KR20160071026A - Organo group 14 metalloid azide precursors and method for dipositing thin film using thereof - Google Patents

Organo group 14 metalloid azide precursors and method for dipositing thin film using thereof Download PDF

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KR20160071026A
KR20160071026A KR1020140178212A KR20140178212A KR20160071026A KR 20160071026 A KR20160071026 A KR 20160071026A KR 1020140178212 A KR1020140178212 A KR 1020140178212A KR 20140178212 A KR20140178212 A KR 20140178212A KR 20160071026 A KR20160071026 A KR 20160071026A
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azide compound
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이근수
조보연
옥광수
한정민
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주식회사 유진테크 머티리얼즈
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Abstract

The organic Group 14 metalloid azide compound according to one embodiment of the present invention is represented by the following Chemical Formula 1.
≪ Formula 1 >

Figure pat00048

Wherein M is any one selected from among Group 14 quasi metal elements; A, B and C independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, An alkylamine group having 2 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an allylic amine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, To 10 carbon atoms, or an azide group.

Description

[0001] The present invention relates to an organic 14-group quasi-metalloid azide compound and a method for depositing a thin film using the same,

The present invention relates to an organic 14-group quasi-metal azide compound and a thin film deposition method using the same, and relates to an organic 14-group quasi-metal azide compound capable of effectively forming a 14-quasimide metal nitride thin film and a method of depositing a nitride thin film using the same .

With the recent trend of high performance and miniaturization of portable devices such as smart phones and tablet PCs, it is required to improve the performance and miniaturization of semiconductor devices which are core parts. As a conventional semiconductor device having a planar structure, there is a limit in the degree of integration, and studies have been actively made to manufacture a multi-layered semiconductor device having a three-dimensional structure and to meet demands for high performance and miniaturization.

The thin film containing silicon plays an important role in the production of the semiconductor device, and the thin film containing silicon includes a silicon film, a silicon nitride film, a silicon carbide nitride film, a silicon oxide film and a silicon oxynitride film . In producing a multi-layered semiconductor device of a three-dimensional structure, a thin film containing silicon requires excellent step coverage.

Korean Patent Registration No. 10-0304694 (issued on November 2, 2001)

It is an object of the present invention to provide an organic Group 14 quasi-metal azide compound capable of effectively forming a Group 14 quasi-metalloid nitride thin film and a method of depositing a nitride thin film using the same.

Other objects of the present invention will become more apparent from the following detailed description.

The organic Group 14 metalloid azide compound according to one embodiment of the present invention is represented by the following Chemical Formula 1.

≪ Formula 1 >

Figure pat00001

Wherein M is any one selected from among Group 14 quasi metal elements; A, B and C independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, An alkylamine group having 2 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an allylic amine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, To 10 carbon atoms, or an azide group.

The M may be Si or Ge.

The organic Group 14 metalloid azide compound may be represented by the following Chemical Formula 2.

(2)

Figure pat00002

Wherein M, B and C are the same as defined in the above formula (1), R 1 and R 2 are independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, An aryl group having 7 to 13 carbon atoms or an acyl group having 2 to 10 carbon atoms, or R 1 and R 2 are bonded to each other, and a nitrogen atom bonded to these groups together with a cyclic amine group having 3 to 10 carbon atoms Or a heterocyclic amine group having 3 to 10 carbon atoms.

The organic Group 14 metalloid azide compound may be represented by the following Chemical Formula 3.

(3)

Figure pat00003

In the above formula (3), M, B, R 1 and R 2 are the same as defined in the formula (2).

The organic Group 14 metalloid azide compound may be represented by the following Chemical Formula 4.

≪ Formula 4 >

Figure pat00004

In the formula 4, M, R 1 and R 2 are the same as defined in the formula 2.

The organic Group 14 metalloid azide compound may be represented by the following Chemical Formula 5.

≪ Formula 5 >

Figure pat00005

The <Formula 5> In, M, R 1 and R 2 are the same as defined the above <Formula 2>, R 3 and R 4 are independently an alkyl group having 1 to 10 carbon atoms, having 6 to 12 carbon atoms, an aryl group, having a carbon number An allyl group having 7 to 13 carbon atoms or an allyl silyl group having 2 to 10 carbon atoms, or R 3 and R 4 are bonded to each other to form a cyclic carbon group having 3 to 10 carbon atoms or a heterocyclic carbon group having 3 to 10 carbon atoms.

The organic Group 14 metalloid azide compound may be represented by the following Chemical Formula 6.

(6)

Figure pat00006

Wherein M, R 1 and R 2 are the same as defined in the above formula (2), R 3 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group having 7 to 13 carbon atoms And an alkylsilyl group having 2 to 10 carbon atoms.

The organic Group 14 metalloid azide compound may be represented by the following Chemical Formula 7.

&Lt; Formula 7 >

Figure pat00007

M, R 1 and R 2 in the above formula (7) are the same as those in the above formula (2).

The organic Group 14 metalloid azide compound may be represented by the following formula (8).

(8)

Figure pat00008

The organic group 14 metalloid azide compound may be represented by the following formula (9).

&Lt; Formula 9 >

Figure pat00009

The organic 14-group quasi-metal azide compound may be represented by the following formula (10).

&Lt; Formula 10 >

Figure pat00010

The organic 14-group quasi-metal azide compound may be represented by the following formula (11).

&Lt; Formula 11 >

Figure pat00011

The organic Group 14 metalloid azide compound may be represented by the following Chemical Formula 12.

&Lt; Formula 12 >

Figure pat00012

The organic Group 14 metalloid azide compound may be represented by the following formula (13).

&Lt; Formula 13 >

Figure pat00013

The organic Group 14 metalloid azide compound may be represented by the following Formula 14.

&Lt; Formula 14 >

Figure pat00014

The method of depositing a thin film according to another embodiment of the present invention includes a deposition process of depositing a Group 14 metal nitride layer on a substrate using the organic Group 14 quasiazide metal azide compound as a precursor.

The deposition process may be performed by Atomic Layer Deposition (ALD) or Metal Organic Chemical Vapor Deposition (MOCVD).

The deposition process may be performed at a temperature ranging from 100 to 700 ° C.

The thin film deposition method may further include a supplying step of supplying the organic Group 14 metal complex azide compound on the substrate, wherein the supplying step is a step of supplying argon (Ar), nitrogen (N 2 ), helium Hydrogen (H 2 ) and the organic 14-quasimmetal azide compound may be mixed and supplied.

The supplying step may be any of a bubbling method, a vapor phase MFC method, a direct liquid injection (DLI) method, or a liquid transfer method which is supplied by dissolving in an organic solvent Can be used to provide the Group 14 metalloid azide compounds.

The supplying step may be performed by heating the organic 14-quasimmetal azide compound at a temperature of 20 to 100 ° C.

The effect of the organic 14-group quasi-metal azide compound and the thin film deposition method using the same according to an embodiment of the present invention will be described below.

Since the organic 14-group quasi-metal azide compound according to an embodiment of the present invention contains an azide group (-N 3 ), it is possible to deposit the group 14-group metal nitride film without supplying a separate nitrogen- can do.

Since the organic 14-group quasi-metal azide compound according to an embodiment of the present invention exists in a liquid state at room temperature, it is easy to store, has excellent thermal stability, has a high vapor pressure, and is suitable for the deposition of a Group 14 quasi- metal nitride film Lt; / RTI &gt;

The thin film deposition method according to one embodiment of the present invention uses an organic Group 14 quasi metal azide compound exhibiting excellent physical properties for thin film deposition as a precursor and does not use a nitrogen-based gas. Therefore, excellent step coverage Lt; RTI ID = 0.0 &gt; 14 &lt; / RTI &gt;

In the thin film deposition method according to an embodiment of the present invention, the deposition rate can be easily controlled by using a relatively low vapor pressure.

The present invention relates to an organic 14-group quasi-metalloid azide compound and a thin film deposition method using the same. Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. The embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below.

The silicon nitride film corresponds to an important configuration of a semiconductor device used as a passivation layer, an interlayer insulating film, a capacitor dielectric layer, or the like. Conventionally, in order to form a silicon nitride thin film, a nitrogen nitride gas is supplied in addition to a silicon precursor to deposit a nitride nitride film. Generally, silicon precursors such as SiH 2 Cl 2 , SiCl 4 , Si 2 Cl 6 and Si 3 Cl 8 have been used as the silicon precursors. As the nitrogen-based gases, NH 3 gas, SiH 4 / N 2 mixed gas And hydrazine. However, there is a problem that the silicon nitride film deposited by supplying a nitrogen-based gas separately from the conventional silicon precursor is scarce of step coverage and is easily cracked due to the formation of voids. Accordingly, the present invention provides a compound for depositing a quaternary metalloid nitride film having excellent film properties and a thin film deposition method using the same.

The organic 14-group quasi-metal azide compound according to one embodiment of the present invention is represented by the following formula (1).

&Lt; Formula 1 >

Figure pat00015

In the organic 14-group quasi-metal azide compound represented by the formula 1, M is any one selected from the group 14 quasi-metalloid elements, and A, B and C independently represent a hydrogen atom, a halogen atom, An alkyl group having 6 to 12 carbon atoms, an alkylamine group having 2 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an allylic amine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, A heterocyclic amine group having 1 to 10 carbon atoms, an alkylsilylamine group having 2 to 10 carbon atoms, or an azide group. The Group 14 metalloid element includes silicon (Si) or germanium (Ge).

Since the organic Group 14 quasiazide metal azide compound represented by Formula 1 contains a Group 14 quasi metal element and an azide group (-N 3 ) in the molecule itself, 14 < / RTI > base metal nitride film. Therefore, the organic 14-group quasi-metal azide compound according to one embodiment of the present invention can be used as a single source to form a silicon nitride film, a germanium nitride film, or the like by a method such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) It is possible to effectively form a film or the like.

The substituent A of the organic Group 14 quasiazide metal azide compound represented by Formula 1 may be an amine group, and is represented by Formula 2 below.

(2)

Figure pat00016

Wherein M, B and C are the same as defined in the above formula (1), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms An alkyl group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group having 7 to 13 carbon atoms, or an acylsilyl group having 2 to 10 carbon atoms. R 1 and R 2 may be bonded to each other to form a cyclic amine group having 3 to 10 carbon atoms or a heterocyclic amine group having 3 to 10 carbon atoms together with the nitrogen atom bonded thereto.

Substituent C of the organic Group 14 quasiazide metal azide compound represented by Formula 2 may be an amine group, which is represented by Formula 3 below.

(3)

Figure pat00017

In the above formula (3), M, B, R 1 and R 2 are the same as defined in the formula (2).

The substituent B of the organic Group 14 quasiazide metal azide compound represented by Formula 3 may be an azide group (-N 3 ), which is represented by the following Formula 4.

&Lt; Formula 4 >

Figure pat00018

In the formula 4, M, R 1 and R 2 are the same as defined in the formula 2.

The substituent B of the organic 14-group quasi-metal azide compound represented by the formula 2 may be R 3 and the substituent C 4 may be represented by the following formula 5.

&Lt; Formula 5 >

Figure pat00019

The <Formula 5> In, M, R 1 and R 2 are the same as defined the above <Formula 2>, R 3 and R 4 are independently an alkyl group having 1 to 10 carbon atoms, having 6 to 12 carbon atoms, an aryl group, having a carbon number An allylic group having 7 to 13 carbon atoms or an allyl silyl group having 2 to 10 carbon atoms. R 3 and R 4 may be bonded to each other to form a cyclic carbon group having 3 to 10 carbon atoms or a heterocyclic carbon group having 3 to 10 carbon atoms.

The chelator B of the organic 14-group quasi-metal azide compound represented by the formula 2 may be R 3 and the substituent C may be an azide group (-N 3 ), which is represented by the following formula (6).

(6)

Figure pat00020

Wherein M, R 1 and R 2 are the same as defined in the above formula (2), R 3 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group having 7 to 13 carbon atoms And an alkylsilyl group having 2 to 10 carbon atoms.

Substituents B and C of the organic Group 14 quasiazide metal azide compound represented by the formula (2) may be an azide group (-N 3 ), which is represented by the following formula (7).

&Lt; Formula 7 >

Figure pat00021

M, R 1 and R 2 in the above formula (7) are the same as those in the above formula (2).

Specific examples of the organic Group 14 quasiazide metal azide compounds represented by the above Chemical Formulas 1 to 7 include organic quasiazane metal azide compounds represented by the following Chemical Formula 8 to Chemical Formula 14 .

(8)

Figure pat00022

&Lt; Formula 9 >

Figure pat00023

&Lt; Formula 10 >

Figure pat00024

&Lt; Formula 11 >

Figure pat00025

&Lt; Formula 12 >

Figure pat00026

&Lt; Formula 13 >

Figure pat00027

&Lt; Formula 14 >

Figure pat00028

The method for preparing the organic Group 14 quasi-metal azide compound according to one embodiment of the present invention is not particularly limited and may be prepared by various methods. Therefore, the organic 14-group quasi-metal azide compound according to one embodiment of the present invention is not limited to the production method described below.

The organic Group 14 quasiazide metal azide compound represented by Formula 3 may be prepared according to Reaction Scheme 1 below.

<Reaction Scheme 1>

Figure pat00029


As shown in Reaction Scheme 1, the organic 14-group quasi-metal azide compound represented by Formula 3 can be prepared by a two-step substitution reaction. Stage reaction between the metal dichloride compound and the secondary amine compound to obtain a resultant product of the first-stage substitution reaction and a two-step substitution reaction of the alkali metal azide compound such as sodium azide, Can be obtained. The alkali metal azide compound used in the two-step substitution reaction may include lithium azide in addition to sodium azide.

As the reaction solvent for the one-step substitution reaction in the above Reaction Scheme 1, a non-polar solvent or a polar solvent can be used. Nonpolar solvents include pentane, hexane, benzene and the like, and the polar solvent includes diethyl ether, tetrahydrofuran (THF), dinormal butyl ether, acetonitrile and methylal. The 1-step substitution reaction in the above Reaction Scheme 1 is carried out at a reaction temperature of -30 ° C to room temperature (about 10-25 ° C) for about 1 hour to about 24 hours, preferably about -10 ° C to room temperature 2 hours to about 10 hours.

The polar solvent may include diethyl ether, tetrahydrofuran (THF), dinormal butyl ether, acetonitrile, and the like. The polar solvent may be used as a reaction solvent for the two-step substitution reaction in the above Reaction Scheme 1. The two-step substitution reaction of the above Reaction Scheme 2 is carried out at a reaction temperature of about 0 ° C to about 140 ° C for about 6 hours to about 100 hours, preferably at a reaction temperature of about 10 ° C to about 80 ° C, It takes about 60 hours.

In the chemical reaction according to Reaction Scheme 1, the amount of the reaction solvent used is adjusted so that the total concentration of the reaction reagent in the reaction solvent is about 5 wt% to about 50 wt%, preferably about 20 wt% to about 40 wt% Weight%.

The organic Group 14 quasi-metal azide compound represented by Formula 4 may be prepared according to Reaction Scheme 2 below.

<Reaction Scheme 2>

Figure pat00030

The organic Group 14 quasi-metal azide compound represented by Formula 5 may be prepared by the following Reaction Scheme 3.

<Reaction Scheme 3>

Figure pat00031

The organic Group 14 quasi-metal azide compound represented by Formula 6 may be prepared by the following Reaction Scheme 4.

<Reaction Scheme 4>

Figure pat00032

The organic Group 14 metalloid azide compound represented by the formula (7) can be prepared by the following Reaction Scheme 5.

<Reaction Scheme 5>

Figure pat00033

The organic 14-group quasi-metal azide compounds of the present invention will be described in more detail by way of the following examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples.

In the following examples, all the synthesis steps were performed using the standard vacuum line Schlenk technique, and all raw materials were synthesized in a nitrogen gas atmosphere. The diisopropylamine, diethylamine, dipropylamine, sodium azide, methylchlorosilane, dichlorodimethylsilane and tetrachlorosilane used in the experiment were prepared by Aldrich, and the solvent used in the reaction was an inert gas (THF), methylal and acetonitrile were refined by refluxing with sodium / benzophenone for 24 hours or more under a nitrogen atmosphere (nitrogen or argon). Structural analysis of the compound was carried out using JEOL JNM-ECS 400 MHz NMR spectrometer ( 1 H-NMR 400 MHz). NMR solvent benzene-d 6 was stirred with CaH 2 for one day to remove residual water completely before use.

&Lt; Example 1 >

((Et) 2 N) 2 Preparation of SiCH 3 N 3:

To a 1,000 mL round bottomed flask was added 58.71 g (0.8 mol) of diethylamine and 600 mL of methylal. 30 g (0.20 mol) of trichloromethylsilane was slowly added to the mixture while stirring the mixture at -10 DEG C, the temperature was raised to room temperature, and the mixture was stirred for 15 hours. Then, 350 mL of acetonitrile was added to the clear solution obtained by filtration under reduced pressure, 26 g (0.4 mol) of sodium azide was added at room temperature, and the mixture was stirred for about 18 hours.

Thereafter, the obtained reaction product solution was filtered, and the resulting solution was distilled under reduced pressure to obtain 26 g (yield: 57%) of ((Et) 2 N) 2 SiCH 3 N 3 in a colorless liquid state.

Boiling point (b.p): 42 ° C at 0.3 torr.

1 H-NMR (C 6 D 6 ):? 0.926 ([(C H 3 ) 2 H 2 C] 2 N-Si,

? 2.947 ([(CH 3 ) 2 H 2 C] 2 N-Si, m, 8H),

δ 0.088 (CH 3 -Si, s , 3H),

13 C-NMR (C 6 D 6 ):? 24.617 ([( C H 3 ) 2 H 2 C] 2 N-Si)

隆 45.717 ([(CH 3 ) 2 H 2 C ] 2 N-Si),

δ -1.155 (CH 3 -Si)

&Lt; Example 2 >

(Pr) 2 NSi (CH 3 ) 2 N 3 :

To a 500 mL round-bottomed flask was added 49.39 g (0.28 mol) of diisopropylamine and 300 mL of acetonitrile. 30 g (0.23 mol) of dichlorodimethylsilane was slowly added to the mixture while stirring the mixture at -10 DEG C, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. Subsequently, 30 g (0.46 mol) of sodium azide was added to the clear solution obtained by filtration under reduced pressure at room temperature, and the mixture was stirred for about 8 hours.

Thereafter, the obtained reaction product solution was filtered, and the resulting solution was distillated under reduced pressure to obtain 23 g (yield: 50%) of (Pr) 2 NSi (CH 3 ) 2 N 3 in a liquid state.

Boiling point (b.p): 25 ° C at 0.38 torr.

1 H-NMR (C 6 D 6 ):? 0.985 ([(C H 3 ) 2 HC] 2 N-Si, d,

? 3.041 ([(CH 3 ) 2 H C] 2 N-Si, m, 2H),

δ 0.136 (CH 3 -Si, s , 6H),

13 C-NMR (C 6 D 6 ):? 24.931 ([( C H 3 ) 2 HC] 2 N-Si)

? 45.946 ([(CH 3 ) 2 H C ] 2 N-Si),

δ 1.028 (CH 3 -Si)

&Lt; Example 3 >

(Pr) 2 NSiCH 3 (N 3) 2 Preparation of:

To a 1,000 mL round bottomed flask was added 40.61 g (0.40 mol) of diisopropylamine and 600 mL of milled alum. 30 g (0.20 mol) of trichloromethylsilane was slowly added to the mixture while stirring the mixture at -10 DEG C, the temperature was raised to room temperature, and the mixture was stirred for 18 hours. Subsequently, 350 mL of acetonitrile was added to the clear solution obtained by vacuum filtration, 39 g (0.6 mol) of sodium azide was added at room temperature, and the mixture was stirred for about 18 hours.

Thereafter, the obtained reaction product solution was filtered, and the resulting solution was distilled under reduced pressure to obtain 24.75 g (yield: 55%) of (Pr) 2 NSiCH 3 (N 3 ) 2 in a colorless liquid state.

Boiling point (b.p): 33 ° C at 0.3 torr.

1 H-NMR (C 6 D 6 ):? 0.947 ([(C H 3 ) 2 HC] 2 N-Si, d,

? 2.950 ([(CH 3 ) 2 H C] 2 N-Si, m, 2H),

δ 0.091 (CH 3 -Si, s , 3H),

13 C-NMR (C 6 D 6 ):? 24.626 ([( C H 3 ) 2 HC] 2 N-Si)

? 45.783 ([(CH 3 ) 2 H C ] 2 N-Si),

δ -1.155 (CH 3 -Si)

<Example 4>

((Pr) 2 N) 2 Si (N 3 ) 2 :

To a 500 mL round-bottom flask was added 73.25 g (0.72 mol) of dipropylamine and 300 mL of methylal. 30 g (0.17 mol) of tetrachlorosilane was slowly added to the mixture while stirring the mixture at -10 ° C, the temperature was raised to room temperature, and the mixture was stirred for 3 to 4 hours. Thereafter, the transparent solution obtained by filtration under reduced pressure was removed at 150 deg. C at -10 deg. 34.44 g (0.52 mol) of sodium azide was dissolved, 250 mL of acetonitrile was added at room temperature, and the mixture was stirred for about 24 hours.

Thereafter, the obtained reaction product solution was filtered, and the resulting solution was distilled under reduced pressure to obtain 30 g (yield: 54.54%) of ((Pr) 2 N) 2 Si (N 3 ) 2 in a colorless liquid state.

Boiling point (b.p): 100 ° C at 0.6 torr.

1 H-NMR (C 6 D 6): δ 0.760 ([C H 3 CH 2 CH 2] 2 N-Si, t, 12H),

δ 1.360 ([CH 3 C H 2 CH 2] 2 N-Si, m, 8H),

δ 2.674 ([CH 3 CH 2 C H 2] 2 N-Si, m, 8H),

13 C-NMR (C 6 D 6 ):? 12.031 ([ C H 3 CH 2 CH 2 ] 2 N-Si)

? 28.806 ([CH 3 C H 2 CH 2 ] 2 N-Si),

δ 48.196 ([CH 3 CH 2 C H 2] 2 N-Si).

&Lt; Example 5 >

(Pr) 2 NSi (N 3 ) 3 Preparation of:

To a 3 L round round flask was added 262.05 g (2.58 mol) of diisopropylamine and 2,000 mL of methylal. 200.00 g (1.17 mol) of tetrachlorosilane was slowly added to the mixture while stirring at -10 DEG C while maintaining the above temperature, and the mixture was stirred at room temperature for 3 to 4 hours. The resulting reaction product was filtered under reduced pressure to obtain 267.84 g (4.12 mol) of sodium azide at room temperature, and the reaction was terminated by stirring for about 50 hours.

Thereafter, the obtained reaction product solution was filtered to obtain 209 g (yield: 70%) of (Pr) 2 NSi (N 3 ) 3 in a colorless liquid state by distillation under reduced pressure.

Boiling point (b.p): 58 ° C at 0.06 torr.

1 H-NMR (C 6 D 6 ):? 0.904 ([(C H 3 ) 2 HC] 2 N-Si.

? 2.911 ([(CH 3 ) 2 H C] 2 N-Si, m, 2H),

13 C-NMR (C 6 D 6 ):? 24.378 ([( C H 3 ) 2 HC] 2 N-Si)

隆 46.098 ([(CH 3 ) 2 H C ] 2 N-Si).

The thin film deposition method according to another embodiment of the present invention includes a deposition process in which a Group 14 quasi metal nitride layer is formed on a substrate using the above-described organic Group 14 quasiazide metal azide compound as a precursor.

The deposition process includes heating (S1) heating the substrate to a temperature of from about 100 ° C to about 700 ° C under vacuum or an inert atmosphere, heating the substrate to a temperature of from about 20 ° C to about 100 ° C, A precursor layer forming step (S3) of forming a precursor layer of an organic 14-quasimmetal azide compound by adsorbing the organic 14-group quasi-metal azide compound on the substrate, and a step (S3) of forming a precursor layer Or an electrical bias to decompose the organic quaternary metal azide compound to form a quaternary quartz metal nitride film. The deposition process may be performed by an Atomic Layer Deposition (ALD) process or a Metal Organic Chemical Vapor Deposition (MOCVD) process, but is not limited thereto.

Supplying step (S2) in the argon (Ar), nitrogen (N 2), helium (He) and hydrogen (H 2) by mixing at least one carrier gas and the semi-metal azide compound Group 14 organic selected from supplying a substrate have. The method of supplying the organic Group 14 metalloid azide compound on the substrate in the supplying step S2 includes a bubbling method, a vapor phase MFC method, a direct liquid injection method Liquid Injection (DLI) method, or a liquid transfer method in which it is dissolved in an organic solvent and supplied.

The precursor layer forming step (S3) may provide a layer forming time so that the organic quatrivalazide precursor compound forms a layer on the substrate, and the layer forming time is preferably less than 1 minute.

The thin film deposition method according to an embodiment of the present invention further includes a purge step (S5) for removing an excess amount of the organic 14-quasimmetal azide precursor compound not adsorbed on the substrate after the precursor layer forming step (S3) can do. Purge step (S5) is argon (Ar), nitrogen (N 2) and helium (He) excess organic Group 14 metalloid azide precursor compounds that are not adsorbed on the substrate by supplying at least one inert gas selected substrate in a Remove it. The purging step (S5) preferably has a purge time of less than 1 minute to remove excess organic Group 14 metalloid azide precursor compound.

The organic 14-group quasi-metal azide compound according to an embodiment of the present invention exists in a liquid state at room temperature, has excellent thermal stability, and has high volatility because of high vapor pressure. Therefore, the organic 14-group quasi-metal azide compound according to one embodiment of the present invention exhibits suitable physical properties as a precursor used in thin film deposition. Further, the organic 14-group quasi-metal azide compound according to an embodiment of the present invention contains an azide group (-N 3 ), so that the nitrogen content in the compound is high. Thus, it is possible to deposit a Group 14 quasi metal nitride film without supplying a separate nitrogen-based source.

The organic 14-group quasi-metal azide compound according to one embodiment of the present invention is used as a precursor and is deposited by atomic layer deposition (ALD) or metal organic chemical vapor deposition (MOCVD) 14 &lt; / RTI &gt; semi-metal nitride films have excellent step coverage.

Claims (21)

An organic Group 14 quasi-metal azide compound represented by the following Chemical Formula 1.
&Lt; Formula 1 >
Figure pat00034

Wherein M is any one selected from among Group 14 quasi metal elements; A, B and C independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, An alkylamine group having 2 to 10 carbon atoms, an arylamine group having 6 to 12 carbon atoms, an allylic amine group having 7 to 13 carbon atoms, a cyclic amine group having 3 to 10 carbon atoms, a heterocyclic amine group having 3 to 10 carbon atoms, To 10 carbon atoms, or an azide group. The method according to claim 1,
Wherein M is Si or Ge. The method according to claim 1,
The organic Group 14 quasiazide metal azide compound is represented by the following Chemical Formula 2:
(2)
Figure pat00035

Wherein M, B and C are the same as defined in the above formula (1), R 1 and R 2 independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, An aryl group having 7 to 13 carbon atoms or an acyl group having 2 to 10 carbon atoms, or R 1 and R 2 are bonded to each other, and a nitrogen atom bonded to these groups together with a cyclic amine group having 3 to 10 carbon atoms Or a heterocyclic amine group having 3 to 10 carbon atoms. The method of claim 3,
The organic Group 14 quasiazide metal azide compound is represented by the following Chemical Formula 3.
(3)
Figure pat00036

In the above formula (3), M, B, R 1 and R 2 are the same as defined in the formula (2). 5. The method of claim 4,
The organic Group 14 quasiazide metal azide compound is represented by the following Chemical Formula 4.
&Lt; Formula 4 >
Figure pat00037

In the formula 4, M, R 1 and R 2 are the same as defined in the formula 2. The method of claim 3,
Wherein the organic Group 14 quasiazide metal azide compound is represented by the following Chemical Formula 5.
&Lt; Formula 5 >
Figure pat00038

The <Formula 5> In, M, R 1 and R 2 are the same as defined the above <Formula 2>, R 3 and R 4 are independently an alkyl group having 1 to 10 carbon atoms, having 6 to 12 carbon atoms, an aryl group, having a carbon number An allyl group having 7 to 13 carbon atoms or an allyl silyl group having 2 to 10 carbon atoms, or R 3 and R 4 are bonded to each other to form a cyclic carbon group having 3 to 10 carbon atoms or a heterocyclic carbon group having 3 to 10 carbon atoms. The method of claim 3,
The organic Group 14 quasiazide metal azide compound is represented by the following Chemical Formula 6.
(6)
Figure pat00039

Wherein M, R 1 and R 2 are the same as defined in the above formula (2), R 3 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group having 7 to 13 carbon atoms And an alkylsilyl group having 2 to 10 carbon atoms. The method of claim 3,
Wherein the organic 14-group quasi-metal azide compound is represented by the following formula (7).
&Lt; Formula 7 >
Figure pat00040

M, R 1 and R 2 in the above formula (7) are the same as those in the above formula (2). The method according to claim 1,
Wherein the organic 14-group quasi-metal azide compound is represented by the following formula (8).
(8)
Figure pat00041
 The method according to claim 1,
Wherein the organic 14-group quasi-metal azide compound is represented by the following formula (9).
&Lt; Formula 9 >
Figure pat00042
 The method according to claim 1,
Wherein the organic 14-group quasi-metal azide compound is represented by the following formula (10).
&Lt; Formula 10 >
Figure pat00043
 The method according to claim 1,
Wherein the organic 14-group quasi-metal azide compound is represented by the following formula (11).
&Lt; Formula 11 >
Figure pat00044
 The method according to claim 1,
Wherein the organic 14-group quasi-metal azide compound is represented by the following formula (12).
&Lt; Formula 12 >
Figure pat00045
 The method according to claim 1,
Wherein the organic 14-group quasi-metal azide compound is represented by the following formula (13).
&Lt; Formula 13 >
Figure pat00046
 The method according to claim 1,
Wherein the organic Group 14 quasiazide metal azide compound is represented by the following Chemical Formula 14.
&Lt; Formula 14 >
Figure pat00047
 15. A method for depositing a thin film comprising depositing a Group 14 quasi-metallic nitride film on a substrate using the organic Group 14 quasi-metal azide compound of any one of claims 1 to 15 as a precursor. 17. The method of claim 16,
The deposition process may include:
(ALD) or Metal Organic Chemical Vapor Deposition (MOCVD). &Lt; Desc / Clms Page number 13 &gt; 17. The method of claim 16,
The deposition process may include:
Is carried out in a temperature range of 100 to 700 占 폚. 17. The method of claim 16,
The deposition process may include:
And a supply step of supplying the organic group-14 metalloid azide compound onto the substrate,
Wherein the supplying step comprises:
Wherein at least one carrier gas selected from the group consisting of argon (Ar), nitrogen (N 2 ), helium (He) and hydrogen (H 2 ) is mixed with the organic 14-group quasi-metal azide compound. 20. The method of claim 19,
Wherein the supplying step comprises:
(14) by any one of a bubbling method, a vapor phase MFC method, a direct liquid injection (DLI) method, or a liquid transfer method in which the liquid is supplied in an organic solvent To provide a ternary metal azide compound. 20. The method of claim 19,
Wherein the supplying step comprises:
Wherein the organic 14-group quasi-metal azide compound is heated and supplied at a temperature of 20 to 100 ° C.

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* Cited by examiner, † Cited by third party
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