WO2007136184A1 - Aluminum compound for forming aluminum films by chemical vapor deposition and their synthesis - Google Patents

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

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Publication number
WO2007136184A1
WO2007136184A1 PCT/KR2007/002377 KR2007002377W WO2007136184A1 WO 2007136184 A1 WO2007136184 A1 WO 2007136184A1 KR 2007002377 W KR2007002377 W KR 2007002377W WO 2007136184 A1 WO2007136184 A1 WO 2007136184A1
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chemical formula
compound
preparing
amine
alane borane
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PCT/KR2007/002377
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French (fr)
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Myoung Won Kim
Jin Dong Kim
Yong Hwan Na
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Dnf Co., Ltd.
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Publication of WO2007136184A1 publication Critical patent/WO2007136184A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C23C16/20—Deposition of aluminium only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds

Definitions

  • the present invention relates to a precursor compound which is used to vapor-deposit an aluminum thin film by means of chemical vapor deposition on a substrate, and a process for preparing the same. More specifically, the present invention intends to provide a compound for forming an alumina thin film layer on an adhesive film or diffusion preventing film which is formed on a substrate such as silicone, and a process for preparing the same.
  • Aluminum (Al) metal wirings currently used for preparing 64M DRAM's absolutely depend on sputtering processes wherein aluminum wirings are vapor-deposited by using Al metal targets. However, it is anticipated that vapor-deposition of metal wirings having the circuit line width of 0.25 ⁇ m or less is not suitable for the vapor-deposition by means of sputtering mode because of high aspect ratio (depth/diameter) of the contact or via.
  • the alkylaluminum compounds mentioned above are advantageous as a CVD precursor in that they are present in liquid state having high vapor pressure at ambient temperature, the process for vapor-deposition is troublesome since the temperature of vapor-depositing the thin film is as high as in the range from 300 ° C to 400 ° C .
  • carbon being an undesirable in purity that raises electric resistance in the aluminum thin film, is incorporated in the aluminum thin film owing to the vapor deposition at such a high temperature, to provide fatal disadvantage.
  • it brings danger needing great care in handling because of explosive flammability upon minute contacting with air.
  • Dimethyl aluminum hydride having high vapor-deposition rate with high vapor pressure (2 torr at 25 ° C), is able to vapor- deposit an aluminum thin film of high purity at a relatively
  • dimethyl aluminum hydride as an alkyl aluminum compound, has explosive flammability upon contacting with air, thereby it is hard to handle. Further, high difficulty of the process for preparing the compound causes low productivity and high cost of the process, thereby resulting in poor economical feasibility.
  • the compound is also disadvantageous in that the control of the delivery rate of the precursor is not easy because it is a liquid compound with high viscosity.
  • alane (AlH 3 ) type compounds have been used as the precursor compound for Al-CVD.
  • an alkylamine alane vapor-deposits an aluminum thin film of high purity at low temperature, that is from 100 ° C to 200 °C .
  • Those compounds are colorless liquids at ambient temperature having
  • alkylamine alanes are slowly decomposed inside the storage vessel containing the precursor owing to their thermal unstableness when they are at ambient temperature or heated at 30-40 " C to be applied to the vapor deposition process.
  • a vapor deposition process having good reproducibility which is the most significant and critical requirement to be applied to a process for preparing semiconductor elements, cannot be developed.
  • the compounds also have fatal disadvantage in that they are not appropriate for storage at ambient temperature.
  • the object of the present invention is to overcome the disadvantages of precursor compounds for Al-CVD in the prior
  • the present invention provides compounds defined by
  • Chemical Formula 1 as a novel precursor compound for aluminum film vapor deposition which is designed to include as much as the advantages of conventional precursors with overcoming the disadvantages .
  • L is a Lewis base, an aminic organic compound which can provide unshared electron pair to the center of aluminum metal, such as a heterocyclic amine represented by
  • n is an integer of 1 or 2.
  • R 1 and R 2 independently represent hydrogen or Ci-C 2 alkyl group
  • R 3 represents linear or branched Ci ⁇ C 4 alkyl group with or without halogen substituent (s)
  • m is an integer from 2 to 8.
  • R 4 to R 6 independently represent hydrogen, linear or branched Ci-C 6 alkyl group with or without halogen substituent (s) or Ci-C 6 alkene group, provided that R 4 , R 5 and R 6 are not methyl all at the same time.
  • the heterocyclic amine represented by Chemical Formula 2 is selected from alkylaziridine, alkylazetidine, alkylpyrrolidine, alkylpiperidine, alkylhexamethyleneimine, and alkylheptamethyleneimine;
  • the substituents Ri and R 2 of Chemical Formula 2 and Chemical Formula 3 are independently selected from hydrogen, methyl and ethyl;
  • R 3 is selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and perfluromethyl;
  • R 4 to R 6 are independently selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and perfluoromethyl .
  • methylpyrrolidine, dimethylethylaraine and dimethylbutylamine are preferable.
  • the amine alane borane compounds defined by Chemical Formula 1 have sufficient thermal stability to overcome any problem owing to stability during mass production, in contrast to the conventional alane compound stabilized by conventional amine used as a precursor for preparing conventional aluminum film, which has weakness in thermal stability.
  • the precursor compounds for aluminum film vapor- deposition defined by Chemical Formula 1 can be easily prepared according to Reaction Formulas 1 to 4. According to the preparation of precursor compounds following Reaction Formulas 1 to 4 , the precursor compound of the present invention represented by Chemical Formula 1 is prepared by making a suspension of the mixture from each stage in diethyl ether or a mixed solution of diethyl ether and hexane,- removing the salt produced; and evaporating the solvent under reduced pressure.
  • L represents Lewis base as defined for Chemical Formula 1; n is an integer of 1 or 2; and M is Na or Li .
  • (4) is prepared by reaction of amine alane compound (5) with lithium aluminum hydride, trichloroaluminum and an amine compound represented by Chemical Formula 2 or 3 , or reaction with mercuric chloride.
  • the chemical reaction for preparing dimethylethylamine alane borane can be represented by following reaction formula.
  • the chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas. LiAlH 4 + AlCl 3 + 2N(CH 2 CH 3 ) (CH 3 J 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
  • the reaction mixture was filtered under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20 ° C) in vacuum to obtain colorless liquid.
  • the chemical reaction for preparing dimethylethylamine alane borane can be represented by following reaction formula.
  • the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient
  • chloroalane compound produced by stirring a suspension having trichloroaluminum (133.3 g, 1 mol) and lithium aluminum hydride (39.4 g, 1.04 mol) in diethyl ether (1000 ml) with cooling at -10°C under nitrogen gas stream for 1 hour.
  • Sodium borohydride (83.1 g, 2.2 mol) was then added dropwise thereto. After stirring the mixture at -10 ° C, to chloroalane compound produced by stirring a suspension having trichloroaluminum (133.3 g, 1 mol) and lithium aluminum hydride (39.4 g, 1.04 mol) in diethyl ether (1000 ml) with cooling at -10°C under nitrogen gas stream for 1 hour.
  • Sodium borohydride (83.1 g, 2.2 mol) was then added dropwise thereto. After stirring the mixture at -10 ° C.
  • reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20 ° C) in vacuum to obtain colorless liquid.
  • the chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas. LiAlH 4 + AlCl 3 + 2Et 2 O ⁇ 2ClH 2 Al: OEt 2 ClH 2 AIiOEt 2 + N(CH 2 CH 3 )(CHa) 2 ⁇ ClH 2 Al : N (CH 2 CH 3 ) (CH 3 ) 2 + Et 2 O ClH 2 AIrN(CH 2 CH 3 ) (CH 3 ) 2 + NaBH 4 ⁇ H 2 AlBH 4 : N (CH 2 CH 3 ) (CH 3 J 2
  • Lithium aluminum hydride (21.3 g, 0.56 mol) was added dropwise under nitrogen gas stream to a suspension of trichloroaluminum (22.7 g, 0.17 mol) in diethyl ether (500 ml)
  • the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20 ° C) in vacuum to obtain colorless liquid. Dried colorless filtrate was distilled while maintaining vacuum state (1.3 torr) at 45 ° C, to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless
  • distillate obtained was purified at 45 "C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (44 g, yield: 56%) .
  • the chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas.
  • Lithium aluminum hydride (21.3 g, 0.56 mol) was added dropwise under nitrogen gas stream to a suspension of trichloroaluminum (22.7 g, 0.17 mol) in diethyl ether (500 ml) for 30 seconds, while cooling at -10 ° C .
  • Dimethylethylamine Dimethylethylamine
  • the chemical reaction for preparing dimethylbutylamine alane borane can be represented by following reaction formula. LiAlH 4 +A1C1 3 +2N (CH 2 CH 2 CH 2 CH 3 ) (CH 3 ) 2 + 2LiBH 4 ⁇ 2H 2 AIBH 4 IN(CH 2 CH 2 CH 2 CH 3 ) (CH 3 J 2
  • Example 10 Preparation of dimethylbutylamine alane borane According to the same procedure as described in Example 2, but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (123 g, yield 43%) as the title compound.
  • the chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas.
  • the chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas. LiAlH 4 + AlCl 3 + 2Et 2 O ⁇ 2ClH 2 AIrOEt 2 ClH 2 Al :OEt 2 +N (CH 2 CH 2 CH 2 CH 3 ) (CH 3 J 2 ⁇ ClH 2 Al : N (CH 2 CH 2 CH 2 CH 3 ) (CH 3 ) 2 +Et 2 0
  • CIH 2 AI N(CH 2 CH 2 CH 2 CH 3 ) (CH 3 J 2 + LiBH 4 - H 2 AIBH 4 IN(CH 2 CH 2 CH 2 CH 3 ) (CH 3 ) 2
  • the chemical reaction for preparing dimethylbutylamine alane borane can be represented by following reaction formula.
  • Example 13 Preparation of dimethylbutylamine alane borane According to the same procedure as described in Example 5, but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (133 g, yield: 46%) as the title compound.
  • Example 14 Preparation of dimethylbutylamine alane borane According to the same procedure as described in Example 6, but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (127 g, yield: 44%) as the title compound.
  • the chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas.
  • Example 15 Preparation of diraethylbutylamine alane borane According to the same procedure as described in Example 7, but using dimethylbutylamine (68.7 g, 0.68 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (41 g, yield: 42%) as the title compound.
  • the chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas.
  • the chemical reaction for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formula.
  • Example 19 Preparation of 1-methylpyrrolidine alane borane According to the same procedure as described in Example 3, but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (129 g, yield: 50%) as the title compound.
  • the chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas .
  • Example 20 Preparation of 1-methylpyrrolidine alane borane According to the same procedure as described in Example 4 , but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (155 g, yield: 60%) as the title compound.
  • the chemical reaction for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formula.
  • Example 22 Preparation of 1-methylpyrrolidine alane borane According to the same procedure as described in Example 6, but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (136 g, yield: 53%) as the title compound.
  • the chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas .
  • the compounds according to the present invention show excellent volatility and thermal stability with low viscosity as compared to alanes stabilized with conventional amines. They can be processed under very similar condition in the process of conventional precursors.
  • the aluminum compounds facilitate control of delivery rate of the precursor compound in thin film vapor deposition by means of chemical vapor deposition by using a bubbler as the precursor present in liquid phase, and can be used as a precursor compound for new aluminum thin film vapor deposition.

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Abstract

The present invention relates to a precursor compound used for vapor -depositing an aluminum film on a substrate by means of chemical vapor deposition, and a process for preparing the compound. The present invention provides an organometallic complex defined by Chemical Formula 1, and a process for preparing the same. H2AlBH4: Ln In the Formula, L is a Lewis base, an aminic organic compound which can provide unshared electron pair to the center of aluminum metal, such as a heterocyclic amine or an alkylamine, and n is an integer of 1 or 2.

Description

ALUMINUM COMPOUND FOR FORMING ALUMINUM FILMS BY CHEMICAL VAPOR
DEPOSITION AND THEIR SYNTHESIS
[Technical Field]
The present invention relates to a precursor compound which is used to vapor-deposit an aluminum thin film by means of chemical vapor deposition on a substrate, and a process for preparing the same. More specifically, the present invention intends to provide a compound for forming an alumina thin film layer on an adhesive film or diffusion preventing film which is formed on a substrate such as silicone, and a process for preparing the same.
[Background Art]
Developments of new technologies and materials in the field of semiconductor industry have realized miniaturization of devices, with high confidence, high speed, high functionality and high integration. For high integration of semiconductor elements, metal wiring that transmits electric signals between those elements should have been miniaturized. Due to the miniaturization, the cross-sectional area is reduced to cause the problems of increase in the wire resistance and in parasitic capacitor owing to reduction of intervals between wirings . The increase of resistance and capacitor induces RC retention time, to make a barrier to prepare a high speed semiconductor element that is sought by- subsequent logic process. In order to prepare a high speed semiconductor element, parasitic capacitor between the metal wirings should be reduced. For this reason, it is essential to use an insulating film with low dielectric constant or metal wirings with low resistance. The process technique of metal wirings with low resistance has much room for improvement in terms of processes and devices, thereby a lot of studies have been proceeded as an important subject to establish a technique to prepare highly integrated and high-speed semiconductors .
Aluminum (Al) metal wirings currently used for preparing 64M DRAM's absolutely depend on sputtering processes wherein aluminum wirings are vapor-deposited by using Al metal targets. However, it is anticipated that vapor-deposition of metal wirings having the circuit line width of 0.25 μm or less is not suitable for the vapor-deposition by means of sputtering mode because of high aspect ratio (depth/diameter) of the contact or via.
In order to overcome such problems, aluminum wiring process has been investigated for a long time, which employs a chemical vapor deposition mode showing the advantage of high step coverage and being advantageous in make-up process of contact/via holes having high aspect ratio. As the result of such investigations, a basis for performing the process for vapor-depositing aluminum wirings via Al-CVD mode has been established, and the use of CVD process is absolutely considered. Vapor-deposition of Al thin film by means of chemical vapor deposition employs an aluminum compound called as a precursor. In the process for vapor-depositing a metal thin film by using such a metal compound, choice and property of the precursor compound is a critical element to determine the success or failure of the chemical vapor deposition (CVD) process. Thus, development or choice of the precursor to be incorporated in the process is one of the first matter to be taken account.
Early studies on chemical vapor deposition of Al metal were performed in the United States and Japan in 1980 's by employing a commercially and widely used alkyl aluminum compound, of which representative compounds that have been primarily used are trimethyl aluminum (Al (CH3) 3) and triisobutylaluminum (Al ( (CH3) 2CHCH2) 3) . Thereafter, among the precursor compounds for chemical vapor deposition of aluminum thin film (Al-CVD) in 1990' s, dimethyl aluminum hydride, [(CH3J2AlH]3 and dimethylethylamine alane, H3Al : N (CH3) 2C2H5 have been the representatives.
Though the alkylaluminum compounds mentioned above are advantageous as a CVD precursor in that they are present in liquid state having high vapor pressure at ambient temperature, the process for vapor-deposition is troublesome since the temperature of vapor-depositing the thin film is as high as in the range from 300°C to 400°C . Moreover, carbon, being an undesirable in purity that raises electric resistance in the aluminum thin film, is incorporated in the aluminum thin film owing to the vapor deposition at such a high temperature, to provide fatal disadvantage. In addition, it brings danger needing great care in handling because of explosive flammability upon minute contacting with air.
In order to solve the problems, development of the process and technique of Al-CVD method using dimethyl aluminum hydride as the precursor was commenced in early 1980' s. Dimethyl aluminum hydride, having high vapor-deposition rate with high vapor pressure (2 torr at 25°C), is able to vapor- deposit an aluminum thin film of high purity at a relatively
low temperature near 230°C, depending upon the vapor-deposition condition using hydrogen gas with a compound which is a colorless liquid at ambient temperature. However, dimethyl aluminum hydride, as an alkyl aluminum compound, has explosive flammability upon contacting with air, thereby it is hard to handle. Further, high difficulty of the process for preparing the compound causes low productivity and high cost of the process, thereby resulting in poor economical feasibility. The compound is also disadvantageous in that the control of the delivery rate of the precursor is not easy because it is a liquid compound with high viscosity.
As an alternative, alane (AlH3) type compounds have been used as the precursor compound for Al-CVD. In general, an alkylamine alane vapor-deposits an aluminum thin film of high purity at low temperature, that is from 100 °C to 200 °C . Those compounds are colorless liquids at ambient temperature having
high vapor pressure (1.5 torr at 25 "C) and somewhat lower flammability as compared to conventionally used dimethyl aluminum hydride. Moreover, they have excellent economical feasibility since they are prepared by simple preparation process .
However, since alkylamine alanes are slowly decomposed inside the storage vessel containing the precursor owing to their thermal unstableness when they are at ambient temperature or heated at 30-40 "C to be applied to the vapor deposition process. Thus, a vapor deposition process having good reproducibility, which is the most significant and critical requirement to be applied to a process for preparing semiconductor elements, cannot be developed. The compounds also have fatal disadvantage in that they are not appropriate for storage at ambient temperature.
[Disclosure] [Technical Problem] The object of the present invention is to overcome the disadvantages of precursor compounds for Al-CVD in the prior
arts, including thermal unstableness, high viscosity and explosive flammability, and to provide novel aluminum precursor compounds to extend the scope of selection of precursor compounds, and a process for preparing the same.
The present invention provides compounds defined by
Chemical Formula 1, as a novel precursor compound for aluminum film vapor deposition which is designed to include as much as the advantages of conventional precursors with overcoming the disadvantages .
[Chemical Formula 1]
H2AlBH4 : Ln wherein, L is a Lewis base, an aminic organic compound which can provide unshared electron pair to the center of aluminum metal, such as a heterocyclic amine represented by
Chemical Formula 2 or an alkylamine represented by Chemical
Formula 3, and n is an integer of 1 or 2.
[Chemical Formula 2]
R3-N (CR1R2 ^-^
In the Formula, R1 and R2 independently represent hydrogen or Ci-C2 alkyl group, R3 represents linear or branched Ci~C4 alkyl group with or without halogen substituent (s) , and m is an integer from 2 to 8. [Chemical Formula 3 ]
N-R5 R6
In the Formula, R4 to R6 independently represent hydrogen, linear or branched Ci-C6 alkyl group with or without halogen substituent (s) or Ci-C6 alkene group, provided that R4, R5 and R6 are not methyl all at the same time.
Other and further objects, features and advantages of the invention will appear more fully from the following description.
[Technical Solution]
The heterocyclic amine represented by Chemical Formula 2 is selected from alkylaziridine, alkylazetidine, alkylpyrrolidine, alkylpiperidine, alkylhexamethyleneimine, and alkylheptamethyleneimine; the substituents Ri and R2 of Chemical Formula 2 and Chemical Formula 3 are independently selected from hydrogen, methyl and ethyl; R3 is selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and perfluromethyl; and R4 to R6 are independently selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and perfluoromethyl .
Among the compounds represented by Chemical Formula 2 or Chemical Formula 3, methylpyrrolidine, dimethylethylaraine and dimethylbutylamine are preferable.
The amine alane borane compounds defined by Chemical Formula 1 have sufficient thermal stability to overcome any problem owing to stability during mass production, in contrast to the conventional alane compound stabilized by conventional amine used as a precursor for preparing conventional aluminum film, which has weakness in thermal stability.
The precursor compounds for aluminum film vapor- deposition defined by Chemical Formula 1 can be easily prepared according to Reaction Formulas 1 to 4. According to the preparation of precursor compounds following Reaction Formulas 1 to 4 , the precursor compound of the present invention represented by Chemical Formula 1 is prepared by making a suspension of the mixture from each stage in diethyl ether or a mixed solution of diethyl ether and hexane,- removing the salt produced; and evaporating the solvent under reduced pressure.
[Reaction Formula 1] LiAlH4+ AlCl3+ 2nL + 2MBH4→ 2H2AlBH4: Ln (1)
[Reaction Formula 2] LiAlH4+ AlCl3+ 2nL → 2ClH2Al: Ln (4) ClH2Al: Ln (4) + MBH4 → H2AlBH4 : Ln (1) [Reaction Formula 3]
LiAlH4+ AlCl3+ 2Et2O → 2ClH2AIiOEt2 ClH2Al: OEt2 + nL → ClH2Al: Ln (4) + Et2O ClH2Al: Ln (4) + MBH4 → H2AlBH4 : Ln (1)
[Reaction Formula 4] AlCl3+ 3LiAlH4+ 4nL → 4H3Al: Ln (5) 2H3Al: Ln (5) + HgCl2 → 2ClH2Al: Ln (4) + Hg + H2 ClH2Al: Ln (4) + MBH4 → H2AlBH4 : Ln (1)
In Reaction Formulas 1 to 4 , L represents Lewis base as defined for Chemical Formula 1; n is an integer of 1 or 2; and M is Na or Li .
As is shown by Reaction Formula 1, an amine alane borane compound of Chemical Formula (1) is prepared by one-step reaction of lithium aluminum hydride, trichloroaluminum, an amine compound represented by Chemical Formula 2 or 3 with alkali metal borohydride (MBH4; M = Na or Li) .
As is shown by Reaction Formulas 2 to 4 , amine alane borane compound of Chemical Formula (1) is obtained by reacting chloroalane compound (4) with alkali metal borohydride (MBH4; M = Na or Li) , and the chloroalane compound
(4) is prepared by reaction of amine alane compound (5) with lithium aluminum hydride, trichloroaluminum and an amine compound represented by Chemical Formula 2 or 3 , or reaction with mercuric chloride.
[Mode for Invention]
Examples are described for more specific explanation of preparation of the aluminum compounds according to the present invention, but the present invention is not limited to those Examples .
[Example 1] Preparation of dimethylethylamine alane borane
To a suspension having trichloroaluminum (133.3 g, 1 mol) in hexane (1000 ml), diethyl ether solution (500 ml) was added under nitrogen gas stream. Lithium aluminum hydride (39.4 g, 1.04 mol) was added to the mixture and the resultant mixture was stirred at ambient temperature for 24 hours. Thereafter, dimethylethylamine (161 g, 2.2 mol) was added at low
temperature (-10°C), and the mixture was stirred for 10 minutes. Then, lithium borohydride (47.8 g, 2.2 mol) was added dropwise to the reaction mixture, and the resultant mixture was stirred at 30°C for 8 hours. By using a filtering apparatus, the reaction mixture was filtered under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20°C) in vacuum to obtain colorless liquid.
Dried colorless filtrate was distilled while maintaining vacuum state (1.3 torr) at 45 °C , to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless distillate obtained was purified at 45°C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (149 g, yield: 64%) .
The chemical reaction for preparing dimethylethylamine alane borane can be represented by following reaction formula.
LiAlH4+AlCl3+ 2N(CH2CH3) (CH3)Z+ 2LiBH4 2H2AlBH4: N (CH2CH3) (CH3J2
[Example 2] Preparation of dimethylethylamine alane borane
To dichloroalane compound produced under nitrogen gas stream in a suspension having trichloroaluminum (133.3 g, 1 mol) and lithium aluminum hydride (39.4 g, 1.04 mol) in hexane
(1000 ml), dimethylethylamine (161 g, 2.2 mol) was added, and lithium borohydride (47.8 g, 2.2 mol) was then added dropwise. After stirring the mixture at 30°C for about 8 hours, the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient
temperature (20°C) in vacuum to obtain colorless liquid.
Dried colorless filtrate was distilled while maintaining
vacuum state (1.3 torr) at 45 °C, to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless
distillate obtained was purified at 45 °C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (125 g, yield: 53%) . The chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas. LiAlH4+ AlCl3+ 2N(CH2CH3) (CH3J2 → 2ClH2Al : N (CH2CH3) (CH3) 2 ClH2Al: N (CH2CH3) (CH3)2 + LiBH4 -> H2AlBH4 : N (CH2CH3) (CH3) 2
[Example 3] Preparation of dimethylethylamine alane borane
Dimethylethylamine (161 g, 2.2 mol) was added, while maintaining at -10°C, to chloroalane compound produced by stirring a suspension having trichloroaluminum (133.3 g, 1 mol) and lithium aluminum hydride (39.4 g, 1.04 mol) in
diethyl ether (1000 ml) with cooling at -10°C under nitrogen gas stream for 1 hour. Lithium borohydride (47.8 g, 2.2 mol) was then added dropwise thereto. After stirring the mixture at 30°C for about 8 hours, the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed
from the filtrate at ambient temperature (20°C) in vacuum to obtain colorless liquid.
Dried colorless filtrate was distilled while maintaining
vacuum state (1.3 torr) at 45 "C, to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless distillate obtained was purified at 45°C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (135 g, yield: 58%) .
The chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas. LiAlH4+ AlCl3+ 2Et2O → 2ClH2Al: OEt2
ClH2AIiOEt2 + N(CH2CH3) (CH3) 2 -→ ClH2Al : N (CH2CH3) (CH3) 2 + Et2O ClH2Al: N (CH2CH3) (CH3)2 + LiBH4 → H2AlBH4 : N (CH2CH3) (CH3)2
[Example 4] Preparation of dimethylethylamine alane borane
To a suspension having trichloroaluminum (133.3 g, 1 mol) in hexane (1000 ml), diethyl ether solution (500 ml) was added under nitrogen gas stream. Lithium aluminum hydride (39.4 g,
1.04 mol) was added to the mixture and the resultant mixture was stirred at ambient temperature for 24 hours. Thereafter, dimethylethylamine (161 g, 2.2 mol) was added at low
temperature (-10°C), and the mixture was stirred for 10 minutes. Then, sodium borohydride (83.1 g, 2.2 mol) was added dropwise to the reaction mixture, and the resultant mixture was stirred
at 30°Cfor 8 hours. By using a filtering apparatus, the reaction mixture was filtered under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20°C) in vacuum to obtain colorless liquid.
Dried colorless filtrate was distilled while maintaining vacuum state (1.3 torr) at 45 °C, to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless distillate obtained was purified at 45°C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (160 g, yield: 68%) .
The chemical reaction for preparing dimethylethylamine alane borane can be represented by following reaction formula.
LiAlH4H-AlCl3+ 2N(CH2CH3) (CH3) 2+ 2NaBH4 2H2AlBH4: N (CH2CH3) (CH3)2
[Example 5] Preparation of dimethylethylamine alane borane To dichloroalane compound produced under nitrogen gas stream in a suspension having trichloroaluminum (133.3 g, 1 mol) and lithium aluminum hydride (39.4 g, 1.04 mol) in hexane
(1000 ml), dimethylethylamine (161 g, 2.2 mol) was added, and sodium borohydride (83.1 g, 2.2 mol) was then added dropwise.
After stirring the mixture at 30°C for about 8 hours, the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient
temperature (20 "C) in vacuum to obtain colorless liquid.
Dried colorless filtrate was distilled while maintaining
vacuum state (1.3 torr) at 45°C, to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless
distillate obtained was purified at 45 °C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (133 g, yield: 57%) . The chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas. LiAlH4+ AlCl3+ 2N(CH2CH3) (CH3) 2 → 2ClH2Al : N (CH2CH3) (CH3) 2 ClH2Al=N(CH2CH3) (CH3)2 + NaBH4 → H2AlBH4 : N (CH2CH3) (CH3J2
[Example 6] Preparation of dimethylethylamine alane borane
Dimethylethylamine (161 g, 2.2 mol) was added, while
maintaining at -10°C, to chloroalane compound produced by stirring a suspension having trichloroaluminum (133.3 g, 1 mol) and lithium aluminum hydride (39.4 g, 1.04 mol) in diethyl ether (1000 ml) with cooling at -10°C under nitrogen gas stream for 1 hour. Sodium borohydride (83.1 g, 2.2 mol) was then added dropwise thereto. After stirring the mixture at
30°C for about 8 hours, the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20°C) in vacuum to obtain colorless liquid.
Dried colorless filtrate was distilled while maintaining vacuum state (1.3 torr) at 45°C, to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless distillate obtained was purified at 45 °C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (120 g, yield: 51%) .
The chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas. LiAlH4+ AlCl3+ 2Et2O → 2ClH2Al: OEt2 ClH2AIiOEt2 + N(CH2CH3)(CHa)2 → ClH2Al : N (CH2CH3) (CH3) 2 + Et2O ClH2AIrN(CH2CH3) (CH3)2 + NaBH4 → H2AlBH4 : N (CH2CH3) (CH3J2
[Example 7] Preparation of dimethylethylamine alane borane
Lithium aluminum hydride (21.3 g, 0.56 mol) was added dropwise under nitrogen gas stream to a suspension of trichloroaluminum (22.7 g, 0.17 mol) in diethyl ether (500 ml)
for 30 seconds, while cooling at -10°C. Dimethylethylamine (49.7 g, 0.68 mol) was added thereto, and the mixture was stirred at -10°C for 5 hours. Thereafter, the reaction mixture was filtered, and the filtrate was cooled at -25°C for 24 hours.
Precipitated solid was filtered to obtain dimethylethylamine alane compound. To the compound obtained, mercuric chloride (92 g, 0.34 mol) was added in diethyl ether solvent (250 ml), and sodium borohydride (28.3 g, 0.75 mol) was added dropwise
thereto. After stirring the mixture at 30°C for 8 hours, the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20°C) in vacuum to obtain colorless liquid. Dried colorless filtrate was distilled while maintaining vacuum state (1.3 torr) at 45°C, to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless
distillate obtained was purified at 45 "C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (44 g, yield: 56%) .
The chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas. AlCl3+ 3LiAlH4+ 4N(CH2CH3) (CH3) 2 → 4H3Al : N (CH2CH3) (CH3) 2 2H3AIiN(CH2CH3) (CH3) 2+HgCl2 → 2ClH2Al = N(CH2CH3) (CH3) 2+Hg+H2 ClH2Al = N(CH2CH3) (CH3)2 + NaBH4 → H2AlBH4 = N(CH2CH3) (CH3) 2
[Example 8] Preparation of dimethylethylamine alane borane
Lithium aluminum hydride (21.3 g, 0.56 mol) was added dropwise under nitrogen gas stream to a suspension of trichloroaluminum (22.7 g, 0.17 mol) in diethyl ether (500 ml) for 30 seconds, while cooling at -10°C . Dimethylethylamine
(49.7 g, 0.68 mol) was added thereto, and the mixture was stirred at -10°Cfor 5 hours. Thereafter, the reaction mixture was filtered, and the filtrate was cooled at -25°Cfor 24 hours.
Precipitated solid was filtered to obtain dimethylethylamine alane compound. To the compound obtained, mercuric chloride
(92 g, 0.34 mol) was added in diethyl ether solvent (250 ml), and lithium borohydride (16.2 g, 0.75 mol) was added dropwise thereto. After stirring the mixture at 30°Cfor about 8 hours, the reaction mixture was filtered by using a filtering apparatus under nitrogen gas stream to obtain the first filtrate, and the by-product filtered on the filter was then rinsed twice by using sufficient amount of hexane to obtain the second filtrate, which was then combined with the first filtrate. All volatile substances were removed from the filtrate at ambient temperature (20 TJ in vacuum to obtain colorless liquid.
Dried colorless filtrate was distilled while maintaining vacuum state (1.3 torr) at 45 °C to obtain colorless distillate condensed in a vessel chilled by dry ice. The first colorless distillate obtained was purified at 45°C through the same procedure to obtain the title compound, colorless high-purity dimethylethylamine alane borane compound (41 g, yield: 52%) . The chemical reactions for preparing dimethylethylamine alane borane can be represented by following reaction formulas.
AlCl3+ 3LiAlH4+ 4N(CH2CH3) (CH3) 2 → 4H3Al : N (CH2CH3) (CH3) 2 2H3Al: N (CH2CH3) (CH3J2+ HgCl2 → 2ClH2Al : N (CH2CH3) (CH3)2+Hg+H2 ClH2AIrN(CH2CH3) (CH3)2 + LiBH4 → H2AlBH4 : N (CH2CH3) (CH3J2
[Example 9] Preparation of dimethylbutylamine alane borane
According to the same procedure as described in Example 1, but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity diraethylbutylamine alane borane compound (143 g, yield: 50%) as the title compound.
The chemical reaction for preparing dimethylbutylamine alane borane can be represented by following reaction formula. LiAlH4+A1C13+2N (CH2CH2CH2CH3) (CH3)2 + 2LiBH4 → 2H2AIBH4IN(CH2CH2CH2CH3) (CH3J2
[Example 10] Preparation of dimethylbutylamine alane borane According to the same procedure as described in Example 2, but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (123 g, yield 43%) as the title compound. The chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas.
LiAlH4+ AlCl3+ 2N(CH2CH2CH2CH3) (CH3) 2 → 2ClH2Al: N (CH2CH2CH2CH3) (CH3)2
C1H2A1:N(CH2CH2CH2CH3) (CH3) 2 + LiBH4 → H2AlBH4: N (CH2CH2CH2CH3) (CH3)2
[Example 11] Preparation of dimethylbutylamine alane borane
According to the same procedure as described in Example 3 , but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (130 g, yield: 45%) as the title compound.
The chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas. LiAlH4+ AlCl3+ 2Et2O → 2ClH2AIrOEt2 ClH2Al :OEt2+N (CH2CH2CH2CH3) (CH3J2 → ClH2Al : N (CH2CH2CH2CH3 ) (CH3 ) 2+Et20
CIH2AI = N(CH2CH2CH2CH3) (CH3J2 + LiBH4- H2AIBH4IN(CH2CH2CH2CH3) (CH3) 2
[Example 12] Preparation of dimethylbutylamine alane borane
According to the same procedure as described in Example 4 , but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (159 g, yield: 55%) as the title compound.
The chemical reaction for preparing dimethylbutylamine alane borane can be represented by following reaction formula.
LiAlH4+AlCl3+2N (CH2CH2CH2CH3) (CH3) 2+ 2NaBH4 → 2H2AlBH4: N (CH2CH2CH2CH3) (CH3) 2
[Example 13] Preparation of dimethylbutylamine alane borane According to the same procedure as described in Example 5, but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (133 g, yield: 46%) as the title compound.
The chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas.
LiAlH4+ AlCl3+ 2N(CH2CH2CH2CH3)(CHa)2-* 2ClH2AIrN(CH2CH2CH2CH3) (CH3)2 CIH2AIIN(CH2CH2CH2CH3) (CH3) 2+ NaBH4 → H2AlBH4: N (CH2CH2CH2CH3) (CH3)2
[Example 14] Preparation of dimethylbutylamine alane borane According to the same procedure as described in Example 6, but using dimethylbutylamine (222 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (127 g, yield: 44%) as the title compound. The chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas. LiAlH4+ AlCl3+ 2Et2O → 2ClH2Al: OEt2 ClH2Al :OEt2+N (CH2CH2CH2CH3) (CH3J2 → ClH2Al : N (CH2CH2CH2CH3 ) (CH3) 2+Et20 ClH2Al: N (CH2CH2CH2CH3) (CH3J2 + NaBH4 → H2AIBH4 = N(CH2CH2CH2CH3) (CH3) 2
[Example 15] Preparation of diraethylbutylamine alane borane According to the same procedure as described in Example 7, but using dimethylbutylamine (68.7 g, 0.68 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (41 g, yield: 42%) as the title compound. The chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas.
AlCl3+ 3LiAlH4+ 4N(CH2CH2CH2CH3) (CH3)2 → 4H3AIIN(CH2CH2CH2CH3) (CH3)2
2H3Al=N(CH2CH2CH2CH3) (CH3) 2+HgCl2 → 2CIH2AI = N(CH2CH2CH2CH3) (CH3) 2+Hg+H2
CIH2AI = N(CH2CH2CH2CH3) (CH3) 2 + NaBH4 → H2AIBH4=N(CH2CH2CH2CH3) (CH3) 2
[Example 16] Preparation of dimethylbutylamine alane borane
According to the same procedure as described in Example 8 , but using dimethylbutylamine (68.7 g, 0.68 mol) instead of dimethylethylamine, obtained was colorless high-purity dimethylbutylamine alane borane compound (43 g, yield: 44%) as the title compound. The chemical reactions for preparing dimethylbutylamine alane borane can be represented by following reaction formulas. AlCl3+ 3LiAlH4+ 4N (CH2CH2CH2CH3) (CH3) 2 → 4H3Al1N(CH2CH2CH2CH3) (CH3)2 2H3Al: N (CH2CH2CH2CH3) (CH3) 2+HgCl2 → 2ClH2Al : N (CH2CH2CH2CH3 ) (CH3 ) 2+Hg+H2 C1H2A1:N(CH2CH2CH2CH3) (CH3) 2 + LiBH4 -→ H2AIBH4 = N(CH2CH2CH2CH3) (CH3) 2
[Example 17] Preparation of 1-methylpyrrolidine alane borane
According to the same procedure as described in Example 1, but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (145 g, yield: 57%) as the title compound.
The chemical reaction for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formula.
LiAIH4 + AICI3 + 2 — N | + 2LiBH4 - 2H2AIBH4 : N
[Example 18] Preparation of 1-methylpyrrolidine alane borane
According to the same procedure as described in Example 2, but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (147 g, yield: 57%) as the title compound.
The chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas
LiAIH4 + AICI3 + 2 — N j 2CIH2AIBH4 : U J
CIH2AIBH4 I N7^] + LiBH4 H2AIBH4 :V^]
[Example 19] Preparation of 1-methylpyrrolidine alane borane According to the same procedure as described in Example 3, but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (129 g, yield: 50%) as the title compound. The chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas .
LiAIH4 + AICI3 + 2Et2O 2CIH2AI : OEt2
CIH2AI : OEt2 + — N | CIH2AI: N | + Et2O
CIH2AI: Ni l + LiBH4 - H2AIBH4 : N
[Example 20] Preparation of 1-methylpyrrolidine alane borane According to the same procedure as described in Example 4 , but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (155 g, yield: 60%) as the title compound.
The chemical reaction for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formula.
LiAIH4 + AICI3 + 2 — ISl J + 2NaBH4 ■* 2H2AIBH4 : V^)
[Example 21] Preparation of 1-methylpyrrolidine alane borane
According to the same procedure as described in Example 5, but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (139 g, yield: 54%) as the title compound.
The chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas.
\ .
LiAIH4 + AICI3 + 2 — N 2CIH2AIBH4 : N
CIH2AIBH4 I N^] + NaBH4 H2AIBH4 V"]
[Example 22] Preparation of 1-methylpyrrolidine alane borane According to the same procedure as described in Example 6, but using 1-methylpyrrolidine (187 g, 2.2 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (136 g, yield: 53%) as the title compound.
The chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas.
LiAIH4 + AICI3 + 2Et2O ► 2CIH2AI : OEt2
CIH2AI : OEt2 + — f/ j + Et2O
CIH2AI: N7 J + NaBH4 * ■ H2AIBH4 : N J
[Example 23] Preparation of 1-methylpyrrolidine alane borane
According to the same procedure as described in Example 7, but using 1-methylpyrrolidine (57.8 g, 0.68 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (40 g, yield: 50%) as the title compound.
The chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas .
LiAIH4 + 3AICI3 + 4 — N J 4H3AI: N "j
Figure imgf000028_0002
CIH2AI: N J + NaBH4 H2AIBH4 : N j [Example 24] Preparation of 1-methy..pyrrolidine alane borane
According to the same procedure as described in Example 8, but using 1-methylpyrrolidine (57.8 g, 0.68 mol) instead of dimethylethylamine, obtained was colorless high-purity 1- methylpyrrolidine alane borane compound (41 g, yield: 52%) as the title compound.
The chemical reactions for preparing 1-methylpyrrolidine alane borane can be represented by following reaction formulas.
LiAIH4 + 3AICI3 + 4 — N 4H3AI
2H3AI: N + HgCI2 ■ 2CIH2AI :V^| Hg + H2
Figure imgf000029_0001
[Table 1]
Figure imgf000029_0002
Figure imgf000030_0001
[industrial Applicability]
As described above, the compounds according to the present invention show excellent volatility and thermal stability with low viscosity as compared to alanes stabilized with conventional amines. They can be processed under very similar condition in the process of conventional precursors. The aluminum compounds facilitate control of delivery rate of the precursor compound in thin film vapor deposition by means of chemical vapor deposition by using a bubbler as the precursor present in liquid phase, and can be used as a precursor compound for new aluminum thin film vapor deposition.

Claims

ICLAIMS] [Claim l] An organometallic complex which can vapor-deposit a high- purity aluminum thin film by means of chemical deposition on a substrate, represented by following chemical structural formula:
[Chemical Formula 1] H2AlBH4 : Ln wherein, L is a Lewis base, an aminic organic compound which can provide unshared electron pair to the center of aluminum metal, such as a heterocyclic amine represented by Chemical Formula 2 or an alkylamine represented by Chemical Formula 3, and n is an integer of 1 or 2. [Chemical Formula 2]
R3-N (CR1R2U V-^-7
[In the Formula, Ri and R2 independently represent hydrogen or Ci-C2 alkyl group, R3 represents linear or branched Cx-C4 alkyl group with or without halogen substituent (s) , and m is an integer from 2 to 8.] [Chemical Formula 3]
Figure imgf000031_0001
[In the Formula, R4 to R6 independently represent hydrogen, linear or branched Ci-C6 alkyl group with or without halogen substituent (s) or Ci-C6 alkene group, provided that R4, R5 and R6 are not methyl all at the same time.]
[Claim 2]
An organometallic complex according to claim 1, wherein R1 and R2 of L represented by Chemical Formula 2 or Chemical Formula 3 independently represent hydrogen, methyl or ethyl, R3 represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n- butyl, i-butyl, t-butyl, n-pentyl, n-hexyl or perfluoromethyl, and R4 to R6 are independently selected from hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl or perfluoromethyl .
[Claim 3]
An organometallic complex according to claim 1, wherein R1 and R2 of Chemical Formula 2 is hydrogen, R3 is methyl, and m is 4.
[Claim 4]
An organometallic complex according to claim 1, wherein R4 and R5 of Chemical Formula 3 is methyl, and R6 is ethyl or butyl.
[Claim 5]
A process for preparing an amine alane borane compound, wherein the amine alane borane compound of Chemical Formula 1 is prepared by reacting a chloroalane compound of Chemical Formula 4 with lithium borohydride (LiBH4) or sodium borohydride (NaBH4) .
[Chemical Formula 1] H2AlBH4 : Ln [Chemical Formula 4] ClH2Al : Ln
[In the Formulas, L and n have same meaning as defined in claim 1.] [Claim 6]
A process for preparing an amine alane borane compound according to claim 5, wherein the chloroalane compound of Chemical Formula 4 is prepared by reacting an amine alane compound of Chemical Formula 5 with mercuric chloride (HgCl2) . [Chemical Formula 4] ClH2Al: Ln
[Chemical Formula 5] H3Al : Ln
[In the Formulas, L and n have same meaning as defined in claim 1.]
[Claim 7]
A process for preparing an amine alane borane compound according to claim 5, wherein the chloroalane compound of
Chemical Formula 4 is prepared by reacting lithium aluminum hydride (LiAlH4) , trichloroaluminum (AlCl3) and an amine compound.
[Chemical Formula 4] ClH2Al : Ln
[In the Formulas, L and n have same meaning as defined in claim 1.]
[Claim 8 ]
A process for preparing an amine alane borane compound according to claim 5, wherein said reaction is carried out in the presence of diethyl ether or a mixed solution of diethyl ether and hexane .
[Claim 9]
A process for preparing an amine alane borane compound wherein the amine alane borane compound of Chemical Formula 1 is prepared by reacting lithium aluminum hydride (LiAlH4) , trichloroaluminum (AlCl3) , an amine compound and lithium borohydride (LiBH4) or sodium borohydride (NaBH4) .
[Claim 10]
A process for preparing an amine alane borane compound according to claim 9, wherein said reaction is carried out in the presence of diethyl ether or a mixed solution of diethyl ether and hexane .
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