crystals and the like.

In particular, fluid particulates contained in the composition for forming the ruthenium oxide layer may cause voids or defects in the ruthenium oxide layer produced using the composition for forming the ruthenium oxide layer, and thus are used for forming ruthenium oxide. The composition of the layer may be a composition that removes fluid particles, which can be analyzed using high sensitivity GPC (gel permeation chromatography).

Removal of the polymer fine particles from the composition for forming the hafnium layer can be achieved by the following method. In the solution state, the composition for forming the ruthenium oxide layer from which the polymer particles are removed may have a number of particles in the liquid of from 0 to about 100/cc.

The polymer microparticles may be one selected from the group consisting of hydrogenated polyazane, hydrogenated polyoxazane, and the like, which are selected from polystyrene when the weight average molecular weight is greater than or equal to about 50,000, for example, converted to polyphenylene. In the case of ethylene, the weight average molecular weight is from about 50,000 to about 5,000,000 of a hydrogenated polyazane, a hydrogenated polyoxazane, and combinations thereof.

In view of the defect, the concentration based on the total amount of the hydrogenated polyazide and the hydrogenated polyoxazane may include a concentration of 0 wt% to about 0.1 wt%, for example, a concentration of 0 wt% to about 0.07 wt%, or a concentration of 0 wt. From about 0.05% by weight of the polymer fine particles comprising one selected from the group consisting of polymer hydrogenated polyazane, hydrogenated polyoxazane, and combinations thereof. Within this range, it can be effectively used for devices requiring high quality electrical characteristics such as semiconductors, liquid crystals and the like. Thereby, the concentration of the polymer hydrogenated polyazane or the hydrogenated polyoxazepine fine particles can be controlled within this range.

The hydrogenated polyazane or hydrogenated polyoxazane may include a moiety represented by the following Chemical Formula 1.

In Chemical 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, Substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxyl group, or a combination thereof.

The hydrogenated polyoxazane may further include a moiety represented by the following Chemical Formula 2.

In Chemical 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, Substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 heterocycloalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxyl group, or a combination thereof.

In this manner, the hydrogenated polyxaazepine contains a 矽-oxygen-(Si-O-Si) bond different from the 矽-nitrogen (Si-N) bond in the structure. The bismuth-oxygen-germanium (Si-O-Si) bond can relieve stress during curing by heat treatment, thereby reducing shrinkage.

In order to inhibit structural shrinkage during the heating (heat) treatment, the oxygen content in the hydrogenated polyxaazepine may range from about 0.2 wt% to about 3 wt%. When included in the range, the stress is sufficiently relaxed by the 矽-oxygen-矽 (Si-O-Si) bond in the structure, thereby preventing shrinkage during heat treatment, so that the obtained load pattern can be prevented (charged) A crack occurs in the pattern).

In this regard, it can be included in this range from about 0.4 to about 2 wt%.

The hydrogenated polyoxazepine may include a moiety represented by the following Chemical Formula 3 at its end.

<Chemical Formula 3>

*-SiH ₃

The portion represented by the above Chemical Formula 3 has a capped end with hydrogen, and may be in an amount of from about 15 wt% to about 35 wt% based on the total amount of Si-H bonds in the hydrogenated polyoxazane. include. Within this range, it is possible to generate a sufficient oxidation reaction during the heat treatment, and it is possible to prevent the SiH _{3 from being} dispersed into the SiH ₄ . Therefore, the Si-H bond can prevent shrinkage, thereby preventing cracks on the loaded pattern.

According to one embodiment, the weight average molecular weight (Mw) of the hydrogenated polyazide and/or the hydrogenated polyoxazane is not particularly limited, but in view of solubility in an organic solvent or coating characteristics on a substrate, The weight average molecular weight can range from about 1000 to about 10,000.

According to another embodiment, from about 0.1 wt% to about 50 wt% of the hydrogenated polyazane and/or the hydrogenated polyxaazepine may be included based on the total amount of the composition used to form the rhodium oxide layer. When included within this range, it can maintain an appropriate viscosity. In addition, when the composition for forming the ruthenium oxide layer including the hydrogenated polyazane and/or the hydrogenated polyxaazepine fills the gap, it can be formed uniformly and without voids.

The composition for forming the ruthenium oxide layer may further include a thermal acid generator (TAG).

The thermal acid generator may be an additive for improving the development performance of the hydrogenated polyazane and/or hydrogenated polyoxazane. The hydrogenated polyazane and/or hydrogenated polyoxazane can be developed at relatively low temperatures.

The thermal acid generator may include any compound which is not particularly limited as long as it generates an acid (H ⁺ ) by heat. In particular, it may include a compound which is activated at 90 ° C or higher and which produces sufficient acid and which has low volatility. Such a thermal acid generator may, for example, be selected from the group consisting of nitrobenzyl p-toluenesulfonate, nitrobenzyl benzenesulfonate, phenol sulfonate, and combinations thereof.

The amount of the thermal acid generator may be included in an amount of from about 0.01% by weight to about 25% by weight based on the total amount of the composition for forming the siloxane layer. Within this range, the hydrogenated polyoxazane can be developed at a low temperature while having improved coating properties.

The composition for forming the ruthenium oxide layer may further include a surfactant.

The surfactant is not particularly limited and includes, for example, a nonionic surfactant: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl group Ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; polyoxyethylene sorbitan fatty acid esters Such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitol trioleate Ester, polyoxyethylene sorbitan tristearate, etc.; fluorine-based surfactants: EFTOP EF301, EF303, EF352 (Tochem Products Co., Ltd.), MEGAFACE F171, F173 (Dainippon Ink & Chem., Inc.) FLUORAD FC430, FC431 (Sumitomo 3M), Asahi guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd., etc.); other anthrone-based surfaces An active agent such as an organic siloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) or the like.

The surfactant may be included in an amount of from 0.001% by weight to 10% by weight based on the total amount of the composition for forming the siloxane layer. Within this range, the dispersion of the solution, the uniformity of thickness of the layers at the same time, and the filling property are improved.

The composition for forming the ruthenium oxide layer may be a solution in which hydrogenated polyazane and/or hydrogenated polyoxazane and other components are dissolved in a solvent.

The solvent is not particularly limited as long as it can dissolve these components, but may include, for example, an aromatic hydrocarbon such as xylene or the like, or an ether such as dibutyl ether.

Based on the total amount of the composition for forming the ruthenium oxide layer, a solvent may be included as an equilibrium in addition to the above components.

A method for preparing a composition for forming a ruthenium oxide layer comprising a hydrogenated polyazane and/or a hydrogenated polyoxazane, which removes polymer microparticles, comprises: mixing a halogenated decane compound with a solvent, and performing the same Co-ammonia hydrolysis to synthesize hydrogenated polyazane or hydrogenated polyoxazane, thereby forming a product solution comprising a hydrogenated polyazane or a hydrogenated polyoxazane; adding a C4 to C10 alkane to the product solution a combination of at least one of a C4 to C10 cycloalkane, a C4 to C10 olefin, a C4 to C10 cycloalkene, decalin, tetrahydronaphthalene, p-isopropyltoluene, p-menthane, alpha-pinene, or the like. An additional solvent to precipitate insoluble precipitates; and to remove precipitated insoluble precipitates.

The composition solution for forming the ruthenium oxide layer prepared by the method removes the polymer hydrogenated polyazane and/or the hydrogenated polyoxazane, and thus is used in the liquid in the composition solution for forming the ruthenium oxide layer. The number of particles can range from 0 to 100/cc.

The additional solvent added to the composition for forming the ruthenium oxide layer is then used to precipitate the polymer hydrogenated polyazane and/or the hydrogenated polyoxazane, and may be borrowed later when it is disadvantageous for forming the ruthenium layer. Removed by evaporation.

The additional solvent may be selected, for example, from n-octane, cyclohexane, n-hexane, p-menthane, alpha-pinene, n-pentane, n-heptane, or combinations thereof.

Since the polymer hydrogenated polyazide and/or the hydrogenated polyoxazane are selectively precipitated by the additional solvent, the polymer fine particles can be removed by, for example, filtration. When the polymer particles are removed, the defects of the silicon oxide layer can be reduced.

The molecular weight range of the polymer hydrogenated polyazane and/or hydrogenated polyoxazepine to be precipitated and separated can be controlled by changing the amount of additional solvent added. Preferably, the weight ratio of the solvent (before adding the additional solvent) to the additional solvent included in the solution is from about 1:1 to about 1:30. For example, the mixing ratio may be about 1:5, about 1:8, about 1:15, and the like. In this case, by increasing the amount of additional solvent, the amount of precipitation of the polymer hydrogenated polyazane and/or hydrogenated polyoxazane will increase, and the polymer hydrogenated polyazane will remain in the solution. And/or the weight average molecular weight of the hydrogenated polyoxazepine is reduced.

In order to remove precipitated insoluble particles of a specific size or larger, the pore size of the filter can be controlled. For example, a filter having a pore size of about 0.01 to 0.2 μm can be used to filter out and remove particles having a size larger than the pore size.

The defect reducing germanium layer can be fabricated by utilizing a composition for forming a germanium oxide layer according to any of the embodiments of the present invention, and the obtained germanium oxide layer has a wafer of less than or equal to about 1000/8 inch. The amount of defects (size less than or equal to about 5 μm).

The silicon oxide layer may not be limited to the method, but may be produced by any known method.

For example, the substrate can be dried by coating the device substrate (such as a semiconductor and a liquid crystal) with the composition for forming a silicon oxide insulating layer described above, and cured in an atmosphere including water vapor at 200 ° C or higher. The formation of a silicon oxide layer.

The following examples illustrate the invention in more detail. However, it should be understood that the invention is not limited to the embodiments.

[Examples]

The amount, the oxygen content, the weight average molecular weight, and the polymer component of the particles in the liquid of each of the polyazirane solution or the polyoxazolidine solution obtained from the following Examples 1 to 5 and Comparative Examples 1 to 5 were measured. And the results are shown in Table 1 below. The measuring device is as follows:

- Particles in liquid: manufactured by Rion; particle sensor in liquid ‧ counter KS-42BF

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

- Weight average molecular weight and polymer composition: GPC (manufactured by Waters); HPLC pump 1515, RI detector 2414 (manufactured by Shodex); KF801, 802, 803

Example 1

The inside of the reactor having a capacity of 2 L and equipped with a stirrer and a temperature controller was replaced with dry nitrogen. 1500 g of dry pyridine was injected into the reactor and the temperature was maintained at 5 °C. 100 g of dichloromethane was slowly injected over 1 hour. 70 g of ammonia was slowly injected over 3 hours with stirring. Dry nitrogen was then injected for 30 minutes and the residual ammonia in the reactor was removed. The obtained white syrupy product was filtered through a 1 m TEFLON (tetrafluoroethylene) filter under a dry nitrogen atmosphere to give 1000 g of filtrate. 1000 g of dry xylene was added thereto, and then the solid concentration was adjusted to 20 wt% by using a rotary evaporator to replace the pyridine with xylene, and a TEFLON (tetrafluoroethylene) filter having a pore diameter of 0.1 μm was used. Filtration gave a hydrogenated polyazane solution.

The inside of the reactor having a capacity of 1 L and equipped with a stirrer was replaced with dry nitrogen. While stirring at room temperature, 100 g of the obtained hydrogenated polyazane solution was injected into the reactor and 800 g of dry n-octane was slowly injected over 30 minutes. Stirring was stopped and allowed to stand for 3 hours. It was filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.1 μm. The solid concentration was adjusted to 20 wt% by repeating the operation of removing n-octane by a rotary evaporator and replacing it with xylene, and then filtering with a TEFLON (tetrafluoroethylene) filter having a pore diameter of 0.02 μm. The weight average molecular weight of the obtained hydrogenated polyazane solution converted to polystyrene was about 1,700, and it was observed that the peak in the polymer region of higher than or equal to 50,000 corresponds to a concentration of about 0.02% by weight. The amount of particles in the liquid having a size of 0.2 μm or more in the solution was about 5.2 / cc.

Example 2

The inside of the reactor having a capacity of 1 L and equipped with a stirrer was replaced with dry nitrogen. While stirring at room temperature, 100 g of the hydrogenated polyazane solution obtained in Example 1 was injected into the reactor and 600 g of dry cyclohexane was slowly injected over 30 minutes. Stirring was stopped and allowed to stand for 3 hours. It was filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.1 μm. The operation of removing cyclohexane and replacing it with xylene using a rotary evaporator was repeated 3 times to adjust the solid concentration to 20 wt%, and filtered with a TEFLON (tetrafluoroethylene) filter having a pore diameter of 0.02 μm. The weight average molecular weight of the obtained hydrogenated polyazirane solution converted to polystyrene was about 1,700, and a peak of a polymer region of 50,000 or more was observed, corresponding to a concentration of about 0.02% by weight. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 3.8/cc.

Example 3

The inside of the reactor having a capacity of 2 L and equipped with a stirrer and a temperature controller was replaced with dry nitrogen. 1500 g of dry pyridine was injected into the reactor and the temperature was maintained at 5 °C. 100 g of dichloromethane was slowly injected over 1 hour. 70 g of ammonia was slowly injected over 3 hours with stirring. Dry nitrogen was then injected for 30 minutes and the residual ammonia in the reactor was removed. The obtained white slurry product was filtered using a 1 m TEFLON (tetrafluoroethylene) filter under a dry nitrogen atmosphere to obtain 1000 g of filtrate. 1000 g of dry xylene was added thereto, and then the solid concentration was adjusted to 20 wt% by using a rotary evaporator to replace the pyridine with xylene in the solution by a total of 3 times, using TEFLON (tetrafluoroethylene) having a pore diameter of 0.1 μm. Filter filter.

The obtained hydrogenated polyoxazane solution was kept under stirring at 40 ° C for 240 hours. Filtration with a TEFLON (tetrafluoroethylene) filter having a pore size of 0.02 μm produced a cloudy ammonium chloride precipitate in the solution.

The inside of the reactor having a capacity of 1 L and equipped with a stirrer was replaced with dry nitrogen. While stirring at room temperature, 100 g of the obtained hydrogenated polyazane solution was injected into the reactor and 700 g of dry n-hexane was slowly injected over 30 minutes. Stirring was stopped and allowed to stand for 3 hours. It was filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.1 μm. The solid concentration was adjusted to 20 wt% by repeating the operation of removing n-hexane using a rotary evaporator and substituting xylene, and filtering with a TEFLON (tetrafluoroethylene) filter having a pore diameter of 0.02 μm. The weight average molecular weight of the obtained hydrogenated polyazirane solution converted to polystyrene was about 2,100, and a peak of a polymer region higher than or equal to 50,000 was observed, corresponding to a concentration of about 0.02% by weight. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 3.2/cc.

Example 4

The inside of the reactor having a capacity of 2 L and equipped with a stirrer and a temperature controller was replaced with dry nitrogen. 1500 g of dry pyridine was injected with 0.6 g of pure water and thoroughly mixed, and then introduced into the reactor and the temperature was maintained at 20 °C. 100 g of dichloromethane was slowly injected over 1 hour. 70 g of ammonia was slowly injected over 3 hours with stirring. Dry nitrogen was then injected for 30 minutes and the residual ammonia in the reactor was removed. The obtained white slurry product was filtered using a 1 m TEFLON (tetrafluoroethylene) filter under a dry nitrogen atmosphere to obtain 1000 g of filtrate. 1000 g of dry xylene was added thereto, and then the solid concentration was adjusted to 20 wt% by using a rotary evaporator to replace pyridine with dibutyl ether in a solvent, and TEFLON (tetrafluoroethylene) having a pore diameter of 0.1 μm was used. Ethylene) filter filtration. The obtained hydrogenated polyxamidine solution had an oxygen content of 0.2% and a weight average molecular weight of 4,300, and a peak was observed in a polymer region of 50,000 or higher.

The obtained hydrogenated polyxaazepine solution was introduced into a stainless steel tank having a capacity of 5 L, and the inside thereof was sufficiently replaced with dry nitrogen gas and a pressure of 1 kg/cm ² G was applied. It was aged for 10 hours or more in a freezer at -10 ° C, and filtered using a TEFLON (tetrafluoroethylene) filter having a pore diameter of 0.02 μm. The obtained hydrogenated polyxaazepine solution had a weight average molecular weight of about 4,400, and a peak was observed in a polymer region of 50,000 or higher.

The inside of the reactor having a capacity of 1 L and equipped with a stirrer was replaced with dry nitrogen. While stirring at room temperature, 100 g of the obtained hydrogenated polyxamidine solution was injected into the reactor and 1000 g of dry p-menthane was slowly injected over 30 minutes. Stirring was stopped and allowed to stand for 3 hours. It was filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.1 μm. The solid concentration was adjusted to 20 wt% by a procedure in which the cyclohexane was removed and replaced with xylene using a rotary evaporator for a total of three times, and filtered with a TEFLON (tetrafluoroethylene) filter having a pore diameter of 0.02 μm. The weight average molecular weight of the obtained hydrogenated polyximezepine solution converted to polystyrene was about 4,200, and a peak of a polymer region higher than or equal to 50,000 was observed, corresponding to a concentration of about 0.04% by weight. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 2.1/cc.

Example 5

The inside of the reactor having a capacity of 2 L and equipped with a stirrer and a temperature controller was replaced with dry nitrogen. 1500 g of dry pyridine was injected with 0.6 g of pure water and thoroughly mixed, and then introduced into the reactor and the temperature was maintained at 20 °C. 100 g of dichloromethane was slowly injected over 1 hour. 70 g of ammonia was slowly injected over 3 hours with stirring. Dry nitrogen was then injected for 30 minutes and the residual ammonia in the reactor was removed. The obtained white slurry product was filtered using a 1 m TEFLON (tetrafluoroethylene) filter under a dry nitrogen atmosphere to obtain 1000 g of filtrate. 1000 g of dry xylene was added thereto, and then the solid concentration was adjusted to 20 wt% by using a rotary evaporator to replace pyridine with dibutyl ether in a solvent, and TEFLON (tetrafluoroethylene) having a pore diameter of 0.1 μm was used. Filter filter. The obtained hydrogenated polyxamidine solution had an oxygen content of 0.2% by weight and a weight average molecular weight of 4,300, and a peak was observed in a polymer region of 50,000 or higher.

The obtained hydrogenated polyxaazepine solution was introduced into a stainless steel tank having a capacity of 5 L, and the inside was sufficiently replaced with dry nitrogen gas and a pressure of 1 kg/cm ² G was applied. It was aged for 10 hours or more in a freezer at -10 ° C, and filtered using a TEFLON (tetrafluoroethylene) filter having a pore diameter of 0.02 μm. The weight average molecular weight of the hydrogenated polyoxazane solution was about 4,400, and a peak was observed in a polymer region of 50,000 or higher.

The inside of the reactor having a capacity of 1 L and equipped with a stirrer was replaced with dry nitrogen. While stirring at room temperature, 100 g of the obtained hydrogenated polyxamidine solution was injected into the reactor and 900 g of dry α-pinene was slowly injected over 30 minutes. Stirring was stopped and allowed to stand for 3 hours. It was filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.1 μm. The solid concentration was adjusted to 20 wt% by a total of three repetitions of the use of a rotary evaporator to remove α-pinene and replaced with xylene, and filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.02 μm. The weight average molecular weight of the obtained hydrogenated polyximezepine solution converted to polystyrene was about 4500, and a peak of a polymer region higher than or equal to 50,000 was observed, corresponding to a concentration of about 0.04% by weight. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 4.1/cc.

Comparative example 1

The inside of the reactor having a capacity of 2 L and equipped with a stirrer and a temperature controller was replaced with dry nitrogen. 1500 g of dry pyridine was injected into the reactor and the temperature was maintained at 5 °C. 100 g of dichloromethane was slowly injected over 1 hour. 70 g of ammonia was slowly injected over 3 hours with stirring. Dry nitrogen was then injected for 30 minutes and the residual ammonia in the reactor was removed. The obtained white slurry product was filtered using a 1 m TEFLON (tetrafluoroethylene) filter under a dry nitrogen atmosphere to obtain 1000 g of filtrate.

1000 g of dry xylene was added thereto, and then the solid concentration was adjusted to 20 wt% by using a rotary evaporator to replace pyridine with xylene in a solvent, and TEFLON (tetrafluoroethylene) having a pore diameter of 0.1 μm was used. Filter filter. The weight average molecular weight of the obtained hydrogenated polyazirane solution converted to polystyrene was about 1600, and a peak of a polymer region higher than or equal to 50,000 was observed, corresponding to a concentration of about 0.21% by weight. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 1220 / cc.

Comparative example 2

The hydrogenated polyoxazane solution obtained in Comparative Example 1 was stirred and maintained at 40 ° C for 240 hours under the conditions described in Example 1, and filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.1 μm. The weight average molecular weight of the obtained hydrogenated polyazane solution converted to polystyrene was about 1800, and a peak of a polymer region higher than or equal to 50,000 was observed, corresponding to a concentration of about 0.28 wt%. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 1460/cc.

Comparative example 3

The hydrogenated polyazane solution obtained in Comparative Example 1 was filtered through a TEFLON (tetrafluoroethylene) filter having a pore size of 0.02 μm. The weight average molecular weight of the obtained hydrogenated polyazane solution converted to polystyrene was about 1800, and a peak of a polymer region higher than or equal to 50,000 was observed, corresponding to a concentration of about 0.13 wt%. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 960/cc.

Comparative example 4

The inside of the reactor having a capacity of 2 L and equipped with a stirrer and a temperature controller was replaced with dry nitrogen. 1500 g of dry pyridine was injected with 2.0 g of pure water and introduced into the reactor and the temperature was maintained at 5 °C. 100 g of dichloromethane was slowly injected over 1 hour. 70 g of ammonia was slowly injected over 3 hours with stirring. Dry nitrogen was then injected for 30 minutes and the residual ammonia in the reactor was removed. The obtained white slurry product was filtered using a 1 m TEFLON (tetrafluoroethylene) filter under a dry nitrogen atmosphere to obtain 1000 g of filtrate. 1000 g of dry xylene was added, and then the solid concentration was adjusted to 20 wt% by using a rotary evaporator to replace pyridine with dibutyl ether in a solvent, and TEFLON (tetrafluoroethylene) having a pore diameter of 0.1 μm was used. Filter filter. The obtained hydrogenated polyxanthracene solution has an oxygen content of 0.5% by weight, a weight average molecular weight of about 2200 when converted to polystyrene, and a peak of a polymer region of 50,000 or higher, corresponding to about A concentration of 0.35 wt%. The oxygen content was about 3.5 ppm. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 690/cc.

Comparative Example 5

The hydrogenated polyazane solution obtained from Comparative Example 1 was kept at 240 ° C for 240 hours with stirring. Filtration of a cloudy ammonium chloride in the solution was then carried out using a TEFLON (tetrafluoroethylene) filter having a pore size of 0.02 μm. The weight average molecular weight of the hydrogenated polyoxazane solution was about 2,200, and a peak of a polymer region higher than or equal to 50,000 was observed, corresponding to a concentration of about 0.25 wt%. The amount of particles in the liquid having a size greater than or equal to 0.2 μm in the solution was about 740/cc.

Fig. 1 is a graph showing the measurement results of a polyazoxide and a polyoxazolidine solution on a high sensitivity GPC (gel permeation chromatography). The solid line indicates the result of the polyximezepine solution obtained from Comparative Example 4; the broken line indicates the result of the polyazinone solution obtained in Example 3. It was confirmed that the peak indicating that the weight average molecular weight when converted to polystyrene was 50,000 or more disappeared in Example 3.

According to the results shown in Table 1, it was confirmed that the polymer component of 50,000 or more was removed in Examples 1 to 5. Specifically, in Comparative Example 2, the polymer component was not removed; on the contrary, in Example 1, in which the insoluble matter was precipitated using n-octane, the polymer component was removed. Further, in Example 2, the polymer component was reduced from the hydrogenated polyxane obtained in the same manner as in Comparative Example 1 by using the cyclohexane to precipitate an insoluble matter. In Examples 3 to 5, the polymer component was effectively removed from the polyxaazepine solution by using insoluble substances precipitated from n-hexane, p-menthane and α-pinene, respectively.

The present invention is described by way of example, and is not to be construed as limited Various changes and equivalent replacements. Therefore, the foregoing embodiments are to be considered as illustrative and not restrictive.

Fig. 1 is a graph showing the results of measurement of a polyoxazane and a siloxazane solution obtained from Example 3 and Comparative Example 4 on a high sensitivity GPC (gel permeation chromatography).

Claims (14)

A composition for forming a ruthenium oxide layer, comprising: one selected from the group consisting of hydrogenated polyazane, hydrogenated polysiloxazane, and combinations thereof, wherein the hydrogenated poly The total amount of the azane and the hydrogenated polyxanthracene, the sum of the weight average molecular weight (converted to polystyrene) greater than or equal to 50,000, and the sum of the hydrogenated polyazane and the hydrogenated polyoxazane is less than or Equal to 0.1 wt%. The composition for forming a ruthenium oxide layer according to claim 1, wherein the weight average molecular weight (converted to polystyrene) is based on the total amount of the hydrogenated polyazide and the hydrogenated polyoxazane. The concentration of the sum of the hydrogenated polyazane and the hydrogenated polyoxazane greater than or equal to 50,000 is in the range of less than or equal to 0.05% by weight. The composition for forming a layer of a ruthenium layer according to the first aspect of the invention, wherein the composition for forming a ruthenium layer has a number of particles of 0 to 100 in a liquid having a size of 0.2 μm or more in a solution. /cc. A composition for forming a layer of a ruthenium oxide according to the first aspect of the invention, wherein the hydrogenated polyazide or the hydrogenated polyoxazane includes a moiety represented by the following Chemical Formula 1: Wherein, in Chemical 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 aromatic group. a substituted, unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxyl group, or a combination thereof. A composition for forming a layer of a ruthenium oxide according to the fourth aspect of the invention, wherein the hydrogenated polyxanthracene further comprises a moiety represented by the following Chemical Formula 2: Wherein, in Chemical 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 aromatic group. a substituted, unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxyl group, or a combination thereof. A composition for forming a layer of a ruthenium oxide according to the fifth aspect of the invention, wherein the hydrogenated polyoxazepine includes a moiety represented by the following Chemical Formula 3 at its end, and has an oxygen content of 0.2% by weight. To 3 wt%, and based on the total amount of Si-H bonds, the portion represented by the following Chemical Formula 3 is included in an amount of 15 wt% to 35 wt%: <Chemical Formula 3>*-SiH ₃ . The composition for forming a layer of a ruthenium layer according to the first aspect of the invention, wherein the hydrogenated polyazide or the hydrogenated polyoxazane has a weight average molecular weight of from 1,000 to 10,000. The composition for forming a ruthenium oxide layer according to the first aspect of the invention, wherein the sum of the hydrogenated polyazide and the hydrogenated polyxanthracene is in the range of 0.1% by weight to 50% by weight. A method for producing a composition for forming a layer of a ruthenium layer according to claim 1, comprising: mixing a halogenated decane compound with a solvent, and coammonolyzing it to synthesize a hydrogenated polyfluorene a nitrogen alkane or a hydrogenated polyoxazepine, thereby forming a product solution comprising the hydrogenated polyazide or the hydrogenated polyxaazepine; adding C4 to C10 alkanes, C4 to the product solution to An additional solvent of a combination of a C10 cycloalkane, a C4 to C10 olefin, a C4 to C10 cycloalkene, decalin, tetrahydronaphthalene, p-isopropyltoluene, p-menthane, alpha-pinene, or the like, To precipitate insoluble precipitates; The precipitated insoluble precipitate was removed. The method of claim 9, wherein the weight ratio of the solvent contained in the solution to the additional solvent before the addition of the additional solvent is in the range of 1:1 to 1:30. The method of claim 9, further comprising removing the additional solvent after removing the precipitated insoluble precipitate. The method of claim 9, wherein the removing the precipitated insoluble precipitate comprises filtering and removing the precipitated insoluble precipitate by a filter having a pore diameter of 0.01 to 0.2 μm. An antimony layer produced by using the composition for forming a hafoxide layer according to any one of claims 1 to 8 and having a defect having a size of less than or equal to 5 μm or less Equal to 1000 / 8 inch wafer. A method of manufacturing a defect-reduced oxygen layer, comprising: coating a composition for forming a layer of a silicon oxide layer according to any one of claims 1 to 8 on a substrate; drying and coating the composition The substrate of the composition forming the silicon oxide layer; and is cured in an atmosphere containing water vapor of 200 ° C or higher.