Composition for depositing silicon-containing thin film containing bis(aminosilyl)alkylamine compound and method for manufacturing silicon-containing thin film using the same

Abstract

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

Claims

1. A composition for depositing a silicon-containing thin film, the composition comprising a bis(aminosilyl)alkylamine compound represented by the following Chemical Formula 1 is represented by the following Chemical Formula 4 or 5: ##STR00020## in Chemical Formula 1, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.1 to R.sub.4 are each independently hydrogen, 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 R.sub.5 to R.sub.8 are each independently hydrogen, halogen, C1-C7 alkyl, or C2-C7 alkenyl; ##STR00021## in Chemical Formulas 4 and 5, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.11 to R.sub.14 are each independently hydrogen, C1-C7 alkyl, or C2-C7 alkenyl; R.sub.5 and R.sub.6 are each independently C1-C7 alkyl, or C2-C7 alkenyl; and n and m are each independently an integer of 1 to 7.

2. The composition of claim 1, wherein in Chemical Formulas 4 and 5, R is C1-C5 alkyl; R.sub.5 and R.sub.6 are each independently C1-C5alkyl; and n and m are each independently an integer of 1 to 4.

3. The composition of claim 1, wherein the bis(aminosilyl)alkylamine compound is selected from the following compounds: ##STR00022##

4. A method for manufacturing a silicon-containing thin film, using a composition for depositing the silicon-containing thin film, wherein the method comprises a) maintaining a temperature of a substrate mounted in a chamber at 30° C. to 500° C.; b) contacting the composition 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 the silicon-containing thin film; wherein the composition comprising a bis(aminosilyl)alkylamine compound represented by the following Chemical Formula 1: ##STR00023## in Chemical Formula 1, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.1 to R.sub.4 are each independently hydrogen, 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 R.sub.5 to R.sub.8 are each independently hydrogen, halogen, C1-C7 alkyl, or C2-C7 alkenyl.

5. The method of claim 4, 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.

6. The method of claim 4, 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.

7. The method of claim 4, wherein the reaction gas is supplied after being activated by generating plasma with a plasma power of 50 to 1000 W.

8. The method of claim 4, wherein in Chemical Formula 1, R.sub.5 to R.sub.7 are each independently hydrogen, halogen, C1-C7 alkyl, or C2-C7 alkenyl, and R.sub.8 is hydrogen.

9. The method of claim 4, wherein the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 is represented by the following Chemical Formula 2 or 3: ##STR00024## in Chemical Formula 2 or 3, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.5 to R.sub.7 are each independently hydrogen, halogen, C1-C7 alkyl, or C2-C7-alkenyl; R.sub.11 to R.sub.14 are each independently hydrogen, C1-C5 alkyl, or C2-C5 alkenyl; and n and m are each independently an integer of 1 to 7.

10. The method of claim 9, wherein in Chemical Formula 2 or 3, R.sub.5 to R.sub.7 are each independently hydrogen or C1-C7 alkyl; R.sub.11 to R.sub.14 are each independently hydrogen, C1-C5 alkyl, or C2-C5 alkenyl; and n and m are each independently an integer of 1 to 4.

11. The method of claim 4, wherein the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 is represented by the following Chemical Formula 4 or 5: ##STR00025## in Chemical Formulas 4 and 5, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.11 to R.sub.14 are each independently hydrogen, C1-C7 alkyl, or C2-C7 alkenyl; R.sub.5 and R.sub.6 are each independently C1-C7 alkyl or C2-C7 alkenyl; and n and m are each independently an integer of 1 to 7.

12. The method of claim 4, wherein the bis(aminosilyl)alkylamine compound represented by following Chemical Formula 1 is selected from the following compounds: ##STR00026## ##STR00027##

13. A bis(aminosilyl)alkylamine compound represented by the following Chemical Formula 1: ##STR00028## in Chemical Formula 1, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.1 to R.sub.4 are each independently hydrogen, 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; R.sub.5 and R.sub.6 are each independent C1-C7 alkyl or C2-C7 alkenyl; and R.sub.7 and R.sub.8 are each hydrogen.

14. The bis(aminosilyl)alkylamine compound of claim 13, wherein the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 is represented by Chemical Formula 2 or 3: ##STR00029## In Chemical Formula 2 or 3, R is C1-C7 alkyl or C2-C7 alkenyl; R.sub.5 and R.sub.6 are each independent C1-C7 alkyl or C2-C7 alkenyl; and R.sub.7 is each hydrogen; R.sub.11 to R.sub.14 are each independently hydrogen, C1-C5 alkyl, or C2-C5 alkenyl; and n and m are each independently an integer of 1 to 7.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 is a view illustrating a result obtained by measuring vapor pressures of bis(aminosilyl)alkylamine compounds prepared in Examples 1 and 2.

(2) FIG. 2 is a view illustrating results obtained by performing thermogravimetric analysis on the bis(aminosilyl)alkylamine compounds prepared in Examples 1 and 2.

(3) FIG. 3 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon oxide thin films manufactured in Examples 3 to 5.

(4) FIG. 4 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon nitride thin films manufactured in Examples 6 to 9.

DETAILED DESCRIPTION

Best Mode

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

(6) ##STR00007##

(7) (In Chemical Formula 1, R is (C1-C7)alkyl or (C2-C7)alkenyl; R.sub.1 to R.sub.4 are each independently hydrogen, (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 R.sub.5 to R.sub.8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)

(8) The composition for depositing a silicon-containing thin film according to the present invention contains a precursor for depositing a thin film represented by Chemical Formula 1, such that film formation may be performed at a low temperature, and at the same time, a high-quality thin film having high durability may be easily manufactured.

(9) Further, the composition for depositing a silicon-containing thin film according to the present invention contains the precursor for depositing a thin film represented by Chemical Formula 1, the thin film may be deposited at a high thin film deposition rate, and the film has excellent stress properties and water vapor transmission rate.

(10) The reason may be that as the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1, contained in the composition for depositing a silicon-containing thin film has two aminosilyl groups and one alkyl or alkenyl group as substituents, the bis(aminosilyl)alkylamine compound has high volatility and excellent thermal stability.

(11) Preferably, in Chemical Formula 1 according to the exemplary embodiment, R.sub.5 to R.sub.7 may be each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl, and R.sub.8 may be hydrogen.

(12) Preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to an exemplary embodiment of the present invention may be represented by the following Chemical Formula 2 or 3.

(13) ##STR00008##

(14) (In Chemical Formula 2 or 3, R is (C1-C7)alkyl or (C2-C7)alkenyl; R.sub.5 to R.sub.7 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl; R.sub.11 to R.sub.14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and m are each independently an integer of 1 to 7.)

(15) In the bis(aminosilyl)alkylamine compound represented by Chemical Formula 2 or 3 according to the present invention, two aminosilyl functional groups and one alkyl or alkenyl group are substituted, such that the bis(aminosilyl)alkylamine compound is thermally stable, and at the same time, the bis(aminosilyl)alkylamine compound has a silazane backbone in which at least one hydrogen atom in at least one of two aminosilyl functional groups is substituted, such that the bis(aminosilyl)alkylamine compound has high volatility as a liquid at room temperature. Therefore, the bis(aminosilyl)alkylamine compound may be significantly usefully used to form a silicon-containing thin film.

(16) More specifically, the bis(aminosilyl)alkylamine compound according to the present invention, which is a compound having the silazane backbone, essentially has two aminosilyl functional groups

(17) ##STR00009##
and silyl in one of the aminosilyl functional groups necessarily has a functional group containing at least one hydrogen atom

(18) ##STR00010##
such that the bis(aminosilyl)alkylamine compound may have excellent effects as the precursor for depositing a thin film.

(19) Preferably, in Chemical Formula 2 or 3 according to the exemplary embodiment of the present invention, R.sub.5 to R.sub.7 may be each independently hydrogen or (C1-C5)alkyl; R.sub.11 to R.sub.14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and m may be each independently an integer of 1 to 4.

(20) More preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the present invention may be represented by the following Chemical Formula 4 or 5.

(21) ##STR00011##

(22) (In Chemical Formulas 4 and 5, R is (C1-C7)alkyl or (C2-C7)alkenyl; R.sub.11 to R.sub.14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl; and R.sub.5 and R.sub.6 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl; and n and m are each independently an integer of 1 to 7.)

(23) Preferably, in Chemical Formulas 4 and 5 according to the exemplary embodiment of the present invention, R may be (C1-C5)alkyl; R.sub.5 and R.sub.6 may be each independently (C1-C5)alkyl; and n and m may be each independently an integer of 1 to 4. More preferably, the bis(aminosilyl)alkylamine compound may be represented by Chemical Formula 4, and in Chemical Formula 4, R may be (C1-C3)alkyl; and R.sub.5 and R.sub.6 may be each independently (C1-C3)alkyl.

(24) Preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 6 or 7.

(25) ##STR00012##

(26) (In Chemical Formulas 6 and 7, R is (C1-C7)alkyl or (C2-C7)alkenyl; R.sub.11 to R.sub.14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl; and n and m are each independently an integer of 1 to 7.)

(27) More preferably, in Chemical Formulas 6 and 7, R may be (C1-C5)alkyl; R.sub.11 to R.sub.14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; n and m may be each independently an integer of 1 to 4. Preferably, R may be (C1-C5)alkyl; R.sub.11 to R.sub.14 may be each independently (C1-C5)alkyl; and n and m may be each independently 1 to 4. More preferably, the bis(aminosilyl)alkylamine compound may be represented by Chemical Formula 6, wherein in Chemical Formula 6, R may be (C1-C3)alkyl; and R.sub.11 to R.sub.14 may be each independently (C1-C3)alkyl.

(28) When silyl groups of two aminosilyl groups in the silazane backbone of the bis(aminosilyl)alkylamine compound according to the present invention have two or four hydrogen atoms, the bis(aminosilyl)alkylamine compound has more excellent reactivity and thermal stability as the precursor for depositing a thin film, such that a higher-quality thin film may be manufactured.

(29) In view of the precursor for depositing a thin film having more excellent properties, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 4 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 4-1.

(30) ##STR00013##

(31) (In Chemical Formula 4-1, R is (C1-C7)alkyl or (C2-C7)alkenyl; R.sub.1 and R.sub.2 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R.sub.1 and R.sub.2 is each independently linked to each other to form a ring; and R.sub.5 is (C1-C7)alkyl or (C2-C7)alkenyl.)

(32) In view of the precursor for depositing a thin film having more excellent properties, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 6 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 6-1.

(33) ##STR00014##

(34) (In Chemical Formula 6-1, R is (C1-C7)alkyl or (C2-C7)alkenyl; and 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.)

(35) Although not limited, but a specific example of the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may include the following compounds.

(36) ##STR00015## ##STR00016##

(37) The composition for depositing a silicon-containing thin film according to the present invention needs to necessarily contain the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 as the precursor for depositing a thin film, and the bis(aminosilyl)alkylamine compound may be contained in the composition for depositing a silicon-containing thin film 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.

(38) 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, isopropyl, butyl, isobutyl, neobutyl, pentyl, and the like.

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

(40) As used 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, the 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.

(41) 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.

(42) As used herein, the term “alicyclic ring” means a compound that is not an aromatic compound among organic compounds having a cyclic bonding structure.

(43) The bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the present invention may be prepared using a method as long as the method may be recognized by those skilled in the art.

(44) 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 present invention.

(45) Since in the method for manufacturing a silicon-containing thin film, the composition for depositing a silicon-containing thin film according to the present invention, containing the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1, which is a liquid art room temperature and normal pressure and has high volatility and excellent thermal stability, as the precursor is used, 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, an excellent water vapor transmission rate, and excellent thin film stress properties at a high deposition rate even at a low temperature and a low power.

(46) The silicon-containing thin film manufactured by the method according to the present invention has excellent durability and electric properties, and resistance against hydrogen fluoride and step coverage thereof are also excellent.

(47) 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.

(48) 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, particularly, a thin film usable as an encapsulant of an organic light emitting diode (OLED), may be manufactured.

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

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

(51) 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

(52) 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.

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

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

(55) 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;

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

(57) 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

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

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

(60) In the method for manufacturing a silicon-containing thin film according to the exemplary embodiment of the present invention, a bis(aminosilyl)alkylamine compound according to the present invention is used as the precursor, such that the reaction gas may be activated at preferably 30 to 500° C., and more preferably 30 to 300° C. by generating plasma at a low plasma power of 50 to 1000 W, preferably 100 to 800 W, and more preferably 400 to 600 W, thereby making it possible to manufacture the thin film.

(61) 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 bis(aminosilyl)alkyl amine 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 80 to 300° C., but the deposition conditions are not limited thereto.

(62) 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.

(63) 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.

(64) 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.

(65) In addition, the present invention provides a bis(aminosilyl)alkyl amine compound capable of being used as a precursor of a silicon-containing thin film. The bis(aminosilyl)alkyl amine compound according to the present invention is represented by the following Chemical Formula 1.

(66) ##STR00017##

(67) (In Chemical Formula 1, R is (C1-C7)alkyl or (C2-C7)alkenyl; and R.sub.1 to R.sub.4 are each independently hydrogen, (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 R.sub.5 to R.sub.8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)

(68) The bis(aminosilyl)alkyl amine compound according to the present invention, represented by Chemical Formula 1 is a liquid at room temperature and has high volatility and excellent thermal stability as described above, such that the bis(aminosilyl)alkyl amine compound is used as a significantly useful precursor in forming a silicon-containing thin film.

(69) Further, since in silyl (silicon) of each aminosilyl group, four hydrogen atoms are present, the bis(aminosilyl)alkyl amine compound has excellent reactivity, such that the thin film may be deposited at a rapid deposition rate, and the thin film with a high purity may be manufactured.

(70) Preferably, the bis(aminosilyl)alkyl amine compound represented by Chemical Formula 1 may be represented by Chemical Formula 2, and more preferably Chemical Formula 6 or 7.

(71) 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.

(72) 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.

(73) 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).

(74) A thickness of a deposited silicon-containing thin film was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and properties of the thin film were analyzed using infrared spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics), X-ray photoelectron spectroscopy, a water vapor transmission rate (WVTR) analyzer (MOCON, Aquatran 2), and a stress analyzer (Frontier Semiconductor, FSM500TC).

[Example 1] Preparation of Bis(methyldimethylaminosilyl)methylamine

(75) ##STR00018##

(76) Under an anhydrous and inert atmosphere, after putting dichloromethylsilane (SiH(CH.sub.3)Cl.sub.2, 115 g (1.0 mol)) and n-pentane (577 g (8 mol)) into a 1000 mL flame-dried flask and slowly adding methylamine (CH.sub.3NH.sub.2, 59 g (1.9 mol)) thereto while maintaining a temperature at −25° C., the mixture was stirred for 3 hours, and methylamine hydrochloride ((CH.sub.3)NH.sub.3Cl) was removed by filtration. While stirring a recovered bis(chloromethylsilyl)methylamine ((SiH(CH.sub.3)C1).sub.2N(CH.sub.3)) solution with n-pentane and maintaining a temperature at −25° C., dimethylamine ((CH.sub.3).sub.2NH, 94 g (7.13 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 removing dimethylamine hydrochloride ((CH.sub.3).sub.2NH.sub.2Cl, white) formed by filtering the resultant, a filtrate was obtained. A solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(methyldimethylaminosilyl)methylamine ((CH.sub.3).sub.2NSiH(CH.sub.3)).sub.2N(CH.sub.3), 71 g (0.35 mol), yield: 70%).

(77) .sup.1H-NMR (inCDCl.sub.3): δ 0.16 (t, 6H (Si—CH.sub.3).sub.2), 2.42 (d, 3H (NCH.sub.3)), 2.48 (s, 12H, ((CH.sub.3).sub.2NSi)).sub.2, 4.39 (m, 2H, (—SiHN).sub.2).

[Example 2] Preparation of Bis(ethylmethylaminosilyl)methylamine

(78) ##STR00019##

(79) Under an anhydrous and inert atmosphere, after putting dichlorosilane (SiH.sub.2Cl.sub.2, 360 g (3.56 mol)) and n-pentane (3,202 g (27.79 mol)) into a 5000 mL flame-dried Sus reactor (a high-pressure reactor) and slowly adding methylamine (CH.sub.3NH.sub.2, 210 g (6.77 mol)) thereto while maintaining a temperature at −25° C., the mixture was stirred for 3 hours, and methylamine hydrochloride ((CH.sub.3)NH.sub.3C1)) was removed by filtration. While stirring a recovered bischlorolsilylamine ((SiH.sub.2C1).sub.2N(CH.sub.3)) solution with n-pentane and maintaining a temperature at −25° C., ethylmethylamine ((CH.sub.3CH.sub.2)(CH.sub.3)NH), 421 g (7.13 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 removing ethylmethylamine hydrochloride ((CH.sub.3CH.sub.2)(CH.sub.3)NH.sub.2Cl), white) formed by filtering the resultant, a filtrate was obtained. A solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(ethylmethylaminosilyl)methylamine ((CH.sub.3CH.sub.2)(CH.sub.3)NSiH.sub.2).sub.2N(CH.sub.3), 219 g (1.07 mol), yield: 60%).

(80) .sup.1H-NMR (inC6D6): δ 0.97 (t, 6H (N—CH.sub.2—CH.sub.3).sub.2), 2.47 (s, 6H (Si—NCH.sub.3).sub.2), 2.53 (s, 3H (SiH.sub.2—NCH.sub.3)), 2.81 (q, 4H (N—CH.sub.2—CH.sub.3).sub.2, 4.77 (m, 4H, (—SiH.sub.2N).sub.2).

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

(81) Film was formed using the bis(ethylmethylaminosilyl)methyl amine compound prepared in Example 2 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.

(82) 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.

(83) A result obtained by analyzing the manufactured silicon oxide thin film was illustrated in Table 2, and a result obtained by analyzing the deposited film using infrared spectroscopy was illustrated in FIG. 3.

[Examples 4 and 5] Manufacturing of Silicon Oxide Thin Film by PEALD Using Bis(ethylmethylaminosilyl)methylamine

(84) Silicon oxide thin films were manufactured in the same manner as in Example 3 except for changing deposition conditions illustrated in the following Table 1 in Example 3, results obtained by analyzing the manufactured silicon oxide thin film were illustrated in the following Table 2, and results obtained by analyzing the deposited film using the infrared spectroscopy were illustrated in FIG. 3.

(85) TABLE-US-00001 TABLE 1 Deposition Conditions of Silicon Oxide Thin Film by PEALD Reaction Gas Reaction No. of Temperature Precursor Purge and Plasma Gas Purge Deposition of Substrate Heating Injection Flow Rate Time Flow Rate RF Time Time Flow Rate Process (° C.) Temperature (° C.) Time (sec) (sccm) (sec) (sccm) Power (W) (sec) (sec) (sccm) Cycle Time (sec) Example 3 90 65 0.1 600 0.4 800 400 0.5 0.1 300 614 675 Example 4 90 65 0.1 600 0.4 800 400 0.7 0.1 300 603 784 Example 5 90 65 0.1 600 0.4 800 400 0.9 0.1 300 603 905

(86) TABLE-US-00002 TABLE 2 Evaluation of Properties of Silicon Oxide Thin Film O/Si Deposition Thickness of Refractive Composition Rate Thin Film Index Ratio Stress of Film WVTR (Å/cycle) (Å) — — (MPa) (g/[m.sup.2-day]) Example 3 1.14 700 1.46 1.72 −201 3.2E−02 Example 4 1.16 700 1.47 1.72 −231 1.5E−02 Example 5 1.16 700 1.47 1.72 −275 3.5E−03

[Example 6] Manufacturing of Silicon Nitride Thin Film by PEALD Using Bis(ethylmethylaminosilyl)methylamine

(87) Film was formed using the bis(ethylmethylaminosilyl)methyl amine compound prepared in Example 2 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 a plasma enhanced atomic layer deposition (PEALD) method known in the art. As a reaction gas, nitrogen and ammonia were used together with plasma as first reaction gas, and nitrogen was used as a second reaction gas. The nitrogen corresponding to an inert gas was used for purging. A specific method for depositing a silicon nitride thin film was illustrated in Table 3.

(88) A specific result obtained by analyzing the silicon nitride thin film was illustrated in Table 4, and a result obtained by analyzing the deposited film using an infrared spectrometer were illustrated in FIG. 4.

[Examples 7 to 9] Manufacturing of Silicon Nitride Thin Film by PEALD Using Bis(ethylmethylaminosilyl)methylamine

(89) Silicon nitride thin films were manufactured in the same manner as in Example 6 except for changing conditions illustrated in the following Table 3 in Example 6, results obtained by analyzing the manufactured silicon oxide thin film were illustrated in the following Table 4, and results obtained by analyzing the deposited film using the infrared spectrometer were illustrated in FIG. 4.

(90) TABLE-US-00003 TABLE 3 Deposition Conditions of Silicon Nitride Thin Film by PEALD Temper- Reaction Gas Reaction Gas ature Precursor Purge and Plasma Purge No. of of Sub- Heating Flow Flow RF Flow RF Flow De- Process strate Tempera- Injection Rate Time Rate Power Time Rate Power Time Time Rate position Time (° C.) ture (° C.) Time (sec) (sccm) (sec) (sccm) (W) (sec) (sccm) (W) (sec) (sec) (sccm) Cycle (sec) Example 6 300 65 0.4 6000 0.4 2000 100 1.5 6000 600 4 0.4 6000 300 2130 Example 7 300 65 0.4 6000 0.4 2000 200 1.5 6000 600 4 0.4 6000 300 2130 Example 8 300 65 0.4 6000 0.4 2000 400 1.5 6000 600 4 0.4 6000 300 2130 Example 9 300 65 0.4 6000 0.4 2000 800 1.5 6000 600 4 0.4 6000 300 2130

(91) TABLE-US-00004 TABLE 4 Evaluation of Properties of Silicon Nitride Thin Film Deposition Rate Thickness of Thin Refractive Index N/Si Composition Stress of Film WVTR Variable (Å/cycle) Film (Å) — Ratio (MPa) (g/[m.sup.2-day]) Example 6 Plasma 0.29 88 1.93 1.13 −301 6.2E−02 Power of 100 W Example 7 Plasma 0.22 67 1.89 1.16 −350 1.1E−02 Power of 200 W Example 8 Plasma 0.34 103 1.95 1.18 −416 3.5E−03 Power of 400 W Example 9 Plasma 0.38 114 1.80 1.21 −517 5.3E−03 Power of 800 W