KR100829472B1 - Aluminum compound for forming aluminum films by chemical vapor deposition and their synthesis - Google Patents

Abstract

The present invention relates to a precursor compound used to deposit an aluminum thin film on a substrate by chemical vapor deposition, and a method for preparing the compound. The present invention provides an organometallic complex defined by the following Chemical Formula 1 and a method for producing the same.

[Formula 1]

H ₂ AlBH ₄ : L _n

[In Formula 1, L is a Lewis base, an amine-based organic compound capable of providing a non-covalent electron pair to an aluminum metal center as a heterocyclic amine or an alkyl amine, where n is 1 Or an integer of 2.]

Aluminum, amine, alan, precursor

Description

Aluminum compound for forming aluminum films by chemical vapor deposition and their synthesis}

The present invention relates to a precursor compound used to deposit an aluminum thin film on a substrate by chemical vapor deposition and a method for preparing the compound, and more particularly, to an adhesive film or a diffusion barrier formed on a substrate such as silicon. It is to provide a compound for forming the alumina thin film layer and a method for producing the compound.

The development of new technologies and materials in the semiconductor industry has made it possible to realize miniaturization, high reliability, high speed, high functionality, and high integration of devices such as semiconductor integrated circuits. The metal wirings that transmit signals had to be miniaturized, and the increase in parasitic capacitors due to the reduction in the cross-sectional area and the wire spacing caused by the reduction in the cross-sectional area caused by such miniaturization. This increase in resistance and capacitor causes RC delay, which is a barrier to manufacturing high-speed semiconductor devices pursued by future logic processes. In order to manufacture high-speed semiconductor devices, parasitic capacitors between metal wirings must be reduced. To this end, the use of a low dielectric constant insulating film or a low resistance metal wiring is essential. In particular, the low resistance metal wiring process technology still has a lot of room for improvement in process and equipment. have.

Currently, aluminum (Al) metal wiring used in 64M DRAM manufacturing is absolutely dependent on the sputtering method of depositing aluminum wiring using a desired aluminum metal target, but the deposition of metal wiring having a circuit line width of 0.25 μm or less is a contact. Due to the large aspect ratio (depth / diameter) of contacts or vias, it is expected to be inappropriate to use sputtering as a deposition process.

In order to overcome this problem, aluminum wiring using the Chemical Vapor Deposition (CVD) method is advantageous for the process of filling contact / via holes with high step ratio by showing the advantages of high step coverage. The process has been studied for a long time.

As a result of this research, the aluminum wire deposition process has been prepared based on the aluminum (Al) -CVD method, and the use of the CVD method is absolutely considered.

Deposition of Al thin film using chemical vapor deposition method uses an aluminum compound called a precursor (Precursor), and in the process of depositing a metal thin film using such a metal compound, the characteristics and selection of the precursor compound is a chemical vapor deposition (CVD) process The development and selection of precursors prior to the introduction of a process is one of the first considerations.

Initial research on Al metal chemical vapor deposition has been conducted in the United States and Japan in the 1980s using commercially widely used alkylaluminum compounds. Representative alkylaluminum compounds include trimethyl aluminum (Al (CH ₃ ) ₃ ). And triisobutylaluminum (Al ((CH ₃ ) ₂ CHCH ₂ ) ₃ ) compounds were mainly used.

Later, as a precursor compound for chemical vapor deposition of aluminum thin films in the 90's, dimethyl aluminum hydride represented by [(CH ₃ ) ₂ AlH] ₃ and H ₃ Al: N (CH ₃ ) ₂ C ₂ H ₅ . Dimethylethylaminealane has been represented as a precursor compound for Al-CVD.

The alkylaluminum compound introduced above has advantages as a CVD precursor, such as being present as a liquid having a high vapor pressure at room temperature, but the deposition process becomes difficult because the deposition temperature of the thin film is made at a high temperature in the range of 300 ° C to 400 ° C. Due to the high temperature deposition, it is a fatal drawback that carbon, which is an unwanted impurity to increase the electrical resistance in the aluminum thin film, and explosive flammability due to contact with minute air, shows the danger of requiring very careful handling. have.

In order to solve this problem, the development of process and technology for Al-CVD method using dimethyl aluminum hydride compound as a precursor began in the early 1980s, and the dimethyl aluminum hydride has a high vapor pressure (2 torr at 25 ° C.). It is a compound having a high deposition rate and a colorless liquid at room temperature, and according to the deposition conditions using hydrogen gas, it is possible to deposit a high purity aluminum thin film at a relatively low deposition temperature of around 230 ° C, but the dimethyl aluminum hydride is alkyl aluminum It is difficult to handle because it has explosive flammability when it is contacted with air as a compound of the series, and because of the difficulty of the compound manufacturing process, it is economically poor due to high productivity due to the decrease in productivity, and because it is a high viscosity liquid compound Disadvantages of Adjusting the Delivery Speed I also have it.

As an alternative to this, alan (AlH ₃ ) -based compound is used as a precursor compound for Al-CVD, and general alkylamine alan deposits a high purity aluminum thin film at a low temperature of 100 to 200 ° C. and a high vapor pressure (1.5 tor at 25 ° C.). It has a slightly less flammability compared to the dimethylaluminum hydride, which is used as a colorless liquid at room temperature, and has excellent economical efficiency because it is manufactured by a simple manufacturing process.

However, the alkylaminealan is decomposed slowly in the container holding the precursor due to thermal instability when heated to 30-40 ° C. at room temperature or to be applied to the deposition process. It has a fatal disadvantage that it is difficult to develop a reproducible deposition process to be realized, and that it is not easy to store at room temperature.

Accordingly, the present invention provides a novel aluminum precursor compound and a method for producing the same to overcome the problems of the prior art of the precursor compound for Al-CVD, that is, thermal instability, high viscosity, explosive flammability, etc. and to expand the selection range of the precursor compound. It is.

The present invention provides a compound defined by the following Chemical Formula 1 as a precursor compound for deposition of a new aluminum thin film designed to fully cover the advantages of the existing precursors for the aluminum (Al) metal thin film deposition and to maximize the disadvantages.

[Formula 1]

H ₂ AlBH ₄ : L _n

[In Formula 1, L is a Lewis base, and is an amine-based organic compound capable of providing a non-covalent electron pair to an aluminum metal center. The heterocyclic amine having the structure of Formula 2 or Formula 3 Alkyl amine having a structure, n is an integer of 1 or 2.]

[Formula 2]

[In Formula 2, R ₁ and R ₂ are independently of each other hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₃ is a linear or branched alkyl group having 1 to 4 carbon atoms which is unsubstituted or substituted with halogen, and m is 2 To an integer of 8]

[Formula 3]

[In Formula 3, R ₄ to R ₆ are independently a hydrogen or a halogen substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms or alkene group having 1 to 6 carbon atoms, and R ₄ and R ₅ And R ₆ are not methyl at the same time.]

The heterocyclic amine represented by the formula (2) is alkylaziridine, alkylazetidine, alkylpyrrolidine, alkylpiperidine, alkylpiperidine, alkylhexamethyleneimine, alkyl Selected from alkylheptamethyleneimine, R ₁ and R _{2, which} are substituents of Formula 2 and Formula 3, independently of one another, are hydrogen, methyl, ethyl, and R ₃ is hydrogen, methyl, ethyl, n-propyl, i-propyl , n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, perfluoromethyl, R ₄ to R ₆ are independently of each other hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, perfluoromethyl.

In addition, the compound of Formula 2 or Formula 3 is preferably selected from methylpyrrolidine, dimethylethylamine and dimethylbutylamine.

The aminealanborane compound defined by Chemical Formula 1 does not cause problems due to stability in the mass production process, which is the weakest disadvantage of an amine stabilized with amine, which is a general structure used as a precursor for manufacturing an aluminum thin film. It has a sufficient degree of thermal stability.

The precursor compound for aluminum thin film deposition defined by Chemical Formula 1 may be easily prepared from Schemes 1 to 4, and the synthesis of the precursor compound according to Schemes 1 to 4 may be carried out using diethyl ether or diether ether in a reaction vessel. Using a mixed solution of hexane as a solvent to make a suspension of the mixture according to each step, the resulting salt is removed and the solvent is distilled under vacuum to prepare a precursor compound of Formula 1 according to the present invention.

Scheme 1

LiAlH ₄ + AlCl ₃ + 2nL + 2MBH ₄ → 2H ₂ AlBH ₄ : L _n (1)

Scheme 2

LiAlH ₄ + AlCl ₃ + 2nL ¡Æ 2ClH ₂ Al: L _n (4)

ClH ₂ Al: L _n (4) + MBH ₄ → H ₂ AlBH ₄ : L _n (1)

Scheme 3

LiAlH ₄ + AlCl ₃ + 2Et ₂ O → 2ClH ₂ Al: OEt ₂

ClH ₂ Al: OEt ₂ + nL → ClH ₂ Al: L _n (4) + Et ₂ O

ClH ₂ Al: L _n (4) + MBH ₄ ¡Æ H ₂ AlBH ₄ : L _n (1)

Scheme 4

AlCl ₃ + 3LiAlH ₄ + 4nL → 4H ₃ Al: L _n (5)

2H ₃ Al: L _n (5) + HgCl ₂ → 2ClH ₂ Al: L _n (4) + Hg + H ₂

ClH ₂ Al: L _n (4) + MBH ₄ → H ₂ AlBH ₄ : L _n (1)

[In Reaction Schemes 1 to 4, L means a Lewis base is the same as defined in Formula 1, n is an integer of 1 or 2; M is Na or Li.]

As shown in Scheme 1, the aminealanborane compound of Formula 1 reacts lithium aluminum hydride, trichloroaluminum, an amine compound of Formula 2 or 3 with an alkali metal borohydride (MBH ₄ ; M = Na or Li). It is prepared in one step.

In addition, as shown in Schemes 2 to 4, the aminealanborane compound of Formula 1 is obtained by reacting a chloroalanine compound (4) with an alkali metal borohydride (MBH ₄ ; M = Na or Li). The chloroalan compound (4) may be prepared by reacting the aminealan compound (5) with lithium aluminum hydride, trichloroaluminum and an amine compound of the formula (2) or (3) or by mercury chloride.

Hereinafter, the method for preparing the aluminum compound of the present invention will be described in more detail with reference to the following examples.

Example 1 Preparation of Dimethylethylamine Alanborane

To a suspension solution containing 133.3 g (1 mol) of trichloroaluminum and 1000 ml of nucleic acid, 500 ml of diethyl ether solution was added under a stream of nitrogen gas, and 39.4 g (1.04 mol) of lithium aluminum hydride was added dropwise, followed by stirring at room temperature for 24 hours. I was. After stirring was complete, 161 g (2.2 mol) of dimethylethylamine was added at a low temperature (-10 ° C), followed by stirring for 10 minutes. After stirring was completed, 47.8 g (2.2 mol) of lithium boron hydride was added dropwise to the reaction mixture and stirred at 30 ° C. for 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification of the reaction product gave 149 g (yield 64%) of the title compound as a colorless high purity dimethylethylaminealanborane compound.

Chemical reactions for the preparation of dimethylethylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + 2LiBH ₄ → 2H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 2 Preparation of Dimethylethylamine Alanborane

161 g (2.2 mole) of dimethylethylamine was added to a dichloroalan compound produced under a stream of nitrogen gas to a 1000 ml suspension of nucleic acid to which 133.3 g (1 mole) of trichloroaluminum and 39.4 g (1.04 mole) of lithium aluminum hydride were added. 47.8 g (2.2 mol) of lithium boron was added dropwise and stirred at 30 ° C. for about 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification was carried out to give 125 g (yield 53%) of the title compound as a colorless high purity dimethylethylaminealanborane compound.

Chemical reactions for the preparation of dimethylethylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₃ ) (CH ₃ ) ₂ → 2ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂

ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + LiBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 3 Preparation of Dimethylethylamine Alanborane

To a chloroalan compound produced by stirring for 13 hours in an aqueous solution of 133.3 g (1 mol) of trichloroaluminum and 39.4 g (1.04 mol) of lithium aluminum hydride, cooled to -10 ° C under a stream of nitrogen gas- 161 g (2.2 mole) of dimethylethylamine was added while maintaining at 10 ° C., and 47.8 g (2.2 mole) of lithium boron hydride was added dropwise and stirred at 30 ° C. for 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification was carried out to give 135 g (yield 58%) of the title compound as a colorless high purity dimethylethylaminealanborane compound.

Chemical reactions for the preparation of dimethylethylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2Et ₂ O → 2ClH ₂ Al: OEt ₂

ClH ₂ Al: OEt ₂ + N (CH ₂ CH ₃ ) (CH ₃ ) ₂ → ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + Et ₂ O

ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + LiBH ₄ ¡Æ H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 4 Preparation of Dimethylethylamine Alanborane

To a suspension solution containing 133.3 g (1 mol) of trichloroaluminum and 1000 ml of nucleic acid, 500 ml of diethyl ether solution was added dropwise under a stream of nitrogen gas, and 39.4 g (1.04 mol) of lithium aluminum hydride was added dropwise, followed by stirring at room temperature for 24 hours. . After stirring was complete, 161 g (2.2 mol) of dimethylethylamine was added at a low temperature (-10 ° C), followed by stirring for 10 minutes. After stirring was completed, 83.1 g (2.2 mol) of sodium borohydride was added dropwise and stirred at 30 ° C. for 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification was carried out to give 160g (yield 68%) of the title compound as a colorless high purity dimethylethylaminealanborane compound.

Chemical reactions for the preparation of dimethylethylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + 2NaBH ₄ → 2H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 5 Preparation of Dimethylethylamine Alanborane

161 g (2.2 mole) of dimethylethylamine was added to a dichloroalan compound produced under a stream of nitrogen gas to a 1000 ml suspension of nucleic acid added with 133.3 g (1 mole) of trichloroaluminum and 39.4 g (1.04 mole) of lithium aluminum hydride. 83.1 g (2.2 mol) of sodium boron was added dropwise and stirred at 30 ° C. for 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification of the reaction product gave 133 g (yield 57%) of the title compound as a colorless high purity dimethylethylaminealanborane compound.

Chemical reactions for the preparation of dimethylethylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₃ ) (CH ₃ ) ₂ → 2ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂

ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + NaBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 6 Preparation of Dimethylethylamine Alanborane

To a chloroalan compound produced by stirring for 13 hours in an aqueous solution of 133.3 g (1 mol) of trichloroaluminum and 39.4 g (1.04 mol) of lithium aluminum hydride, cooled to -10 ° C under a stream of nitrogen gas- 161 g (2.2 mole) of dimethylethylamine was added while maintaining at 10 ° C., and 83.1 g (2.2 mole) of sodium borohydride was added dropwise and stirred at 30 ° C. for 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification was carried out to give 120 g (yield 51%) of the title compound as a colorless high purity dimethylethylaminealanborane compound.

Chemical reactions for the preparation of dimethylethylalanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2Et ₂ O → 2ClH ₂ Al: OEt ₂

ClH ₂ Al: OEt ₂ + N (CH ₂ CH ₃ ) (CH ₃ ) ₂ → ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + Et ₂ O

ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + NaBH ₄ ¡Æ H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 7 Preparation of Dimethylethylamine Alanborane

21.3 g (0.56 mol) of lithium aluminum hydride was added dropwise over 30 seconds while cooling 500 ml of diethyl ether floating solution to which 22.7 g (0.17 mol) of trichloro aluminum was added dropwise at -10 ° C, followed by dimethylethylamine. 49.7 g (0.68 mol) was added and stirred at -10 ° C for 5 hours. After stirring was completed, the reaction mixture was filtered, and then the filtrate was cooled at −25 ° C. for 24 hours to add 92 g (0.34 mole) of mercuric chloride in 250 ml of a diethyl ether solvent. Then, 28.3 g (0.75 mol) of sodium borohydride was added dropwise, followed by stirring at 30 ° C. for 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification was carried out to give 44 g (56% yield) of the title compound as a colorless high purity dimethylethylaminealanborane compound.

Chemical reactions for the preparation of dimethylethylaminealanborane are as follows.

AlCl ₃ + 3LiAlH ₄ + 4N (CH ₂ CH ₃ ) (CH ₃ ) ₂ → 4H ₃ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂

2H ₃ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + HgCl ₂ → 2ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + Hg + H ₂

ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + NaBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 8 Preparation of Dimethylethylamine Alanborane

21.3 g (0.56 mol) of lithium aluminum hydride was added dropwise over 30 seconds while cooling 500 ml of diethyl ether floating solution to which 22.7 g (0.17 mol) of trichloro aluminum was added dropwise at -10 ° C, followed by dimethylethylamine. 49.7 g (0.68 mol) was added and stirred at -10 ° C for 5 hours. After stirring was completed, the reaction mixture was filtered, and then the filtrate was cooled at -25 ° C for 24 hours to add 92 g (0.34 mole) of mercuric chloride in 250 ml of a diethyl ether solvent. Then, 16.2 g (0.75 mol) of lithium boron hydride was added dropwise, followed by stirring at 30 ° C. for 8 hours. The reaction mixture was filtered under a nitrogen stream using a filter to obtain a primary filtrate, and the by-product filtered was rinsed twice with a sufficient amount of hexane, filtered to obtain a secondary filtrate, and then combined with the first filtrate. . The filtrate was removed at room temperature (20 ℃) using a vacuum to remove all volatile substances to obtain a colorless liquid.

When the dried colorless filtrate is distilled while maintaining a vacuum (1.3 torr) at 45 ° C., the colorless distillate is condensed in a vessel cooled with dry ice, and the resulting colorless primary distillate is obtained at 45 ° C. in the same manner. Purification was carried out to give 41 g (yield 52%) of colorless high purity dimethylethylaminealanborane compound as the title compound.

Chemical reactions for the preparation of dimethylethylaminealanborane are as follows.

AlCl ₃ + 3LiAlH ₄ + 4N (CH ₂ CH ₃ ) (CH ₃ ) ₂ → 4H ₃ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂

2H ₃ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + HgCl ₂ → 2ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + Hg + H ₂

ClH ₂ Al: N (CH ₂ CH ₃ ) (CH ₃ ) ₂ + LiBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 9 Preparation of Dimethyl Butylamine Alanborane

143 g (yield 50%) of colorless high purity dimethylbutylaminealanborane compound, the title compound, was obtained in the same manner as in Example 1, except that 222 g (2.2 mol) of dimethylbutylamine was used instead of dimethylethylamine. .

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + 2LiBH ₄ ¡Æ 2H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 10 Preparation of Dimethylbutylamine Alanborane

123 g (yield 43%) of colorless high-purity dimethylbutylaminealanlanane compound, the title compound, was obtained in the same manner as in Example 2, except that 222 g (2.2 mol) of dimethylbutylamine was used instead of dimethylethylamine. .

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ → 2ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + LiBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 11 Preparation of Dimethyl Butylamine Alanborane

130 g (yield 45%) of colorless high-purity dimethylbutylaminealanborane compound, the title compound, was obtained in the same manner as in Example 3, except that 222 g (2.2 mol) of dimethylbutylamine was used instead of dimethylethylamine.

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2Et ₂ O → 2ClH ₂ Al: OEt ₂

ClH ₂ Al: OEt ₂ + N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ → ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + Et ₂ O

ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + LiBH ₄ ¡Æ H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 12 Preparation of Dimethylbutylamine Alanborane

159 g (yield 55%) of colorless high-purity dimethylbutylaminealanborane compound, the title compound, was obtained in the same manner as in Example 4, except that 222 g (2.2 mol) of dimethylbutylamine was used instead of dimethylethylamine.

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + 2NaBH ₄ ¡Æ 2H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 13 Preparation of Dimethylbutylamine Alanborane

133 g (yield 46%) of colorless high-purity dimethylbutylaminealanborane compound, the title compound, was obtained in the same manner as in Example 5, except that 222 g (2.2 mol) of dimethylbutylamine was used instead of dimethylethylamine.

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ → 2ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + NaBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 14 Preparation of Dimethylbutylamine Alanborane

127 g (yield 44%) of colorless high-purity dimethylbutylaminealanborane compound, the title compound, was obtained in the same manner as in Example 6, except that 222 g (2.2 mol) of dimethylbutylamine was used instead of dimethylethylamine.

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

LiAlH ₄ + AlCl ₃ + 2Et ₂ O → 2ClH ₂ Al: OEt ₂

ClH ₂ Al: OEt ₂ + N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ → ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + Et ₂ O

ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + NaBH ₄ ¡Æ H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 15 Preparation of Dimethylbutylamine Alanborane

41 g (yield 42%) of colorless, high-purity dimethylbutylaminealanborane compound, the title compound, was obtained in the same manner as in Example 7, except that 68.7 g (0.68 mol) of dimethylbutylamine was used instead of dimethylethylamine. It was.

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

AlCl ₃ + ₃ LiAlH ₄ + 4N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ → 4H ₃ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

2H ₃ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + HgCl ₂ → 2ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + Hg + H ₂

ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + NaBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 16 Preparation of Dimethylbutylamine Alanborane

43 g (yield 44%) of colorless, high-purity dimethylbutylaminealanborane compound, the title compound, was obtained in the same manner as in Example 8, except that 68.7 g (0.68 mol) of dimethylbutylamine was used instead of dimethylethylamine. Obtained.

Chemical reactions for the preparation of dimethylbutylaminealanborane are as follows.

AlCl ₃ + ₃ LiAlH ₄ + 4N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ → 4H ₃ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

2H ₃ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + HgCl ₂ → 2ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + Hg + H ₂

ClH ₂ Al: N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂ + LiBH ₄ → H ₂ AlBH ₄ : N (CH ₂ CH ₂ CH ₂ CH ₃ ) (CH ₃ ) ₂

Example 17 Preparation of 1-methylpyrrolidinealanborane

145 g of a colorless high-purity 1-methylpyrrolidinealanborane compound, the title compound, in the same manner as in Example 1, except that 187 g (2.2 mol) of 1-methylpyrrolidine was used instead of dimethylethylamine. 57%) was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

Example 18 Preparation of 1-methylpyrrolidinealanborane

147 g of a colorless, high-purity 1-methylpyrrolidinealanborane compound, the title compound, in the same manner as in Example 2, except that 187 g (2.2 mol) of 1-methylpyrrolidine was used instead of dimethylethylamine. %) Was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

Example 19 Preparation of 1-methylpyrrolidinealanborane

129 g (yield 50) of colorless, high-purity 1-methylpyrrolidinealanborane, the title compound, in the same manner as in Example 3, except that 187 g (2.2 mol) of 1-methylpyrrolidine was used instead of dimethylethylamine. %) Was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

Example 20 Preparation of 1-methylpyrrolidinealanborane

155 g of a colorless, high-purity 1-methylpyrrolidinealanborane compound, the title compound, in the same manner as in Example 4, except that 187 g (2.2 mol) of 1-methylpyrrolidine was used instead of dimethylethylamine. %) Was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

Example 21 Preparation of 1-methylpyrrolidinealanborane

139 g of a colorless high-purity 1-methylpyrrolidinealanborane compound, the title compound, in the same manner as in Example 5, except that 187 g (2.2 mol) of 1-methylpyrrolidine was used instead of dimethylethylamine. %) Was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

Example 22 Preparation of 1-methylpyrrolidinealanborane

136 g of a colorless high purity 1-methylpyrrolidinealanborane compound (yield 53) as the title compound in the same manner as in Example 6, except that 187 g (2.2 mol) of 1-methylpyrrolidine was used instead of dimethylethylamine. %) Was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

Example 23 Preparation of 1-methylpyrrolidinealanborane

40 g (yield) of colorless high purity 1-methylpyrrolidinealanborane which is the title compound, in the same manner as in Example 7, except that 57.8 g (0.68 mol) of 1-methylpyrrolidine was used instead of dimethylethylamine. 50%) was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

Example 24 Preparation of 1-methylpyrrolidinealanborane

41 g (yield 52) of colorless, high-purity 1-methylpyrrolidinalanborane, the title compound, in the same manner as in Example 8, except that 57.8 g (0.68 mol) of 1-methylpyrrolidin was used instead of dimethylethylamine. %) Was obtained.

Chemical reactions for preparing 1-methylpyrrolidinealanborane are as follows.

TABLE 1

As described above, the compound of the present invention has excellent thermal stability and low viscosity as compared to alan stabilized with good volatility and conventional amine, and can be processed under conditions very similar to those of using a conventional precursor. In addition, the aluminum compound facilitates the control of the transfer rate of the precursor compound in the deposition of a thin film using a chemical vapor deposition method using a bubbler as a precursor present in the liquid phase, it can be used as a precursor compound for new aluminum thin film deposition.

Claims (10)

An organometallic complex compound having a structure of Chemical Formula 1 below capable of depositing a high purity aluminum thin film on a substrate by a chemical vapor deposition method. [Formula 1] H ₂ AlBH ₄ : L _n [In Formula 1, L is a Lewis base, an amine-based organic compound capable of providing a non-covalent electron pair to the center of an aluminum metal, and a heterocyclic amine having a structure of Formula 2 below, where n is Is an integer of 1 or 2.] [Formula 2]

[In Formula 2, R ₁ and R ₂ are independently of each other hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₃ is a linear or branched alkyl group having 1 to 4 carbon atoms which is unsubstituted or substituted with halogen, and m is 2 To an integer of 8] The method of claim 1, R ₁ of L represented by Formula 2 is hydrogen, methyl or ethyl, R ₂ is hydrogen, methyl or ethyl, R ₃ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl organometallic complexes selected from t-butyl or perfluoromethyl. The method of claim 1, In Formula 2, R ₁ and R ₂ is hydrogen, R ₃ is methyl, m is 4, characterized in that the organometallic complex. delete Lithium aluminum hydride (LiAlH ₄ ), trichloroaluminum (AlCl ₃ ) and an amine compound were reacted to prepare a chloroalan compound of formula (4), and the chloroalan compound of formula ( ₄ ) was again lithium borohydride (LiBH ₄ ) or sodium hydride A method for producing the amine alanborane compound of formula (1), wherein boron (NaBH ₄ ) is reacted to produce an amine arabolane compound of formula (1). [Formula 1] H ₂ AlBH ₄ : L _n [Formula 4] ClH ₂ Al: L _n [Wherein L and n are the same as defined in claim 1 above.] delete delete The method of claim 5, The reaction is a method for producing an aminealanborane compound, characterized in that the reaction occurs under diethyl ether or a mixed solution of diethyl ether and hexane. Lithium aluminum hydride (LiAlH ₄ ), trichloroaluminum (AlCl ₃ ), an amine compound and lithium boron hydride (LiBH ₄ ) or sodium borohydride (NaBH ₄ ) by reacting to prepare an amine allaborane compound of formula 1 Method for producing an amine alanborane compound of formula (1). [Formula 1] H ₂ AlBH ₄ : L _n [Wherein L and n are the same as defined in claim 1 above.] The method of claim 9, The reaction is a method for producing an aminealanborane compound, characterized in that the reaction occurs under diethyl ether or a mixed solution of diethyl ether and hexane.