Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition

Abstract

Provided are a silylamine compound, a composition for depositing a silicon-containing thin film containing the same, and a method for manufacturing a silicon-containing thin film using the composition, and more particularly, to a silylamine compound capable of being usefully used as a precursor of a silicon-containing thin film, a composition for depositing a silicon-containing thin film containing the same, and a method for manufacturing a silicon-containing thin film using the composition.

Claims

1. A silylamine compound represented by the following Chemical Formula 1: ##STR00015## in Chemical Formula 1, R.sub.1 to R.sub.4 are each independently C1-C7alkyl or C2-C7alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4 are each independently linked to each other to form a ring.

2. The silylamine compound of claim 1, wherein in Chemical Formula 1, R.sub.1 to R.sub.4 are each independently C1-C5alkyl or C2-C5alkenyl.

3. The silylamine compound of claim 1, wherein the silylamine compound represented by Chemical Formula 1 is represented by the following Chemical Formula 2 or 3: ##STR00016## in Chemical Formulas 2 and 3, R.sub.11 to R.sub.14 are each independently C1-C5alkyl or C2-C5alkenyl; and n and m are each independently an integer of 1 to 7.

4. The silylamine compound of claim 3, wherein in Chemical Formula 2, R.sub.11 to R.sub.14 are each independently C1-C3alkyl or C2-C3alkenyl; and wherein in Chemical Formula 3, n and m are each independently an integer of 1 to 4.

5. The silylamine compound of claim 1, wherein the silylamine compound represented by Chemical Formula 1 is selected from the following compounds: ##STR00017##

6. A composition for depositing a silicon-containing thin film, the composition comprising the silylamine compound of claim 1.

7. A method for manufacturing a silicon-containing thin film comprising depositing the composition of claim 6 onto a substrate.

8. The method of claim 7, wherein deposition is performed by an atomic layer deposition method, a chemical vapor deposition method, a metal-organic chemical vapor deposition method, a low-pressure chemical vapor deposition method, a plasma-enhanced chemical vapor deposition method, or a plasma-enhanced atomic layer deposition method.

9. The method of claim 7, wherein the silicon-containing thin film is a silicon oxide film, a silicon oxy carbide film, a silicon nitride film, a silicon oxy nitride film, a silicon carbonitride film, or a silicon carbide film.

10. The method of claim 7, comprising: a) maintaining a temperature of a substrate mounted in the chamber at 30 to 500□; b) contacting the composition of claim 6 with the substrate to adsorb the composition in the substrate; and c) injecting a reaction gas into the substrate in which the composition is adsorbed to form a silicon-containing thin film.

11. The method of claim 7, wherein the reaction gas is supplied after being activated by generating plasma with a plasma power of 50 to 1000 W.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 is a view illustrating results obtained by measuring vapor pressures of bis(ethylmethylaminosilyl)amine and bis(diethylaminosilyl)amine compounds prepared in Examples 1 and 2.

(2) FIG. 2 is a view illustrating results obtained by analyzing silicon oxide thin films manufactured in Example 3 and Comparative Examples 3 and 4 using infrared spectroscopy.

(3) FIG. 3 is a view illustrating results obtained by analyzing silicon oxide thin films manufactured in Example 3 and Comparative Examples 3 and 4 using a transmission electron microscope (TEM).

DETAILED DESCRIPTION

BEST MODE

(4) The present invention provides a silylamine compound, which is a liquid at room temperature and has high volatility and excellent thermal stability to thereby be used as a significantly useful precursor of forming a silicon-containing thin film, wherein the silylamine compound is represented by the following Chemical Formula 1.

(5) ##STR00004##

(6) (In Chemical Formula 1, R.sub.1 to R.sub.4 are each independently (C1-C7)alkyl or (C2-C7)alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4 are each independently linked to each other to form a ring.)

(7) In the silylamine compound contained in the composition for depositing a silicon-containing thin film, amine has two aminosilyl functional groups as substituents, and each silicon atom in these two aminosilyl functional groups necessarily has two hydrogen atoms attached thereto, such that the silylamine compound, which is a liquid at room temperature, has high volatility and excellent reactivity with a surface and a reaction gas. Therefore, the silylamine compound may be significantly usefully used to form the silicon-containing thin film.

(8) More specifically, the silylamine compound is a compound having a silazane backbone, but a compound which necessarily has two aminosilyl functional groups

(9) ##STR00005##
and in which each silicon atom of the aminosilyl functional groups necessarily has two hydrogen atoms attached thereto may be more useful as a precursor for depositing a thin film.

(10) More preferably, in Chemical Formula 1 according to the present invention, R.sub.1 to R.sub.4 are each independently (C1-C5)alkyl or (C2-C5)alkenyl, and more preferably, (C1-C3)alkyl or (C2-C3)alkenyl.

(11) Preferably, the silylamine compound represented by Chemical Formula 1 according to the present invention may be represented by the following Chemical Formula 2 or 3.

(12) ##STR00006##

(13) (In Chemical Formulas 2 and 3, R.sub.11 to R.sub.14 are each independently (C1-C5)alkyl or (C2-C5)alkenyl; and n and m are each independently an integer of 1 to 7.)

(14) In the silylamine compound, each silicon atom of two aminosilyl groups in the silazane backbone necessarily has two hydrogen atoms attached thereto, such that the silylamine compound has a more excellent effect as the precursor for depositing a silicon-containing thin film.

(15) Preferably, in Chemical Formula 2 or 3 according to the exemplary embodiment of the present invention, R.sub.11 to R.sub.14 may be each independently (C1-C3)alkyl or (C2-C3)alkenyl; and n and m may be each independently an integer of 1 to 4. More preferably, R.sub.11 to R.sub.14 may be each independently (C1-C3)alkyl; and n and m may be each independently an integer of 1 to 3.

(16) It is more preferable that the silylamine compound represented by Chemical Formula 1 according to the present invention is a compound represented by the following Chemical Formula 4 in which both sides of an NH group are symmetric to each other in order to have more excellent effect as the precursor for depositing a silicon-containing thin film.

(17) ##STR00007##

(18) (In Chemical Formula 4, R.sub.1 and R.sub.2 are each independently (C1-C7)alkyl or (C2-C7)alkenyl, or are linked to each other to form a ring.)

(19) The silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be selected from the following compounds, but is not limited thereto.

(20) ##STR00008##

(21) In addition, the present invention provides a composition for depositing a silicon-containing thin film, containing the silylamine compound according to the exemplary embodiment of the present invention.

(22) The composition for depositing a silicon-containing thin film according to the present invention necessarily contains the silylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention as the precursor for depositing a thin film, and the silylamine compound in the composition for depositing a silicon-containing thin film may be contained in a content range in which the content may be recognized by those skilled in the art in consideration of film formation conditions, a thickness, properties, or the like, of the thin film.

(23) As used herein, the term “alkyl” means linear, branched, and cyclic saturated and unsaturated hydrocarbons having 1 to 7 carbon atoms, preferably, 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms, and examples thereof may include methyl, ethyl, propyl, isobutyl, pentyl, and the like.

(24) As used herein, the term “halogen” means a halogen element, and examples thereof include fluoro, chloro, bromo, iodo.

(25) As disclosed herein, the term “alkenyl” as a single group or a part of another group means a straight-chain, branched-chain, or cyclic hydrocarbon radical having 2 to 7 carbon atoms and one or more carbon-carbon double bonds. A more preferable alkenyl radical is a lower alkenyl radical having 2 to 5 carbon atoms. The most preferable lower alkenyl radical is a lower alkenyl radical having about 2 to 3 carbon atoms. Further, an alkenyl group may be substituted at a random usable attachment point. Examples of the alkenyl radical include ethenyl, propenyl, allyl, butenyl, and 4-methylbutenyl. The terms “alkenyl” and “lower alkenyl” include radicals having cis and trans orientations or alternatively, E and Z orientations.

(26) As used herein, the phrase “R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4 are each independently linked to each other to form a ring” includes the case in which R.sub.1 and R.sub.2 are linked to each other to form a ring but R.sub.3 and R.sub.4 do not form a ring; the case in which on the contrary, R.sub.1 and R.sub.2 do not form a ring but R.sub.3 and R.sub.4 are linked to each other to form a ring; and the case in which R.sub.1 and R.sub.2 are linked to each other to form a ring and R.sub.3 and R.sub.4 are linked to each other to form a ring, wherein the formed ring may be an alicyclic or aromatic ring containing N, and preferably, an alicyclic ring.

(27) The silylamine compound represented by Chemical Formula 1 according to the present invention may be prepared by any method as long as the method may be recognized by those skilled in the art. As an example, the silylamine compound may be prepared by reacting compounds represented by the following Chemical Formulas 11, Chemical Formulas and Chemical Formulas 13.

(28) ##STR00009##

(29) (In Chemical Formulas 11 to 13, R.sub.1 to R.sub.4 are each independently (C1-C7)alkyl or (C2-C7)alkenyl, or R.sub.1 and R.sub.2, and R.sub.3 and R.sub.4 are each independently linked to each other to form a ring, and X.sub.1 is halogen.)

(30) Preferably, the compounds represented by Chemical Formulas 12 and 13 according to the exemplary embodiment of the present invention may be used in a content of 1.1 to 4.2 moles based on 1 mole of the compound represented by Chemical Formula 11, and a reaction may be performed at room temperature, specifically at 18 to 35° C. for 2 to 8 hours.

(31) The compound represented by Chemical Formula 11 according to the exemplary embodiment of the present invention may be synthesized by any method as long as the method may be recognized by those skilled in the art. As an example, the compound may be prepared by reacting compounds represented by the following Chemical Formulas 14 and 15 with each other in the presence of an acid.

(32) ##STR00010##

(33) (In Chemical Formulas 14 and 15, R is (C1-C7)alkyl, and X.sub.1 is halogen.)

(34) As an acid according to the exemplary embodiment of the present invention, any acid may be used as long as it is a Lewis acid, but AlCl.sub.3 may be preferably used.

(35) The compound represented by Chemical Formula 15 may be used in a content of 2 to 4.5 moles based on 1 mole of the compound represented by Chemical Formula 14, and the Lewis acid may be used 0.005 to 1 mole, more preferably 0.005 to 0.01 moles based on 1 mole of the compound represented by Chemical Formula 14. A reaction may be performed at −30 to −5° C. for 1 to 6 hours.

(36) In addition, the present invention provides a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the exemplary embodiment of the present invention.

(37) In the method for manufacturing a silicon-containing thin film according to the present invention, the composition for depositing a silicon-containing thin film according to the exemplary embodiment of the present invention, containing the silylamine compound represented by Chemical Formula 1 which is a liquid at room temperature and has high volatility and excellent thermal stability as the precursor is used, such that the handling may be easy, it is possible to manufacture various thin films, and it is possible to manufacture a silicon-containing thin film having a high purity at a high deposition rate even at a low temperature and a low power.

(38) Further, a silicon-containing thin film manufactured by the method according to the present invention has excellent durability and electric properties, and resistance against hydrogen fluoride, water vapor transmission rate, and step coverage thereof are also excellent.

(39) In the method for manufacturing a silicon-containing thin film according to the present invention, the silicon-containing thin film may be formed by any method as long as it may be recognized by those skilled in the art. However, preferably, the silicon-containing thin film may be formed by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma enhanced chemical vapor deposition (PECVD) method, or a plasma enhanced atomic layer deposition (PEALD) method, but PECVD, ALD, or PEALD is more preferable in order to allow the thin film to be more easily deposited, and allow the manufactured thin film to have excellent properties.

(40) The silicon-containing thin film according to the present invention may be a silicon oxide (SiO.sub.2) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film, and various thin films having high quality may be manufactured.

(41) More specifically, the method for manufacturing a silicon-containing thin film according to the present invention may include:

(42) a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500° C., preferably 30 to 150° C., and more preferably 30 to 100° C.;

(43) b) contacting the composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate; and

(44) c) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film.

(45) More specifically, the method for manufacturing a silicon-containing thin film according to the present invention may include:

(46) a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500° C.;

(47) b) contacting the composition for depositing a silicon-containing thin film with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate;

(48) c) purging the remaining composition for depositing a silicon-containing thin film and by-products;

(49) d) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film; and

(50) e) purging the remaining reaction gas and by-products, wherein the reaction gas in step D) may remove a ligand of the silylamine compound contained in the composition for depositing a silicon-containing thin film to form a Si—O atomic layer.

(51) Preferably, the reaction gas according to the exemplary embodiment may be supplied after being activated by generating plasma at a plasma power of 50 to 1000 W.

(52) In the method for manufacturing a silicon-containing thin film according to the exemplary embodiment of the present invention, the silylamine compound according to the present invention is used as the precursor, such that deposition may be performed at a low temperature of 50 to 90° C., and the reaction gas may be activated by generating plasma at a low plasma power of 50 to 400 W, thereby making it possible to manufacture the thin film. In the method for manufacturing a silicon-containing thin film according to the exemplary embodiment of the present invention, deposition conditions may be adjusted depending on a structure or thermal properties of a desired thin film. Examples of the deposition condition according to the exemplary embodiment of the present invention may include an injection flow rate of the composition for depositing a silicon-containing thin film containing the silylamine compound, injection flow rates of the reaction gas and a carrier gas, pressure, RF power, the temperature of the substrate, and the like. As non-restrictive examples of the deposition conditions, the injection flow rate of the composition for depositing a silicon-containing thin film may be adjusted in a range of 10 to 1000 cc/min, the injection flow rate of the carrier gas may be adjusted in a range of 10 to 1000 cc/min, the injection flow rate of the reaction gas may be adjusted in a range of 1 to 1500 cc/min, the pressure may be adjusted in a range of 0.5 to 10 torr, the RF power may be adjusted in a range of 50 to 1000 W, and the temperature of the substrate may be adjusted in a range of 30 to 500° C., preferably 30 to 200° C., but the deposition conditions are not limited thereto.

(53) The reaction gas used in the method for manufacturing a silicon-containing thin film according to the present invention is not limited, but may be one selected from hydrogen (H.sub.2), hydrazine (N.sub.2H.sub.4), ozone (O.sub.3), oxygen (O.sub.2), nitrous oxide (N.sub.2O) ammonia (NH.sub.3), nitrogen (N.sub.2), silane (SiH.sub.4), borane (BH.sub.3), diborane (B.sub.2H.sub.6), and phosphine (PH.sub.3), or a mixed gas of one or more thereof, and the carrier gas may be one selected from nitrogen (N.sub.2), argon (Ar), and helium (He), or a mixed gas of two or more thereof.

(54) The substrate used in the method for manufacturing a silicon-containing thin film according to the present invention may be a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon-on-insulator (SOI) substrate; a quartz substrate; a glass substrate for a display; or a flexible plastic substrate made of polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), polyester, and the like, but is not limited thereto.

(55) Further, the silicon-containing thin film may be directly formed on the substrate. Alternatively, a large number of conductive layers, dielectric layers, insulating layers, or the like, may also be formed between the substrate and the silicon-containing thin film.

(56) Preferably, the composition for depositing a silicon-containing thin film according to the exemplary embodiment of the present invention may be used as an encapsulant of an organic light emitting diode (OLED).

(57) The present invention will be described in detail with reference to the following Examples. The terms and words used in the present specification and claims should not be interpreted as being limited to typical meanings or dictionary definitions, but should be interpreted as having meanings and concepts relevant to the technical scope of the present invention based on the rule according to which an inventor can appropriately define the concept of the term to describe most appropriately the best method he or she knows for carrying out the present invention.

(58) Therefore, configurations described in the embodiments and shown in the drawings of the present specification indicate only the most preferred example rather than indicating all the technical ideas of the present invention and therefore, it is to be understood that various equivalents and modifications that can replace the above configurations may be present.

(59) Further, in all the following Examples, deposition was performed by a plasma enhanced atomic layer deposition (PEALD) method known in the art using a commercialized 200 mm single wafer shower head type ALD apparatus (CN1, Atomic Premium). In addition, deposition was performed by a plasma enhanced chemical vapor deposition (PECVD) method known in the art using a commercialized 200 mm single wafer shower head type CVD (PECVD) apparatus (CN1, Atomic Premium).

(60) A thickness of a deposited silicon-containing thin film was measured using an ellipsometer (OPTI-PROBE 2600, THERNIA-WAVE), and a composition of the manufactured silicon-containing thin film was analyzed using infrared spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics) and X-ray photoelectron spectroscopy.

(61) Further, a step coverage was confirmed using a transmission electron microscope (Tecnai F30 S-Twin, FEI Korea).

[Example 1] Preparation of Bis(Ethylmethylaminosilyl)Amine

(62) ##STR00011##

(63) Under an anhydrous and inert atmosphere, after putting hexamethyl disilazane (((CH.sub.3).sub.3Si).sub.2NH, 1,695 g (10.5 mol)) and aluminum chloride (AlCl.sub.3, 7 g (0.05 mol)) into a 5000 mL Sus flame-dried reactor, dichloro silane (SiH.sub.2Cl.sub.2, 2,121 g (21 mol)) was slowly added thereto while stirring the mixture and maintaining a temperature at −25° C. Then, a reaction solution was stirred at −10° C. This mixture reaction solution was stirred for 3 hours, aluminum chloride (AlCl.sub.3) was removed therefrom by filtration, and the formed chlorotrimethylsilane ((CH.sub.3).sub.3SiCl) was removed by simple distillation or distillation under reduced pressure. While stirring a recovered bis(chlorosilyl)amine ((SiH.sub.2Cl).sub.2NH) solution with n-pentane and maintaining a temperature at −25° C., ethylmethylamine ((CH.sub.3CH.sub.2)CH.sub.3NH), 676 g (11.44 mol)) were slowly added thereto. After the addition was completed, the reaction solution was slowly heated to room temperature and stirred at room temperature for 6 hours. The formed white solid was removed by filtration, thereby obtaining a filtrate. A solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(ethylmethylaminosilyl)amine (((SiH.sub.2NCH.sub.3(CH.sub.2CH.sub.3)).sub.2NH, 200 g (1.04 mol), yield: 33%).

(64) .sup.1H-NMR(in CDCl.sub.3): δ 2.52 (s, 6H, (((SiH2NCH3(CH2CH3))2NH), δ 4.48 (d, 4H, (((SiH2NCH3(CH2CH3))2NH), δ 1.04 (t, 6H, ((SiH2NCH3(CH2CH3))2NH, δ 2.86 (q, 4H ((SiH2NCH3(CH2CH3))2NH).

[Example 2] Preparation of Bis(Diethylaminosilyl)Amine

(65) ##STR00012##

(66) Bis(diethylaminosilyl)amine was prepared in the same manner as in Example 1 except for using diethylamine instead of ethylmethylamine in Example 1.

(67) .sup.1H-NMR (in CDCl.sub.3): δ1.02 (t, 12H, (((SiH2(N(CH2CH3)2))2NH), δ 2.89 (q, 8H, (((SiH2(N(CH2CH3)2))2NH), δ 4.51 (d, 4H, (((SiH2(N(CH2CH3)2))2NH)

[Comparative Example 1] Preparation of Bis(Diethylamino)Silane

(68) ##STR00013##

(69) Under an anhydrous and inert atmosphere, after putting dichlorosilane (SiH.sub.2Cl.sub.2, 300 g (2.97 mol)) and n-hexane (2,887 g (33.5 mol)) into a 5000 mL flame-dried Sus reactor (a high-pressure reactor) and slowly adding diethylamine (CH.sub.3CH.sub.2).sub.2NH, 931 g (12.47 mol)) thereto while maintaining a temperature at −25° C., the mixture was stirred for 3 hours, and diethylamine hydrochloride ((CH.sub.3CH.sub.2).sub.2NHHCl)) was removed by filtration, thereby obtaining a filtrate. A solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(diethylaminosilane) (SiH.sub.2(N(CH.sub.2CH.sub.3).sub.2).sub.2, 388 g (2.22 mol), yield: 75%).

(70) .sup.1H-NMR(inC6D6): δ 0.98 (t, 12H (SiH2(N(CH2CH3)2)2), 2.86 (q, 8H)(SiH2(N(CH2CH3)2)2), 4.71 (s, 2H (SiH2(N(CH2CH3)2)2)

[Comparative Example 2] Preparation of [Bis (Diethylaminodimethylsilyl)]Trimethylsilylamine

(71) ##STR00014##

(72) Under an anhydrous and inert atmosphere, after putting hexamethyl disilazane (((CH.sub.3).sub.3Si).sub.2NH, 250 g (1.55 mol)) and aluminum chloride (AlCl.sub.3, 10 g (0.075 mol)) into a 2000 mL flame-dried Schlenk flask, dichloro dimethylsilane ((CH.sub.3).sub.2SiCl.sub.2, 499.80 g (3.87 mol)) was slowly added thereto while stirring the mixture and maintaining a temperature at 25° C. Then, a reaction solution was slowly heated to 40° C. This mixture reaction solution was stirred for 3 hours, and formed chloro trimethylsilane ((CH.sub.3).sub.3SiCl) and excessively added dichloro dimethylsilane ((CH.sub.3).sub.2SiCl.sub.2) were removed by simple distillation or distillation under reduced pressure. While stirring the recovered chloro dimethyldisilazane (((CH.sub.3).sub.2SiCl).sub.2NH)) solution with hexane (C.sub.6H.sub.14) and maintaining a temperature at −15° C., diethyl amine ((CH.sub.3CH.sub.2).sub.2NH, 475.45 g (6.5 mol)) was slowly added thereto. After the addition was completed, the reaction solution was slowly heated to room temperature and stirred at room temperature for 6 hours. After obtaining a filtrate by removing the formed white solid by filtration, a solvent was removed from the filtrate under reduced pressure. After putting the recovered diethylamino dimethyldisilazane ((CH.sub.3).sub.2SiN(CH.sub.2CH.sub.3).sub.2).sub.2NH) and n-hexane (organic solvent, 200 mL), 2.29M normal butyl lithium (n-C.sub.4H.sub.9Li) hexane (C.sub.6H.sub.14) solution (202.16 g (0.65 mol)) was slowly added thereto while stirring the mixture and maintaining a temperature at −15° C. After the addition was completed, the reaction solution was slowly heated to room temperature and stirred for 12 hours. Then, tetrahydrofuran (O(C.sub.2H.sub.2).sub.2, 200 mL) was added thereto. Chloro trimethylsilane (70.94 g (0.65 mol)) was slowly added to the reaction solution while maintaining a temperature at −20° C. After the addition was completed, the reaction solution was slowly heated, and stirred for 12 hours while maintaining the temperature at 65° C. After obtaining a filtrate by filtering the reaction mixture in which a reaction was terminated to remove a formed white solid, a solvent was removed from the filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bisdiethylaminodimethylsilyl trimethylsilylamine ((CH.sub.3).sub.3SiN(Si(CH.sub.3).sub.2N(CH.sub.2CH.sub.3).sub.2).sub.2, 159 g (0.46 mol), yield: 70%).

(73) .sup.1H-NMR (inC6D6): δ 0.30 (s, 12H, NSi(CH3)2N), 0.32 (s, 9H, Si(CH3)3), 0.99 (t, 12H, Si(NCH2CH3)2), 2.82 (q, 8H, Si(NCH2CH3)2)

[Example 3] Manufacturing of Silicon Oxide Thin Film by PEALD Using Bis(Ethylmethylaminosilyl)Amine

(74) Film formation was evaluated using the silylamine compound prepared in Example 1 according to the present invention as a composition for forming a silicon oxide film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art. As a reaction gas, nitrous oxide was used together with plasma, and nitrogen corresponding to an inert gas was used for purging. The film was formed at reaction gas and plasma time of 0.5 seconds. A specific method for depositing a silicon oxide thin film was illustrated in Table 1.

(75) A thickness of a deposited thin film was measured using the Ellipsometer, formation of the silicon oxide thin film was analyzed using infrared spectroscopy, and a composition of the silicon oxide thin film was analyzed using X-ray photoelectron spectroscopy. Further, a step coverage was confirmed using a transmission electron microscope (TEM). Specific analysis results of the silicon oxide thin film were illustrated in Table 2, and a result obtained by analyzing the deposited film using infrared spectroscopy was illustrated in FIG. 2.

[Comparative Example 3] Manufacturing of Silicon Oxide Thin Film by PEALD Using Bis(Diethylamino)Silane

(76) Film formation was evaluated using the bis(diethylamino)silane compound for forming a silicon oxide film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art. As a reaction gas, nitrous oxide was used together with plasma, and nitrogen corresponding to an inert gas was used for purging. The film was formed at reaction gas and plasma time of 0.5 seconds. A specific method for depositing a silicon oxide thin film was illustrated in Table 1.

(77) A thickness of a deposited thin film was measured using the Ellipsometer, formation of the silicon oxide thin film was analyzed using infrared spectroscopy, and a composition of the silicon oxide thin film was analyzed using X-ray photoelectron spectroscopy. Further, a step coverage was confirmed using a transmission electron microscope (TEM). Specific analysis results of the silicon oxide thin film were illustrated in Table 2, and a result obtained by analyzing the deposited film using infrared spectroscopy was illustrated in FIG. 2.

[Comparative Example 4] Manufacturing of Silicon Oxide Thin Film by PEALD Using [Bis(Diethylaminodimethylsilyl)]Trimethylsilylamine

(78) Film formation was evaluated using a [bis(diethylaminodimethylsilyl)]trimethylsilylamine compound in order to form a silicon oxide film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art. As a reaction gas, nitrous oxide was used together with plasma, and nitrogen corresponding to an inert gas was used for purging. The film was formed at reaction gas and plasma time of 0.5 seconds. A specific method for depositing a silicon oxide thin film was illustrated in Table 1.

(79) A thickness of a deposited thin film was measured using the Ellipsometer, formation of the silicon oxide thin film was analyzed using infrared spectroscopy, and a composition of the silicon oxide thin film was analyzed using X-ray photoelectron spectroscopy. Further, a step coverage was confirmed using a transmission electron microscope (TEM). Specific analysis results of the silicon oxide thin film were illustrated in Table 2, and a result obtained by analyzing the deposited film using infrared spectroscopy was illustrated in FIG. 2.

(80) TABLE-US-00001 TABLE 1 Deposition Conditions of Silicon Oxide Thin Film by PEALD Reaction Gas Reaction Precursor Purge and Plasma Gas Purge Temperature Heating Injection Flow Flow RF Flow Number of Process of Substrate Temperature Time Rate Time Rate Power Time Rate Time Deposition Time (° C.) (° C.) (sec) (sccm) (sec) (sccm) (W) (sec) (sccm) (sec) Cycle (sec) Example 3 50 38 0.1 600 0.4 300 400 0.5 300 0.1 150 165 Comparative 50 51 0.1 600 0.4 300 400 0.5 300 0.1 150 165 Example 3 Comparative 50 50 0.1 600 0.4 300 400 0.5 300 0.1 150 165 Example 4

(81) TABLE-US-00002 TABLE 2 Evaluation of Properties of Silicon Oxide Thin Film Refrac- O/Si Deposition Thickness Step tive Composition Rate of Film Coverage Index Ratio (Å/cycle) (Å) (%) — — Example 3 2.48 372 100 1.48 1.7 Comparative 1.37 206 100 1.48 1.73 Example 3 Comparative 1.71 257 93 1.48 1.71 Example 4

(82) As illustrated in Table 2, it may be appreciated that the silicon oxide film manufactured using a composition for depositing a silicon-containing thin film containing the silylamine compound according to the present invention as a precursor has an excellent step coverage while having an excellent deposition rate as compared to the silicon oxide films in Comparative Examples 3 and 4.

(83) That is, as illustrated in Table 2 and FIG. 3, in the silicon oxide film in Example 3 according to the present invention, the refractive index and the O/Si composition rate were similar to those in Comparative Examples 3 and 4, the deposition rate was excellent, the thickness of the thin film was significantly increased, and the step coverage also was excellent, as compared to the silicon oxide films in Comparative Examples 3 and 4.