WO2024067469A1 - Procédé de préparation et utilisation de dialkylaminosilane - Google Patents

Procédé de préparation et utilisation de dialkylaminosilane Download PDF

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Publication number
WO2024067469A1
WO2024067469A1 PCT/CN2023/121047 CN2023121047W WO2024067469A1 WO 2024067469 A1 WO2024067469 A1 WO 2024067469A1 CN 2023121047 W CN2023121047 W CN 2023121047W WO 2024067469 A1 WO2024067469 A1 WO 2024067469A1
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WO
WIPO (PCT)
Prior art keywords
bis
preparation
monosilane
reaction
dialkylaminosilane
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PCT/CN2023/121047
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English (en)
Chinese (zh)
Inventor
鲁铮
王忠英
赵彬驭
蔡崇玄
周晓兵
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江苏南大光电材料股份有限公司
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Publication of WO2024067469A1 publication Critical patent/WO2024067469A1/fr

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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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages

Definitions

  • the present invention relates to the technical field of organic synthesis, and in particular to a preparation method of dialkylaminosilane and application thereof.
  • Polyaminosilane is usually used as a raw material (precursor) to manufacture silicon-based semiconductor thin film materials such as silicon oxide, silicon nitride and silicon carbide through traditional vapor deposition and more precisely controlled atomic layer deposition. These silicon-based semiconductor thin film materials have been used to manufacture high-end capacitors, solar cells, memory devices, lasers, light-emitting diodes, and gas sensors.
  • dialkylaminosilane can be prepared by traditional chlorosilane amination reaction.
  • JPWO2016152226A1 produces dialkylaminosilane by direct reaction of chlorosilane and dialkylamine, and in addition to the target product, a large amount of by-product hydrochloride is generated.
  • Patent CN107365416A proposes a method for preparing side chain modified polysiloxane, by mixing dichlorosilane with an organic solvent, then adding acrylic acid, acryl alcohol or allylamine to the mixed solution, and removing the organic solvent by vacuum distillation after the reaction is completed to obtain a chlorosilane substitution product; the chlorosilane substitution product and a catalyst are added to a solvent for reaction, and the organic solvent is removed by vacuum distillation to obtain a hydrosilylation product; the hydrosilylation product is then co-hydro
  • the raw materials are cheap and easy to obtain and the product yield is high, but there are too many operating steps and the product contains chlorine impurities.
  • a large amount of solid byproduct hydrochloride is formed during the reaction process, and the reaction requires the use of a large amount of solvent, which will reduce the volume efficiency, and the product contains chlorine impurities.
  • the main purpose of the present invention is to provide a preparation method of dialkylaminosilane and its use, so as to overcome the shortcomings of the prior art.
  • the technical solution adopted by the present invention includes:
  • An embodiment of the present invention provides a method for preparing dialkylaminosilane, which comprises:
  • the monosilane is introduced into a sealed reaction chamber containing a mixture of an amine source and a catalyst, and reacted at a temperature of -10 to 30° C. to obtain dialkylaminosilane;
  • the molar ratio of monosilane to amine source is ⁇ 0.5; the catalyst includes any one of dibutyl magnesium, potassium bis(trimethylsilyl)amide, calcium bis(hexamethyldisilazide), and strontium bis(hexamethyldisilazide); and the input rate of monosilane is 1 to 5 L/min.
  • the dialkylaminosilane includes any one of bis( diethylamino )silane ( SiH2 [N( CH2CH3 ) 2 ] 2 ), bis(tert-butylamino)silane ( SiH2 [ NH ( C4H9 )] 2 ), and bis(n-propylamino)silane ( SiH2 [ N (CH2CH2CH3 ) 2 ] 2 ).
  • the embodiment of the present invention also provides the use of the dialkylaminosilane prepared by the above-mentioned preparation method in the preparation of silicon-based semiconductor thin film materials.
  • the present invention has the following beneficial effects:
  • the preparation method of dialkylaminosilane provided by the present invention is a one-step reaction, and the yield of dialkylaminosilane is as high as 95.9%.
  • FIG1 is a nuclear magnetic spectrum of bis(diethylamino)silane prepared in Example 1 of the present invention.
  • FIG. 2 is a mass spectrum of bis(diethylamino)silane prepared in Example 1 of the present invention.
  • a method for preparing a dialkylaminosilane includes:
  • the monosilane is introduced into a sealed reaction chamber containing a mixture of an amine source and a catalyst, and reacted at a temperature of -10 to 30° C. to obtain dialkylaminosilane;
  • the molar ratio of monosilane to amine source is ⁇ 0.5; the catalyst includes any one of dibutyl magnesium, potassium bis(trimethylsilyl)amide, calcium bis(hexamethyldisilazide), and strontium bis(hexamethyldisilazide); and the input rate of monosilane is 1 to 5 L/min.
  • the amine source includes any one of diethylamine, tert-butylamine, and di-n-propylamine, but is not limited thereto.
  • the water content in the amine source is ⁇ 300 ppm.
  • the silane used in the present invention is in excess relative to the amine source.
  • the dialkylaminosilane includes any one of bis( diethylamino )silane ( SiH2 [N( CH2CH3 ) 2 ] 2 , also referred to as BDEAS), bis(tert - butylamino)silane ( SiH2 [NH( C4H9 )] 2 , also referred to as BTBAS), and bis(n -propylamino)silane (SiH2[N(CH2CH2CH3 ) 2 ] 2 ) , but is not limited thereto.
  • the catalyst includes any one of potassium bis(trimethylsilyl)amide, calcium bis(hexamethyldisilazide), and strontium bis(hexamethyldisilazide).
  • the raw materials used in the present invention and the generated products are all chlorine-free materials and there will be no chlorine pollution.
  • the first pressure in the closed reaction device is controlled to be 1 to 15 bar.
  • the mass ratio of the catalyst to the amine source is 0.01 to 0.05:1.
  • the reaction temperature is 15-25°C.
  • monosilane is introduced into the sealed reaction chamber by means of back pressure or pressure suppression.
  • the preparation method specifically includes: introducing monosilane into the sealed reaction chamber at one time by means of holding pressure, and carrying out the reaction, and when the pressure no longer rises during the reaction, ending the reaction.
  • the preparation method specifically comprises: continuously introducing monosilane into the sealed reaction chamber by back pressure, The reaction is carried out, and the pressure in the sealed reaction chamber is kept constant during the reaction. When the amount of monosilane introduced into the sealed reaction chamber reaches a specified value, the reaction is terminated.
  • the pressure relief pressure of the back pressure valve at the gas outlet of the reactor is adjusted to a specified value, and then monosilane is continuously introduced into the reactor.
  • the pressure of the reactor reaches the specified value of the back pressure valve, the reactor is depressurized through the back pressure valve. In this way, monosilane is continuously introduced into the reactor during the reaction process, and the pressure is always maintained at the specified value of the back pressure valve. This process is called a back pressure reaction method.
  • the preparation method of the dialkylaminosilane includes (taking the preparation of BDEAS, BTBAS, and bis(n-propylamino)silane as an example):
  • the catalyst includes dibutyl magnesium (Mg(C 4 H 9 ) 2 ), bis(trimethylsilyl) potassium amide (KN((CH 3 ) 3 Si) 2 ), bis(hexamethyldisilazide) calcium (Ca(N((CH 3 ) 3 Si) 2 ) 2 ) or bis(hexamethyldisilazide) strontium (Sr(N((CH 3 ) 3 Si) 2 ) 2 );
  • Another aspect of the technical solution of the present invention also provides the use of the dialkylaminosilane prepared by the aforementioned preparation method in the preparation of silicon-based semiconductor thin film materials.
  • the silicon-based semiconductor thin film material includes any one of silicon oxide, silicon nitride, and silicon carbide, but is not limited thereto.
  • experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a method for synthesizing bis(diethylamino)silane under pressure holding conditions comprises the following steps:
  • the NMR spectrum of the bis(diethylamino)silane prepared in this example is shown in FIG1 , and the mass spectrum is shown in FIG2 .
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • a method for synthesizing bis(tert-butylamino)silane under back pressure conditions comprises the following steps:
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • a method for synthesizing bis(n-propylamino)silane under pressure holding conditions comprises the following steps:
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • a method for synthesizing bis(diethylamino)silane under pressure holding conditions comprises the following steps:
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • a method for synthesizing bis(diethylamino)silane under pressure holding conditions comprises the following steps:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation et une utilisation de dialkylaminosilane. Le procédé de préparation comprend : l'introduction de monosilane dans une chambre de réaction scellée contenant un mélange d'une source d'amine et d'un catalyseur, et la réaction de celui-ci à une température de -10 °C à 30 °C pour préparer du dialkylaminosilane, le rapport molaire du monosilane à la source d'amine étant ≥ 0,5 ; le catalyseur comprend l'un quelconque parmi le dibutylmagnésium, le bis(triméthylsilyl)amide de potassium, le bis(hexaméthyldisilazide) de calcium et le bis(hexaméthyldisilazide) de strontium ; et le taux d'entrée du monosilane est de 1 à 5 L/min. Le procédé de préparation de dialkylaminosilane selon la présente invention implique une réaction en une étape ; de plus, la formation d'une grande quantité de solides est évitée pendant le processus de réaction, et le taux d'utilisation de l'espace est élevé.
PCT/CN2023/121047 2022-09-26 2023-09-25 Procédé de préparation et utilisation de dialkylaminosilane WO2024067469A1 (fr)

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CN202211172427.0 2022-09-26
CN202211172427.0A CN115260222B (zh) 2022-09-26 2022-09-26 一种二烷基氨基硅烷的制备方法及其用途

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CN115260222B (zh) * 2022-09-26 2023-01-31 江苏南大光电材料股份有限公司 一种二烷基氨基硅烷的制备方法及其用途
CN117143141B (zh) * 2023-10-30 2024-01-12 江苏南大光电材料股份有限公司 一种三（二甲胺基）硅烷的制备方法及制备系统

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