WO2010121871A1 - Procédé pour la mesure du taux de conversion de la réaction de tétrachlorure de silicium avec de l'hydrogène pour former du tétrachlorosilane et du chlorure d'hydrogène - Google Patents

Procédé pour la mesure du taux de conversion de la réaction de tétrachlorure de silicium avec de l'hydrogène pour former du tétrachlorosilane et du chlorure d'hydrogène Download PDF

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Publication number
WO2010121871A1
WO2010121871A1 PCT/EP2010/053575 EP2010053575W WO2010121871A1 WO 2010121871 A1 WO2010121871 A1 WO 2010121871A1 EP 2010053575 W EP2010053575 W EP 2010053575W WO 2010121871 A1 WO2010121871 A1 WO 2010121871A1
Authority
WO
WIPO (PCT)
Prior art keywords
measuring
hydrogenchloride
trichlorsilan
reaction
gas mixture
Prior art date
Application number
PCT/EP2010/053575
Other languages
English (en)
Inventor
Daniel Rische
Original Assignee
Centrotherm Sitec Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centrotherm Sitec Gmbh filed Critical Centrotherm Sitec Gmbh
Publication of WO2010121871A1 publication Critical patent/WO2010121871A1/fr

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Classifications

    • 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
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof

Definitions

  • the invention is related to a method for measuring the 10 conversion rate of a reaction during the conversion of silicon tetraxchloride with hydrogen to trichlorsilan and hydrogenchloride in a conversion reactor.
  • Silicon tetraxchloride is a by-product of the so called Siemens process during the deposition of silicon from trichlorsilan and hydrogen (equations (1) - (2)) .
  • STC is not effective to use for fabrication of silicon and must be decontaminated at this reason or must be converted to trichlorsilan again whereby latter generates higher investment 25 costs indeed but the recycling of STC during the continuous fabrication will be more cost effective.
  • a mixture of chlorsilan comprising in the main STC with admixtures of trichlorsilan as a quench liquid.
  • the method shall be advantageous in acquisition and operation.
  • a special embodiment of the invention is characterized by discharging of a given sample of the reaction product hydrogenchloride from the gas mixture leaving the reactor in a given amount of a sample liquid and subsequent measuring of the pH value of the resulting aqueous solution of the hydrogenchloride .
  • the di- and trichlorsilan covered in the gas mixture are separated before the measurement of the pH value.
  • the di- and trichlorsilan including in the gas mixture are separated before delivering into a sample of water according a further embodiment of the invention.
  • the separation of the chlorsilan happens preferred by condensation due to cooling of the gas mixture.
  • the cooling of the gas mixture can be effected by quenching, direct gas cooling or by heat exchanging.
  • the cooling is effected by a cryo trap and the controlling of the temperature is effected with a cryostat.
  • the measuring of the hydrogenchloride or of the pH value of an aqueous solution of this hydrogenchloride in a sample of water is repeated in periodic intervals using new distilled or de-ionized water for each measurement .
  • Fig. 1 a schematic depiction of a measuring apparatus according the inventive method.
  • Fig. 2 a tabular overview of the boiling point of several material .
  • the measuring device incorporates a cryo trap 1, receiving di- and trichlorsilan as well as HCl + H 2 with high temperature from a not shown reactor via a pipe 2.
  • a cryo trap 1 receiving di- and trichlorsilan as well as HCl + H 2 with high temperature from a not shown reactor via a pipe 2.
  • the cryo trap 1 is realized a fast cooling of the gases connected with a condensation of chlorsilan.
  • the hydrogenchloride and hydrogen remaining in the cryo trap after the cooling is guided via another pipe 3 into a container 5 filled with a defined amount of water (distilled or de-ionized) .
  • a defined amount of water distilled or de-ionized
  • This liquid level sensor can be an ultrasonic sensor, a reflection light barrier or a simple floating switch.
  • a pH sensor 7 is positioned in the container 5.
  • the base of the present invention provides the reaction according equation (3) .
  • the pH value is defined as:
  • the gas mixture of the reaction ace. equation (3) consist of silicon tetrachloride, trichlorsilan, hydrogenchloride and hydrogen and optionally of a minor quantity of dichlorsilan . All of this silicon containing compound hydrolyze during contact with water by generating HCl (equation (6)) .
  • chlorsilan would be delivered into the sample water 4 also would result a clearly higher pH amount, in consequence it will be necessary to remove such material from the gas mixture before.
  • Such a separation can be accomplished by all methods known from the stat of the art. Preferred is the separation of chlorsilan by condensation.
  • table 1 depicted the cooking points of all materials covered in the reaction mixture. It can be seen easily that the cooking temperatures are sufficient far away from one another so that the chlorsilan can be separated quantitative from hydrogenchloride and hydrogen. The hydrogen can be separated also but this is not necessary since this would not amend the pH value of the sample water 4.
  • a cryo trap 1 In an especially embodiment of the present invention is used for condensing the chlorsilan a cryo trap 1. Cooling is also possible by quenching, with a heat exchanger or by direct gas cooling.
  • Controlling of the temperature can be performed with all known methods from the state of art. Preferred is controlling with a cryostat.
  • the temperature in the cryo trap 1 is arranged so that it is assured that all chlorsilan will condense und that the gas stream which leaves the cryo trap consist only of hydrogen- chloride and hydrogen.
  • This gas stream i.e. e pre defined sample amount is delivered into a pre defined amount of sample water 4 with known pH value residing in the container 5.
  • the container is provided with the liquid level sensor 6 as described already.
  • salt acid according equation (4) whereas the pH value of the water alters.
  • the measuring of the pH value can be performed with all known methods according the state of the art.
  • an electronic pH meter (pH sensor 5) for the measuring.
  • From the metered pH value amendment can be designated the generated ratio of trichlorsilan in the sample quantity.
  • the measuring respective the determination of the reaction conversion can be done in regular intervals like hourly or in greater intervals like daily or shiftly.
  • Contrary to measuring with a gas chromatograph offers the method according the invention a simple and definite measuring method what can be accomplished easy by untrained personnel after a short briefing and is moreover little accident-sensitive because of the few instruments needed.
  • the calibration of electronic pH measuring devices can be performed easy with standard solutions and needs no experience.
  • Consumable materials are not necessary except a low amount of sample water. Since the device can be constructed very small and have sensors with low fault liability there can manufactured a mobile variant what is optimal for use by a implementing team. Also an automating of the method can be realised easily so that any further error source for the measuring can be removed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Silicon Compounds (AREA)

Abstract

L'invention porte sur un procédé pour la mesure du taux de conversion d'une réaction pendant la conversion de tétrachlorure de silicium avec de l'hydrogène en tétrachlorosilane et chlorure d'hydrogène, dans un réacteur de conversion. L'invention vise à développer un procédé pour la mesure du taux de conversion avec un procédé qui peut être facilement mis en œuvre, nécessitant un faible effort assisté par ordinateur et peu sensible à une défaillance ou à un accident. Le procédé fonctionne par la mesure de la quantité du produit réactionnel chlorure d'hydrogène pendant la conversion dans le réacteur, ainsi que par la conversion en la quantité de trichlorosilane par soutirage d'un échantillon donné du produit réactionnel chlorure d'hydrogène provenant du mélange gazeux quittant le réacteur dans une quantité donnée d'échantillon liquide, et mesure subséquente de la valeur de pH de la solution aqueuse ainsi obtenue du chlorure d'hydrogène.
PCT/EP2010/053575 2009-03-30 2010-03-18 Procédé pour la mesure du taux de conversion de la réaction de tétrachlorure de silicium avec de l'hydrogène pour former du tétrachlorosilane et du chlorure d'hydrogène WO2010121871A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009014843.4 2009-03-30
DE102009014843 2009-03-30

Publications (1)

Publication Number Publication Date
WO2010121871A1 true WO2010121871A1 (fr) 2010-10-28

Family

ID=42269521

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/053575 WO2010121871A1 (fr) 2009-03-30 2010-03-18 Procédé pour la mesure du taux de conversion de la réaction de tétrachlorure de silicium avec de l'hydrogène pour former du tétrachlorosilane et du chlorure d'hydrogène

Country Status (3)

Country Link
DE (1) DE102010003032A1 (fr)
TW (1) TW201041804A (fr)
WO (1) WO2010121871A1 (fr)

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
F.A. CAREY, R.J. SUNDBERG: "Advanced Organic Chemistry: Structure and Mechanisms", 2007, SPRINGER SCIENCE AND BUSINESS METHODS, LLC, ISBN: 978-0-387-44897-8, pages: 270 - 285, XP008123973 *
M. SUGIURA, H. KURITA, T. NISIDA, A. FUWA: "Hydrogenation reactions and their kinetics for SiCl4(g)-H2(g) and SiCl4(g)-Si(s)-H2(g) systems using a fixed bed type reactor", MATERIALS TRANSACTIONS, JIM, vol. 33, 1992, pages 1138 - 1148, XP002589890 *
W.M. INGLE, M.S. PEFFLEY: "Kinetics of the hydrogenation of silicon tetrachloride", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 132, May 1985 (1985-05-01), pages 1236 - 1240, XP002589892 *

Also Published As

Publication number Publication date
DE102010003032A1 (de) 2010-10-14
TW201041804A (en) 2010-12-01

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