Cyclodisilazane derivative, method for preparing the same and silicon-containing thin film using the same

Abstract

Provided are a novel cyclodisilazane derivative, a method for preparing the same, and a silicon-containing thin film using the same, wherein the cyclodisilazane derivative having thermal stability, high volatility, and high reactivity and being present in a liquid state at room temperature and under a pressure where handling is easy, may form a high purity silicon-containing thin film having excellent physical and electrical properties by various deposition methods.

Claims

1. A cyclodisilazane derivative represented by the following Chemical Formula 1: ##STR00006## in Chemical Formula 1, R.sup.1 to R.sup.3 are each independently hydrogen, halogen, (C1-C5)alkyl or (C2-C5)alkenyl, and R.sup.4 is C3 alkyl or (C2-C5)alkenyl.

2. The cyclodisilazane derivative of claim 1, wherein it is selected from the following compounds: ##STR00007##

3. A method for preparing a cyclodisilazane derivative represented by the following Chemical Formula 1, comprising: preparing a diaminosilane derivative represented by the following Chemical Formula 4 by reacting a silane derivative represented by the following Chemical Formula 2 with an amine derivative represented by the following Chemical Formula 3; and preparing the cyclodisilazane derivative represented by the following Chemical Formula 1 by an intramolecular cyclization reaction of the diaminosilane derivative represented by the following Chemical Formula 4 with a silane derivative represented by the following Chemical Formula 5 in the presence of (C1-C7)alkyllithium: ##STR00008## in Chemical Formulas 1 to 5, R.sup.1 to R.sup.3 are each independently hydrogen, halogen, (C1-C5)alkyl or (C2-C5)alkenyl, and R.sup.4 is C3 alkyl or (C2-C5)alkenyl, and X is halogen.

4. The method of claim 3, wherein the preparing of the diaminosilane derivative represented by Chemical Formula 4 is performed in the presence of a base represented by the following Chemical Formula 10 or (C1-C7)alkyllithium:
N(R.sup.6)(R.sup.7)(R.sup.8)  [Chemical Formula 10] in Chemical Formula 10, R.sup.6 to R.sup.8 are each independently (C1-C7)alkyl.

5. A method for preparing a cyclodisilazane derivative represented by the following Chemical Formula 1-2, the method comprising: preparing the cyclodisilazane derivative represented by the following Chemical Formula 1-2 by reacting a halocyclodisilazane derivative represented by the following Chemical Formula 1-1 with a metal hydride or an alkali metal derivative represented by the following Chemical Formula 8: ##STR00009## in Chemical Formulas 1-1, 1-2, and 8, M is an alkali metal; R.sup.10 is each independently hydrogen or (C1-C5)alkyl; at least one of R.sup.1 to R.sup.3 is halogen, and the remainder is hydrogen, halogen, (C1-C5)alkyl or (C2-C5)alkenyl; R.sup.4 is C3 alkyl or (C2-C5)alkenyl; and at least one of R.sup.1a to R.sup.3a is hydrogen, and the remainder is hydrogen, (C1-C5)alkyl or (C2-C5)alkenyl, wherein when R.sup.1 is halogen, R.sup.1a is hydrogen, and when R.sup.2 is halogen, R.sup.2a a is hydrogen, and when R.sup.3 is halogen, R.sup.3a a is hydrogen.

6. A method for preparing a cyclodisilazane derivative represented by the following Chemical Formula 9, the method comprising: preparing an aminosilane derivative represented by the following Chemical Formula 6 by reacting a silane derivative represented by the following Chemical Formula 2 with an amine derivative represented by the following Chemical Formula 3; preparing a halocyclodisilazane derivative represented by the following Chemical Formula 7 by an intramolecular cyclization reaction of the aminosilane derivative represented by the following Chemical Formula 6 in the presence of (C1-C7)alkyllithium; and preparing the cyclodisilazane derivative represented by the following Chemical Formula 9 by reacting the halocyclodisilazane derivative represented by the following Chemical Formula 7 with a metal hydride or an alkali metal derivative represented by the following Chemical Formula 8: ##STR00010## in Chemical Formulas 2, 3 and 6 to 9, R.sup.1 is halogen; R.sup.2 is hydrogen, halogen, (C1-C5)alkyl or (C2-C5)alkenyl; R.sup.4 is C3 alkyl or (C2-C5)alkenyl; X is halogen; M is an alkali metal; R.sup.10 is hydrogen or (C1-C5)alkyl; R.sup.1a is hydrogen; wherein when R.sup.2 is hydrogen or halogen, R.sup.2a a is hydrogen, and when R.sup.2 is (C1-C5)alkyl or (C2-C5)alkenyl, R.sup.2a is (C1-C5)alkyl or (C2-C5)alkenyl.

7. The method of claim 6, wherein the preparing of the aminosilane derivative represented by Chemical Formula 6 is performed in the presence of a base represented by the following Chemical Formula 10 or (C1-C7)alkyllithium:
N(R.sup.6)(R.sup.7)(R.sup.8)  [Chemical Formula 10] in Chemical Formula 10, R.sup.6 to R.sup.8 are each independently (C1-C7)alkyl.

8. The method of claim 6, wherein the metal hydride is one or a mixture of two or more, selected from the group consisting of LiH, NaH, KH and LiAlH.sub.4.

9. A composition for depositing a silicon-containing thin film, comprising the cyclodisilazane derivative of claim 1.

10. A method for manufacturing a silicon-containing thin film by using the cyclodisilazane derivative of claim 1.

11. A silicon-containing thin film manufactured by including the cyclodisilazane derivative of claim 1.

12. The method of claim 5, wherein the metal hydride is one or a mixture of two or more, selected from the group consisting of LiH, NaH, KH and LiAlH4.

Description

DESCRIPTION OF DRAWINGS

(1) The above and other objects, features and advantages of the present invention will become apparent from the following description of preferred embodiments given in conjunction with the accompanying drawings, in which:

(2) FIG. 1 shows a result obtained by thermogravimetric analysis of 1,3-diisopropyl-2,4-dimethylcyclodisilazane prepared by Example 1.

(3) FIG. 2 shows a result obtained by vapor pressure measurement of 1,3-diisopropyl-2,4-dimethylcyclodisilazane prepared by Example 1.

(4) FIG. 3 shows a result obtained by thermogravimetric analysis of 1,3-diisopropyl-4,4-dimethylcyclodisilazane prepared by Example 6.

(5) FIG. 4 shows a result obtained by vapor pressure measurement of 1,3-diisopropyl-4,4-dimethylcyclodisilazane prepared by Example 6.

(6) FIG. 5 shows a method for depositing silicon-containing thin films practiced by Example 7 and Comparative Example 1.

(7) FIG. 6 shows results obtained by a step coverage analysis of the silicon-containing thin films practiced by Example 7, using Transmission Electron Microscopy.

(8) FIG. 7 shows results obtained by an infrared spectroscopic analysis of the silicon-containing thin films practiced by Example 7 and Comparative Example 1.

(9) FIGS. 8A and 8B show results obtained by an auger electron spectroscopic analysis of the silicon-containing thin films practiced by Example 7.

(10) FIG. 9 shows results obtained by an etch rate analysis of the silicon-containing thin films practiced by Example 7 and Comparative Example 1, using an Ellipsometer.

(11) FIG. 10 is a diagram showing a method for depositing a silicon-containing thin film practiced by Example 8.

(12) FIG. 11 shows a result obtained by an infrared spectroscopic analysis of the silicon-containing thin film practiced by Example 8.

BEST MODE

(13) Hereinafter, the present invention will be described in more detail with reference to the following exemplary embodiments. However, the following exemplary embodiments describe the present invention by way of example only but are not limited thereto.

(14) The following Examples of all compounds were practiced under anhydrous and inert atmosphere using a glovebox or a Schlenk pipe, products were analyzed by .sup.1H Nuclear Magnetic Resonance (NMR, 400 MHz Ultrashield, Buruker), thermogravimetric analysis (TGA, L81-II, LINSEIS) and gas chromatography (GC, 7890A, Agilent Technologies), thickness of deposited thin films were measured by an Ellipsometer (M2000D, Woollam), and components of the films were analyzed by infrared spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optiks) and auger electron spectroscopy (Microlab 350, Thermo Electron).

EXAMPLE 1

Synthesis of 1,3-diisopropyl-2,4-dimethylcyclodisilazane

(15) 1) Synthesis of 1,3-diisopropyl-2,4-dichlorodimethylcyclodisilazane

(16) 127 g (0.86 mol) of trichloro(methyl)silane (CH.sub.3SiCl.sub.3) and 1200 ml of an organic solvent (n-hexane) were put into a 2000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, and 101.7 g (1.72 mol) of isopropylamine (H.sub.2NCH(CH.sub.3).sub.2) was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 3 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate. 200 ml of an organic solvent (n-hexane) was put into dichloro(methyl)(isopropylamino)silane (Cl.sub.2CH.sub.3SiNHCH(CH.sub.3).sub.2) recovered after the solvent was removed from the filtrate under reduced pressure, and stirred, and then 367.0 g (0.90 mol) of 1.7M t-butyllithium (t-C.sub.4H.sub.9Li) hexane (C.sub.6H.sub.14) solution was slowly added thereto while maintaining temperature at 40° C. After the addition was completed, a temperature of the reaction solution was slowly raised to 65° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 81.4 g (0.30 mol) of 1,3-diisopropyl-2,4-dichlorodimethylcyclodisilazane ((ClCH.sub.3SiNCH(CH.sub.3).sub.2).sub.2) was obtained by reduced pressure distillation with a yield of 70%.

(17) .sup.1H NMR (in C.sub.6D.sub.6) δ 0.50, 0.53(s, 6H, csi-NSi(CH.sub.3)Cl, trans-NSi(CH.sub.3)Cl), 1.07(d, 12H, Si(NCH(CH.sub.3).sub.2), 3.27(m, 2H, Si(NCH(CH.sub.3).sub.2); Boiling Point 197° C.

(18) 2) Synthesis of 1,3-diisopropyl-2,4-dimethylcyclodisilazane

(19) 100 g (0.37 mol) of 1,3-diisopropyl-2,4-dichlorodimethyl cyclodisilazane ((ClCH.sub.3SiNCH(CH.sub.3).sub.2).sub.2) synthesized in the above 1) and 200 ml of an organic solvent (THF) were put into a 1000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, and 7.33 g (0.92 mol) of lithium hydride (LiH) was slowly added thereto while maintaining temperature at −15° C. After the addition was completed, a temperature of the reaction solution was slowly raised to 65° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 60 g (0.3 mol) of 1,3-diisopropyl-2,4-dimethylcyclodisilazane ((HCH.sub.3SiNCH(CH.sub.3).sub.2).sub.2) was obtained by reduced pressure distillation with a yield of 80%.

(20) .sup.1H NMR (in C.sub.6D.sub.6) δ 0.33(m, 6H, NSiH(CH.sub.3)), 1.05(m, 12H, Si(NCH(CH.sub.3).sub.2), 3.20(m, 2H, Si(NCH(CH.sub.3).sub.2), 5.52(m, 2H, NSiH(CH.sub.3)); Boiling Point 173˜175° C.

EXAMPLE 2

Synthesis of 1,3-diisopropyl cyclodisilazane

(21) 1) Synthesis of 1,3-diisopropyl-2,2,4,4-tetrachlorocyclodisilazane

(22) 150 g (0.89 mol) of tetrachlorosilane (SiCl.sub.4) and 500 ml of an organic solvent (n-hexane) were put into a 2000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, and 104.76 g (1.77 mol) of isopropylamine (H.sub.2NCH(CH.sub.3).sub.2) was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 3 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate. 200 ml of an organic solvent (n-hexane) was put into trichloro(isopropylamino)silane (Cl.sub.3SiNHCH(CH.sub.3).sub.2) recovered after the solvent was removed from the filtrate under reduced pressure, and stirred, and then 368.38 g (0.90 mol) of 1.7M t-butyllithium (t-C.sub.4H.sub.9Li) hexane (C.sub.6H.sub.14) solution was slowly added thereto while maintaining temperature at 40° C. After the addition was completed, a temperature of the reaction solution was slowly raised to 65° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 121.7 g (0.35 mol) of 1,3-diisopropyl-2,2,4,4-tetrachlorocyclodisilazane ((Cl.sub.2SiNCH(CH.sub.3).sub.2).sub.2) was obtained by reduced pressure distillation with a yield of 88%.

(23) .sup.1H NMR (in C.sub.6D.sub.6) δ 1.10(d, 12H, Si(NCH(CH.sub.3).sub.2), 3.34(m, 2H, Si(NCH(CH.sub.3).sub.2); Boiling Point 216˜217° C.

(24) 2) Synthesis of 1,3-diisopropyl cyclodisilazane

(25) 80 g (0.26 mol) of 1,3-diisopropyl-2,2,4,4-tetrachlorocyclodisilazane ((Cl.sub.2SiNCH(CH.sub.3).sub.2).sub.2) synthesized in the above 1) and 400 ml of an organic solvent (diethylether) were put into a 2000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, and 12.35 g (1.55 mol) of lithium aluminum hydride (LiAlH.sub.4) was slowly added thereto while maintaining temperature at −15° C. After the addition was completed, a temperature of the reaction solution was slowly raised to 60° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 26.8 g (0.16 mol) of 1,3-diisopropylcyclodisilazane ((H.sub.2SiNCH(CH.sub.3).sub.2).sub.2) was obtained by reduced pressure distillation with a yield of 60%.

(26) .sup.1H NMR (in C.sub.6D.sub.6) δ 1.11(d, 12H, Si(NCH(CH.sub.3).sub.2), 3.23(m, 2H, Si(NCH(CH.sub.3).sub.2), 4.48(s, 2H, NSiH); Boiling Point 155˜160° C.

EXAMPLE 3

Synthesis of 1,3-diisopropyl-2-chloro-4,4-dimethyl cyclodisilazane

(27) 214 g (1.66 mol) of dichlorodimethylsilane (Si(CH.sub.3).sub.2Cl.sub.2) and 1000 ml of an organic solvent (n-hexane) were put into a 2000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, and 392.1 g (6.63 mol) of isopropylamine (H.sub.2NCH(CH.sub.3).sub.2) was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 3 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate. 300 ml of an organic solvent (n-hexane) was put into di(isopropylamino)dimethylsilane ((CH.sub.3).sub.2Si(NHCH(CH.sub.3).sub.2).sub.2) recovered after the solvent was removed from the filtrate under reduced pressure, and stirred, and then 1005.3 g (3.32 mol) of 2.5M n-butyllithium (n-C.sub.4H.sub.9Li) hexane (C.sub.6H.sub.14) solution was slowly added thereto while maintaining temperature at −15° C. After the addition was completed, a temperature of the reaction solution was slowly raised to 25° C., and the reaction solution was stirred for 12 hours, and then, 224.6 g (1.66 mol) of trichlorosilane (SiHCl.sub.3) was slowly added thereto. After the addition was completed, a temperature of the reaction solution was slowly raised to 65° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 255.3 g (1.08 mol) of 1,3-diisopropyl-2-chloro-4,4-dimethylcyclodisilazane (((CH.sub.3).sub.2SiNCH(CH.sub.3).sub.2)(ClSiHNCH(CH.sub.3).sub.2)) was obtained by reduced pressure distillation with a yield of 65%.

(28) .sup.1H NMR (in C.sub.6D.sub.6) δ 0.19 and 0.21 (s, 6H, NSi(CH.sub.3).sub.2), 1.03(d, 12H, Si(NCH(CH.sub.3).sub.2), 3.17(m, 2H, Si(NCH(CH.sub.3).sub.2), 5.99(s, 1H, NSiHCl); Boiling Point 190° C.

EXAMPLE 4

Synthesis of 1,3-diisopropyl-2-chloro-4,4-dimethyl cyclodisilazane

(29) 107 g (0.83 mol) of dichlorodimethylsilane ((CH.sub.3).sub.2SiCl.sub.2) and 400 ml of an organic solvent (n-hexane) were put into a 1000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, and 167.7 g (1.66 mol) of triethylamine (C.sub.2H.sub.5).sub.3N) was slowly added thereto while maintaining temperature at −10° C., and then 98.0 g (1.65 mol) of isopropylamine (H.sub.2NCH(CH.sub.3).sub.2) was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 3 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate. 200 ml of an organic solvent (n-hexane) was put into di(isopropylamino)dimethylsilane ((CH.sub.3).sub.2Si(NHCH(CH.sub.3).sub.2).sub.2) recovered after the solvent was removed from the filtrate under reduced pressure, and stirred, and then 351.8 g (1.16 mol) of 2.5M n-butyllithium (n-C.sub.4H.sub.9Li) hexane (C.sub.6H.sub.14) solution was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred for 12 hours, and then, 224.6 g (1.66 mol) of trichlorosilane (SiHCl.sub.3) was slowly added thereto. After the addition was completed, a temperature of the reaction solution was slowly raised to 65° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 255.3 g (1.08 mol) of 1,3-diisopropyl-2-chloro-4,4-dimethylcyclodisilazane (((CH.sub.3).sub.2SiNCH(CH.sub.3).sub.2)(ClSiHNCH(CH.sub.3).sub.2)) was obtained by reduced pressure distillation with a yield of 65%.

(30) .sup.1H NMR (in C.sub.6D.sub.6) δ 0.19 and 0.21 (s, 6H, NSi(CH.sub.3).sub.2), 1.03(d, 12H, Si(NCH(CH.sub.3).sub.2), 3.17(m, 2H, Si(NCH(CH.sub.3).sub.2), 5.99(s, 1H, NSiHCl); Boiling Point 190° C.

EXAMPLE 5

Synthesis of 1,3-diisopropyl-2-chloro-4,4-dimethyl cyclodisilazane

(31) 98.0 g (1.65 mol) of isopropylamine (H.sub.2NCH(CH.sub.3).sub.2) and 400 ml of an organic solvent (n-hexane) were put into a 1000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, and 500.4 g (1.65 mol) of 2.5M n-butyllithium (n-C.sub.4H.sub.9Li) hexane (C.sub.6H.sub.14) solution was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 3 hours, and then 107 g (0.83 mol) of dichlorodimethylsilane ((CH.sub.3).sub.2SiCl.sub.2) was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred at room temperature for 3 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate. 200 ml of an organic solvent (n-hexane) was put into di(isopropylamino)dimethylsilane ((CH.sub.3).sub.2Si(NHCH(CH.sub.3).sub.2).sub.2) recovered after the solvent was removed from the filtrate under reduced pressure, and stirred, and then 351.8 g (1.16 mol) of 2.5M n-butyllithium (n-C.sub.4H.sub.9Li) hexane (C.sub.6H.sub.14) solution was slowly added thereto while maintaining temperature at −10° C. After the addition was completed, a temperature of the reaction solution was slowly raised to room temperature, and the reaction solution was stirred for 12 hours, and then, 224.6 g (1.66 mol) of trichlorosilane (SiHCl.sub.3) was slowly added thereto. After the addition was completed, a temperature of the reaction solution was slowly raised to 65° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 196.4 g (0.83 mol) of 1,3-diisopropyl-2-chloro-4,4-dimethylcyclodisilazane (((CH.sub.3).sub.2SiNCH(CH.sub.3).sub.2)(ClSiHNCH(CH.sub.3).sub.2)) was obtained by reduced pressure distillation with a yield of 50%.

(32) .sup.1H NMR (in C.sub.6D.sub.6) δ 0.19 and 0.21 (s, 6H, NSi(CH.sub.3).sub.2), 1.03(d, 12H, Si(NCH(CH.sub.3).sub.2), 3.17(m, 2H, Si(NCH(CH.sub.3).sub.2), 5.99(s, 1H, NSiHCl); Boiling Point 190° C.

EXAMPLE 6

Synthesis of 1,3-diisopropyl-4,4-dimethylcyclodisilazane

(33) 200 g (0.84 mol) of 1,3-diisopropyl-2-chloro-4,4-dimethylcyclodisilazane (((CH.sub.3).sub.2SiNCH(CH.sub.3).sub.2)(ClSiHNCH(CH.sub.3).sub.2)) synthesized in Example 3 above and 600 ml of an organic solvent (THF) were put into a 2000 mL flame-dried Schlenk flask and stirred under anhydrous and inert atmosphere, 7.4 g (0.93 mol) of lithium hydride (LiH) was slowly added thereto while maintaining temperature at −15° C. After the addition was completed, a temperature of the reaction solution was slowly raised to 65° C., and the reaction solution was stirred for 12 hours. After the stirring was completed, the reaction solution was filtrated, and a white solid obtained by the filtration was removed to obtain a filtrate, and then a solvent was removed from the filtrate under reduced pressure, and 85.46 g (0.42 mol) of 1,3-diisopropyl-4,4-dimethylcyclodisilazane (((CH.sub.3).sub.2SiNCH(CH.sub.3).sub.2)(SiH.sub.2NCH(CH.sub.3).sub.2)) was obtained by reduced pressure distillation with a yield of 50%.

(34) .sup.1H NMR (in C.sub.6D.sub.6) δ 0.26(s, 6H, NSi(CH.sub.3).sub.2), 1.06(d, 12H, Si(NCH(CH.sub.3).sub.2), 3.18(m, 2H, Si(NCH(CH.sub.3).sub.2), 5.51(s, 1H, NSiH.sub.2); Boiling Point 175° C.

EXAMPLE 7

Deposition of Silicon Oxide Film by Plasma Enhanced Atomic Layer Deposition (PEALD) Using Cyclodisilazane Derivative

(35) Film forming evaluation was conducted by using 1,3-diisopropyl-2,4-dimethylcyclodisilazane of Example 1 and 1,3-diisopropyl-4,4-dimethylcyclodisilazane of Example 6 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 the known PEALD method. Oxygen together with plasma was used as the reaction gas, and argon which is an inert gas was used for purge. Hereinafter, FIG. 5 and Table 1 specifically show a method for depositing a silicon oxide thin film.

(36) TABLE-US-00001 TABLE 1 Deposition Condition of Silicon Oxide Thin film Precursor 1,3-diisopropyl-2,4- 1,3-diisopropyl-4,4- dimethylcyclodisilazane dimethylcyclodisilazane (Example 1) (Example 6) Heating Temperature (° C.) of 40 40 40 40 Precursor Substrate Temperature (° C.) 100 100 100 100 Kind of Substrate Si wafer Si Pattern wafer. Si wafer Si Pattern wafer. Hole Size 200 nm Hole Size 200 nm Aspect Ratio: 5 Aspect Ratio: 5 Injection Time (sec) of Precursor 6 18 9 18 Purge Flow Amount (sccm) 1100 1100 1100 1100 Time (sec) 20 60 20 60 400 W Flow Amount (sccm) 300/100 300/100 300/100 300/100 Oxygen of Oxygen/Argon Plasma Time (sec) 10 20 10 20 Purge Flow Amount (sccm) 1100 1100 1100 1100 Time (sec) 15 30 15 30 Frequency of Cycle 50 273 50 406 Deposition

(37) A thickness of the deposited thin film was measured by an Ellipsometer, and formation of SiO.sub.2 thin film and components of the thin film were analyzed by infrared spectroscopy and auger electron spectroscopy. In 50 cycles on a Si wafer, a thickness of the thin film of 1,3-diisopropyl-2,4-dimethylcyclodisilazane (Example 1) was 76.98 Å and a thickness of the thin film of 1,3-diisopropyl-4,4-dimethylcyclodisilazane (Example 6) was 78.84 Å. In addition, in 273 cycles on a Si pattern wafer, a thickness of the thin film manufactured by including 1,3-diisopropyl-2,4-dimethylcyclodisilazane (Example 1) was 317 Å, and in 406 cycles on a Si pattern wafer, a thickness of the thin film manufactured by including 1,3-diisopropyl-4,4-dimethylcyclodisilazane (Example 6) was 436 Å. Further, step coverage was 98.17 to 101.89%. Therefore, it is determined that these thin films are capable of being effectively used throughout all silicon oxide thin film application fields requiring a high deposition rate and excellent step coverage (FIG. 6).

(38) In addition, as shown in FIGS. 7 and 8, all of the deposited thin films were formed as silicon oxide films, and peak of impurities such as C—H, Si—OH was not observed (FIG. 7). A ratio between oxygen and silicon in the thin film formed by using 1,3-diisopropyl-2,4-dimethylcyclodisilazane (Example 1) was 2.07:1 and a ratio between oxygen and silicon in the thin film formed by using 1,3-diisopropyl-4,4-dimethylcyclodisilazane (Example 6) was 2.03:1, and carbon and nitrogen had a content of 0%, and therefore, it could be confirmed that high purity silicon oxide thin film was formed (FIG. 8).

(39) In addition, an etch rate of the deposited thin film was confirmed by using buffered oxide etchant (BOE) solution (300:1). The silicon oxide thin film deposited by using 1,3-diisopropyl-2,4-dimethylcyclodisilazane (Example 1) was etched at a rate of 0.58 Å/sec, and the silicon oxide thin film deposited by using 1,3-diisopropyl-4,4-dimethylcyclodisilazane (Example 6) was etched at a rate of 0.59 Å/sec. As a result obtained by thermal treating each sample at 750° C. for 30 minutes and confirming an etch rate, an etch rate of the oxide thin film of 1,3-diisopropyl-2,4-dimethylcyclodisilazane was 0.47 Å/sec and an etch rate of the oxide thin film of 1,3-diisopropyl-4,4-dimethylcyclodisilazane was 0.54 Å/sec, which was confirmed that an etch rate was decreased. It was confirmed that an etch rate of a thermal oxide thin film deposited at 1000° C. used as a comparative sample was 0.30 Å/sec (FIG. 9).

(40) That is, it was confirmed that the novel cyclodisilazane derivative prepared by the present invention has high utilization value in forming a high purity silicon oxide thin film having a high deposition rate, excellent step coverage, and etch resistance by plasma enhanced atomic layer deposition (PEALD).

COMPARATIVE EXAMPLE 1

Deposition of Silicon Oxide Film by Plasma Enhanced Atomic Layer Deposition (PEALD) Using Known Aminosilyl Amine Compound

(41) The film forming evaluation of Comparative Example was conducted by the known PEALD under the same deposition conditions as practiced by Example 7 above except for using known aminosilyl amine compound as shown in the following Table 2, then, the deposited thin film was analyzed by the same analysis method and conditions as practiced by Example 7 above, and the analysis result thereof was obtained. Hereinafter, FIG. 5 and Table 2 specifically show a method for depositing the silicon oxide thin film.

(42) TABLE-US-00002 TABLE 2 Silicon Oxide Thin film Deposition Condition Precursor Bis- Bis- diethylamino ethylmethylamino silane silane (Precursor A) (Precursor B) Heating Temperature (° C.) of 40 40 Precursor Substrate Temperature (° C.) 100 100 Kind of Substrate Si wafer Si wafer Injection Time (sec) of Precursor 0.5 0.2 Purge Flow Amount (sccm) 1100 1100 Time (sec) 20 20 400 W Flow Amount (sccm) 300/100 300/100 Oxygen of Oxygen/Argon Plasma Time (sec) 10 10 Purge Flow Amount (sccm) 1100 1100 Time (sec) 15 15 Frequency of Cycle 50 50 Deposition

(43) A thickness of each deposited thin film was measured by an Ellipsometer, and formation of SiO.sub.2 thin film was analyzed by infrared spectroscopy. In 50 cycles on a Si wafer, the thickness of the thin films were 72.5 Å (precursor A) and 68.5 Å (precursor B), which showed low deposition rate as compared to the cyclodisilazane derivatives practiced by Example 7, and all of the thin films were formed as silicon oxide films (FIG. 7).

(44) In addition, an etch rate of the deposited thin film was confirmed by using buffered oxide etchant (BOE) solution (300:1). The silicon oxide thin film deposited by using precursor A was etched at a rate of 0.86 Å/sec, and the silicon oxide thin film deposited by using precursor B was etched at a rate of 0.94 Å/sec. As a result obtained by thermal treating each sample at 750° C. for 30 minutes and confirming an etch rate, an etch rate of the oxide thin film of the precursor A was 0.66 Å/sec and an etch rate of the oxide thin film of the precursor B was 0.69 Å/sec, which was confirmed that an etch rate was decreased. It was confirmed that an etch rate of a thermal oxide thin film deposited at 1000° C. used as a comparative sample was 0.30 Å/sec (FIG. 9).

EXAMPLE 8

Deposition of Silicon Nitride Film by Plasma Enhanced Atomic Layer Deposition (PEALD) Using Cyclodisilazane Derivative

(45) Film formation evaluation was conducted by using 1,3-diisopropyl-2,4-dimethylcyclodisilazane of Example 1 according to the present invention as a composition for forming a silicon nitride film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using the known PEALD method. Nitrogen together with plasma was used as a reaction gas, and the same nitrogen gas was used for purge. Hereinafter, FIG. 10 and Table 3 specifically show a method for depositing the silicon nitride thin film.

(46) TABLE-US-00003 TABLE 3 Silicon Nitride Thin-Film Deposition Conditions Precursor 1,3-diisopropyl-2,4- dimethylcyclodisilazane (Example 1) Heating Temperature (° C.) of Precursor 40 Substrate Temperature (° C.) 300 Kind of Substrate Si wafer Injection Time (sec) of Precursor 5 Purge Flow Amount (sccm) 2000 Time (sec) 16 100 W Flow Amount (sccm) 400 Nitrogen of Nitrogen Plasma Time (sec) 10 Purge Flow Amount (sccm) 2000 Time (sec) 12 Frequency of Cycle 500 Deposition

(47) A thickness of the deposited thin film was measured by an Ellipsometer, and formation of SiN thin film and components of the thin film were analyzed by infrared spectroscopy and auger electron spectroscopy. In 500 cycles on a Si wafer, a thickness of the thin film was 150.70Å.

(48) In addition, as shown in FIG. 11, it was observed that all of the deposited thin films were formed as silicon nitride films, and a small number of bonds such as N—H, Si—H were included.

(49) Further, an etch rate of the deposited thin film was confirmed by using buffered oxide etchant (BOE) solution (300:1). The deposited silicon nitride thin film was etched at a rate of 0.05 Å/sec, and a thermal oxide thin film deposited at 1000° C. used as a comparative sample was etched at a rate of 0.34 Å/sec, and a silicon nitride thin film deposited by low pressure chemical vapor deposition (LPCVD) at 770° C. using dichlorosilane was etched at a rate of 0.02 Å/sec.

(50) That is, it was confirmed that the novel cyclodisilazane derivative prepared by the present invention has high utilization value in forming a high purity silicon nitride thin film having a high deposition rate and excellent etch resistance by plasma enhanced atomic layer deposition (PEALD).

INDUSTRIAL APPLICABILITY

(51) The cyclodisilazane derivative of the present invention has excellent thermal stability and high reactivity, such that the silicon-containing thin film manufacturing by using the cyclodisilazane derivative as a precursor may have high purity and significantly excellent physical and electrical properties.

(52) In addition, the cyclodisilazane derivative of the present invention may have high content of silicon and is present in a liquid state at room temperature and under atmospheric pressure to thereby be easily stored and handled, and may have high volatility and high reactivity to be rapidly and easily deposited, and it is possible to deposit a thin film having excellent cohesion and superior step coverage.