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CN-117164618-B - Preparation method of metal complex precursor and metal oxide film

CN117164618BCN 117164618 BCN117164618 BCN 117164618BCN-117164618-B

Abstract

The invention relates to a preparation method of a metal complex precursor and a metal oxide film. The preparation method of the metal complex precursor comprises the following steps of reacting a Grignard reagent with alkylamine, adding MCl 4 into a reaction system after the reaction is finished to continue the reaction, and preparing the metal complex precursor, wherein the alkylamine has the structural formula of HNR 1 R 2 ,R 1 and R 2 which respectively and independently comprise C 1 ～C 3 alkyl, M comprises one or more of Ge and Sn, and the structural formula of the metal complex precursor has the structural formula of M (NR 1 R 2 ) 4 . The preparation method can improve the reaction safety, improve the yield and the purity, and is easy for industrialized mass production.

Inventors

  • PANG ZENGBO
  • HUANG KAIYUAN
  • HONG CHANGWEN

Assignees

  • 苏州欣诺科生物科技有限公司

Dates

Publication Date
20260505
Application Date
20230906

Claims (11)

  1. 1. The preparation method of the metal complex precursor is characterized by comprising the following steps of: Reacting a Grignard reagent with alkylamine, and adding MCl 4 into a reaction system to continue the reaction after the reaction is finished, so as to prepare a metal complex precursor; Wherein the alkylamine has a structural formula of HNR 1 R 2 ,R 1 and R 2 each independently comprises a C 1 ~C 3 alkyl group, M comprises one or both of Ge and Sn, and the metal complex precursor has a structural formula of M (NR 1 R 2 ) 4 .
  2. 2. The method of preparing a metal complex precursor according to claim 1, wherein the grignard reagent comprises one or more of ethynylmagnesium bromide, vinylmagnesium bromide, n-propylmagnesium bromide, 1-propynylmagnesium bromide, isopropenylmagnesium bromide, propenyl magnesium bromide, cyclopropylmagnesium bromide, n-butylmagnesium bromide, sec-butylmagnesium bromide, 3-butenylmagnesium bromide, hexylmagnesium bromide, methylmagnesium chloride, ethylmagnesium chloride, ethynylmagnesium chloride, vinylmagnesium chloride, propenyl magnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, sec-butylmagnesium chloride, and tert-butylmagnesium chloride.
  3. 3. The method of preparing a metal complex precursor according to claim 2, wherein the grignard reagent comprises n-propyl magnesium bromide.
  4. 4. The method for preparing a metal complex precursor according to claim 1, wherein the molar ratio of the grignard reagent to the alkylamine is 1 (1-1.5).
  5. 5. The method of preparing a metal complex precursor according to claim 1, wherein the alkylamine comprises one or more of dimethylamine, diethylamine, and methylethylamine.
  6. 6. The method for preparing a metal complex precursor according to any one of claims 1 to 5, wherein the step of reacting the grignard reagent with the alkylamine comprises the steps of adding the alkylamine into the grignard reagent and an anhydrous hydrocarbon solvent at-15 ℃ to 0 ℃ under a protective atmosphere, and reacting for 6 to 10 hours at 20 ℃ to 30 ℃ after the addition is completed.
  7. 7. The method of preparing a metal complex precursor according to claim 6, wherein the anhydrous hydrocarbon solvent comprises anhydrous n-hexane.
  8. 8. The method for preparing the metal complex precursor according to claim 1, wherein the step of adding MCl 4 into a reaction system for continuous reaction comprises the steps of reducing the reaction system to-15 ℃ to 0 ℃, adding MCl 4 into the reaction system under a protective atmosphere, and stirring and reacting for 10h to 14h at 20 ℃ to 30 ℃ after the addition is finished.
  9. 9. The method for preparing a metal complex precursor according to claim 1 or 8, wherein the molar ratio of the alkylamine to the MCl 4 is (4-5): 1.
  10. 10. The method for preparing a metal complex precursor according to any one of claims 1 to 5 and 7 to 8, further comprising the steps of filtering and distilling after the step of adding MCl 4 to continue the reaction.
  11. 11. The preparation method of the metal oxide film is characterized by comprising the following steps: preparing a metal complex precursor by the preparation method according to any one of claims 1 to 10; and (3) reacting the metal complex precursor with an oxygen source to form a film, so as to prepare the metal oxide film.

Description

Preparation method of metal complex precursor and metal oxide film Technical Field The invention relates to the field of organic metal compounds, in particular to a preparation method of a metal complex precursor and a metal oxide film. Background With the development of the very large scale integrated circuit industry, more stringent requirements are being placed on the properties of semiconductor materials and their manufacturing processes. According to moore's law, as the size of individual electronic devices is reduced, integrated circuit technology is continually evolving and the thickness of the gate dielectric layer is one of the determining factors affecting the size of the electronic devices. At present, siO 2 is widely used as a gate dielectric material of an electronic device in the integrated circuit industry, but as the characteristic size of the device is reduced, when the thickness of a SiO 2 gate dielectric layer is reduced to the nanometer level, the leakage current passing through SiO 2 is exponentially increased along with the reduction of the thickness of the SiO 2 gate dielectric layer, so that the device performance is seriously affected by the huge leakage current, and finally, the SiO 2 cannot play an insulating role. Finding a high dielectric constant material (high-K material) to replace the conventional SiO 2, reducing the tunneling effect by increasing the physical thickness of the dielectric layer is an effective technical means for improving the stability of the electronic device. It is therefore important to find high K and metal gate material precursors suitable for ALD (atomic layer deposition) and CVD (chemical vapor deposition) use. Based on this, in recent years, germanium complex precursors and tin complex precursors have gradually come into the field of view of developers. For example, tetra (dimethylamino) germanium is a liquid at normal temperature, is a compound very sensitive to air and water vapor, can be dissolved in organic solvents such as hydrocarbons, carbon tetrachloride and the like, has better stability and higher vapor pressure, and also has quite high reactivity. However, the preparation methods of the germanium complex precursor and the tin complex precursor are few at present, the highly flammable raw materials of butyl lithium and intermediate dimethyl amino lithium are generally needed in the preparation process, and the high potential safety hazard exists, and meanwhile, the lithium chloride which is a reaction byproduct is easy to remain in the product, so that the metal purity of the product is influenced, and the product needs to be purified for many times to meet the requirement of semiconductor purity, thereby reducing the product yield and limiting the industrialized amplification production of the germanium complex precursor and the tin complex precursor. Disclosure of Invention Based on the above, some embodiments of the present invention provide a method for preparing a metal complex precursor, which can improve the reaction safety and the yield and purity, and is easy for industrial mass production. In addition, other embodiments of the invention also provide a preparation method of the metal oxide film. A method for preparing a metal complex precursor, comprising the steps of: Reacting a Grignard reagent with alkylamine, and adding MCl 4 into a reaction system to continue the reaction after the reaction is finished, so as to prepare a metal complex precursor; The structural formula of the alkylamine is HNR 1R2,R1 and R 2, wherein the structural formula of the alkylamine is HNR 1R2,R1 and R 2 respectively and independently comprise C 1～C3 alkyl, M comprises one or more of Ge and Sn, and the structural formula of the metal complex precursor is M (NR 1R2)4. In some of these embodiments, the grignard reagent comprises one or more of ethynylmagnesium bromide, vinyl magnesium bromide, n-propylmagnesium bromide, 1-propynylmagnesium bromide, isopropenylmagnesium bromide, propenyl magnesium bromide, cyclopropylmagnesium bromide, n-butylmagnesium bromide, sec-butylmagnesium bromide, 3-butenylmagnesium bromide, hexylmagnesium bromide, methylmagnesium chloride, ethylmagnesium chloride, ethynylmagnesium chloride, vinyl magnesium chloride, propenyl magnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, sec-butylmagnesium chloride, and tert-butylmagnesium chloride; optionally, the grignard reagent comprises n-propyl magnesium bromide. In some embodiments, the molar ratio of the grignard reagent to the alkylamine is 1 (1-1.5). In some of these embodiments, the alkylamine comprises one or more of dimethylamine, diethylamine, and methylethylamine. In some embodiments, the step of reacting the Grignard reagent with the alkylamine comprises the steps of adding the alkylamine into the Grignard reagent and an anhydrous hydrocarbon solvent at-15 ℃ to 0 ℃ under a protective atmosphere, and reacting for 6h to 10h at 20 ℃ to 30 ℃ after the addit