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WO2019067139A1 - Réduction sélective de chlorodisilanes avec de l'hydrure de tri-n-butyle étain - Google Patents

Réduction sélective de chlorodisilanes avec de l'hydrure de tri-n-butyle étain Download PDF

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Publication number
WO2019067139A1
WO2019067139A1 PCT/US2018/048276 US2018048276W WO2019067139A1 WO 2019067139 A1 WO2019067139 A1 WO 2019067139A1 US 2018048276 W US2018048276 W US 2018048276W WO 2019067139 A1 WO2019067139 A1 WO 2019067139A1
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WO
WIPO (PCT)
Prior art keywords
tri
butyl tin
tin hydride
solvent
hexachlorodisilane
Prior art date
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Ceased
Application number
PCT/US2018/048276
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English (en)
Inventor
Travis SUNDERLAND
Brian D. Rekken
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Dow Silicones Corp
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Dow Silicones Corp
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Filing date
Publication date
Application filed by Dow Silicones Corp filed Critical Dow Silicones Corp
Publication of WO2019067139A1 publication Critical patent/WO2019067139A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes

Definitions

  • This invention relates to a method for selectively reducing hexachlorodisilane to produce 1,1,1-trichlorodisilane.
  • 1,1,1-trichlorodisilane (1,1,1-3CDS) with a high degree of selectivity for 1,1,1-3CDS over other disilanes including other isomers of trichlorodisilane as well as other chloro(di)silanes and alkyl(di)silane impurities.
  • the present invention solves the problem of providing a method for making 1,1,1- 3CDS with a high degree of selectivity for 1,1,1-3CDS over other disilanes including other isomers of trichlorodisilane as well as other chloro(di)silanes and alkyl(di)silane impurities.
  • the present invention provides a method for producing 1,1,1-3CDS with 99 weight-percent (wt%) selectivity over the 1,1,2-trichlorodisilane isomer relative to combined weight of the two trichlorodisilane isomers.
  • the method of the present invention produces 1,1,1-3CDS at 65 wt% or higher selectivity over other chlorodisilane byproducts. Wt% values for selectivity are determined by gas
  • the method of the present invention is a result of discovering that 1,1,1-3CDS can be made with a high level of selectivity by starting with tri-n-butyl tin hydride in a solvent to form a mixture and then adding to the mixture hexachlorodisilane (HCDS) at a temperature of 20 degrees Celsius (°C) or colder.
  • HCDS hexachlorodisilane
  • the present invention is a method for producing 1,1,1- trichlorodisilane; said method comprising adding hexachlorodisilane to a mixture of tri-n- butyl tin hydride in a solvent at a temperature no greater than 20 °C.
  • Tri-n-butyl tin hydride (Bu3SnH) has CAS No. 688-73-3 and is also known as Tri-n-butylstannane.
  • the method of the present invention requires forming a mixture of tri-n-butyl tin hydride (TBTH) in a solvent.
  • TBTH can be added to solvent or solvent can be added to TBTH to form the mixture.
  • the solvent is a non-polar organic solvent.
  • Preferred non-polar organic solvents include C4-C20 hydrocarbons and ethers; preferably C6-C20 linear or branched alkanes, C6-C20 aromatic hydrocarbons or C4-C20 ethers; preferably decane, isododecane, toluene, xylene, diisopropylbenzene, mesitylene, diethyl ether or dibutyl ether; preferably xylene, decane or isododecane. Mixtures of organic solvents mentioned herein may be used.
  • the non-polar organic solvent can be aromatic or non-aromatic.
  • the solvent is generally present at a concentration of 1 to 99 wt%, based on the weight of the organic solvent and TBTH. Desirably, the solvent is present at a concentration of 10 wt% or more, preferably 20 wt% or more and can be 30 wt% or more, 40 wt% or more, 50 wt% or more while at the same time is preferably 90 wt% or less, preferably 80 wt% or less, preferably 70 wt% or less and can be 60 wt% or less, 50 wt% or less, 30 wt% or less, even 25 wt% or less with wt% relative to combined weight of solvent and TBTH.
  • the mixture of organic solvent and tri-n-butyl tin hydride is substantially free of Lewis bases, which means the mixture has less than 5 wt% of Lewis bases (Lewis bases do not include ether solvents), preferably less than 2 wt%, preferably less than 1 wt%, preferably less than 0.5 wt%, preferably less than 0.1 wt%, as a percentage of the total amount of solvent and tri-n-butyl tin hydride.
  • the method requires addition of hexachlorodisilane (HCDS) to the mixture of organic solvent and TBTH.
  • HCDS hexachlorodisilane
  • the solvent is selected so as to remain liquid at the temperature maintained during the addition of HCDS.
  • HCDS hexachlorodisilane
  • tri-n-butyl tin hydride a molar ratio of hexachlorodisilane (HCDS) to tri-n-butyl tin hydride that is from 1:3 to 1:2, preferably 1:2.8 to 1:2.2, and more preferably 1:2.7 to 1:2.3.
  • 1,1,1-3CDS is formed by the reaction of HCDS and TBTH during the addition of HCDS and during the time after completion of HCDS addition. It is desirable to purify the 1,1,1-3CDS by distillation, preferably at a pressure below 760 millimeters mercury.
  • 1,1,1-3CDS may be used to form a silicon-heteroatom film by known techniques, including, e.g., physical vapor deposition, atomic layer deposition (ALD), or chemical vapor deposition (CVD).
  • the physical vapor deposition method may comprise sputtering. Suitable sputtering methods include direct current (DC) magnetron sputtering, ion-beam sputtering, reactive sputtering, and ion-assisted sputtering.
  • the deposition method comprises ALD or CVD.
  • the heteroatoms are selected from carbon, oxygen and nitrogen.
  • Suitable ALD methods include plasma enhanced atomic layer deposition methods (PEALD), spatial atomic layer deposition (SALD) and thermal atomic layer deposition (TALD) methods.
  • PEALD methods the plasma may be any one of the foregoing plasmas.
  • the plasma may optionally further contain a carrier gas such as molecular nitrogen or argon gas.
  • Plasmas are formed from plasma-forming gases, which may comprise a mixture of molecular nitrogen and molecular hydrogen.
  • Suitable CVD methods include simple thermal vapor deposition, plasma enhanced chemical vapor deposition (PECVD), electron cyclotron resonance (ECRCVD), atmospheric pressure chemical vapor deposition (APCVD), low pressure chemical vapor deposition (LPCVD), ultrahigh vacuum chemical vapor deposition (UHVCVD), aerosol-assisted chemical vapor deposition (AACVD), direct liquid injection chemical vapor deposition (DLICVD), microwave plasma-assisted chemical vapor deposition (MPCVD), remote plasma-enhanced chemical vapor deposition (RPECVD), atomic layer chemical vapor deposition (ALCVD), hot wire chemical vapor deposition (HWCVD), hybrid physical- chemical vapor deposition (HPCVD), rapid thermal chemical vapor deposition (RTCVD), and vapor-phase epitaxy chemical vapor deposition (VPECVD), photo-assisted chemical vapor disposition (PACVD), and flame assisted chemical vapor deposition (FACVD).
  • PECVD plasma enhanced chemical vapor deposition
  • Comparative Example 1 showing low selectivity for 1,1,1-3CDS over other chlorodisilanes by using Bu3SnH at room temperature in a solvent with a Lewis base catalyst (/. Organomet. Chem. 1995, 494, 143)
  • Comparative Example 2 showing low selectivity for 1,1,1-3CDS over other chlorodisilanes by using Bu3SnH at room temperature and in a solvent absent of a Lewis base catalyst (Batch 27003-16-1)
  • tri-n-butyltin hydride (2.15 mL, 2.33 g, 2.0 eq) and toluene (0.75 mL, 0.65 g. 37 wt%) were loaded into a 250 mL 3-neck half -jacketed round bottom flask equipped with a glass thermowell and held at 23 °C.
  • hexachlorodisilane (HCDS, 0.69 mL, 1.1 g, 1 eq) was added to the Bu3SnH solution over 6 min, followed by continued stirring for 50 min.
  • the solution was analyzed by GC-TCD, showing a solution containing 16.5 wt% 1,1,1-3CDS, 53.1 wt% combined other chlorodisilanes, and no detectable alkyl(di)silane with wt% relative to all mono and disilanes present as determined by gas chromatography (GC) using the method described hereinbelow.
  • tri-n-butyltin hydride (3.75 mL, 4.06 g, 2.5 eq) and decane (1.69 mL, 1.23 g. 45 wt%) were loaded into a 250 mL 3-neck half -jacketed round bottom flask equipped with a glass thermowell and held at -14 °C.
  • hexachlorodisilane (HCDS, 0.96 mL, 1.50 g, 1 eq) was added to the Bu3SnH solution over 5 min, followed by continued stirring for 165 min.
  • the solution was analyzed by GC-TCD, showing a solution containing 43.4 wt% 1,1,1- 3CDS, 22.5 wt% combined other chlorodisilanes, and no detectable alkyl(di)silane with wt% relative to all mono and disilanes present as determined by gas chromatography (GC) using the method described herein below. Notably, no 1 , 1 ,2-trichlorodisilane was detected indicating greater than 99 wt% selectivity of 1,1,1-3CDS over the combination of 1,1,1 -and 1,1,2-trichlorodisilane isomers.
  • GC-TCD thermal conductivity detector

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de 1,1,1-trichlorodisilane comprenant l'ajout d'hexachlorodisilane à l'hydrure de tri-n-butyle étain dans un solvant à une température de 20 °C ou moins.
PCT/US2018/048276 2017-09-28 2018-08-28 Réduction sélective de chlorodisilanes avec de l'hydrure de tri-n-butyle étain Ceased WO2019067139A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762564347P 2017-09-28 2017-09-28
US62/564,347 2017-09-28

Publications (1)

Publication Number Publication Date
WO2019067139A1 true WO2019067139A1 (fr) 2019-04-04

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Application Number Title Priority Date Filing Date
PCT/US2018/048276 Ceased WO2019067139A1 (fr) 2017-09-28 2018-08-28 Réduction sélective de chlorodisilanes avec de l'hydrure de tri-n-butyle étain

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TW (1) TW201914956A (fr)
WO (1) WO2019067139A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4798713A (en) * 1987-12-28 1989-01-17 Dow Corning Corporation Method of selective reduction of halodisilanes with alkyltin hydrides
EP0301678A2 (fr) * 1987-07-27 1989-02-01 Dow Corning Corporation Procédé de réduction sélective de polyhalosinanes avec des hydrures d'alkylétain

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0301678A2 (fr) * 1987-07-27 1989-02-01 Dow Corning Corporation Procédé de réduction sélective de polyhalosinanes avec des hydrures d'alkylétain
US4798713A (en) * 1987-12-28 1989-01-17 Dow Corning Corporation Method of selective reduction of halodisilanes with alkyltin hydrides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HERZOG U ET AL, JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 494, no. 1, 31 May 1995 (1995-05-31), pages 143 - 147, XP004023965, ISSN: 0022-328X, DOI: 10.1016/0022-328X(95)05398-9 *
J. ORGANOMET. CHEM., vol. 494, 1995, pages 143
U. HERZOG ET AL., J. ORGANOMETALLIC CHEM., vol. 161, 1978, pages 165 - 169

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