EP0648865B1 - Verfahren und Vorrichtung zur elektrolytischen Herstellung von Arsin - Google Patents

Verfahren und Vorrichtung zur elektrolytischen Herstellung von Arsin Download PDF

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Publication number
EP0648865B1
EP0648865B1 EP94401974A EP94401974A EP0648865B1 EP 0648865 B1 EP0648865 B1 EP 0648865B1 EP 94401974 A EP94401974 A EP 94401974A EP 94401974 A EP94401974 A EP 94401974A EP 0648865 B1 EP0648865 B1 EP 0648865B1
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EP
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Prior art keywords
cathode
arsine
membrane
hydrogen
ions
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EP94401974A
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English (en)
French (fr)
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EP0648865A1 (de
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Pascal Bouard
Philippe Labrune
Panayotis Cocolios
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals

Definitions

  • the invention relates to a method and a device for generating arsine (AsH 3 ) electrolytically.
  • Gas hydrides are a key point in the semiconductor industry. We may thus cite the example of the silane used as a precursor for the manufacture of silicon or for the production of silica deposits, or even the example of arsine as source of arsenic for doping semiconductors or for growing layers epitaxial from GaAsP.
  • arsine is not without posing safety problems linked to the character highly toxic of this gas, justifying its handling under very great conditions precautions (use of hoods, etc.), both in terms of production and storage, or still transported in the form of bottles containing a concentration generally reduced arsine in a carrier gas.
  • document US-A-1,375,819 proposes a process for the production of arsine by electrolysis of a solution of an arsenic oxide (such as As 2 O 3 ) in an acid medium (sulfuric acid) in which is also present potassium sulfate (K 2 SO 4 )
  • an arsenic oxide such as As 2 O 3
  • an acid medium sulfuric acid
  • potassium sulfate K 2 SO 4
  • the electrolyser used is of the tank type, the cathode is made of carbon covered with mercury, the anode is made of simple carbon.
  • the configuration adopted gives rise to the production of a gas which is in fact a mixture of oxygen, hydrogen and arsine.
  • the electrolytic cell is here also of the tank type, but consists of two concentric compartments playing the role of electrodes. These two electrodes are separated in their upper part by a solid cylindrical barrier (and concentric around the anode) whose objective is the separation of the gases produced at the anode and the cathode, before their evacuation from the top of the cell. .
  • This "upper” barrier is supplemented by a “lower” barrier (always cylindrical and concentric around the anode), continuous or not with the preceding barrier, the objective of which is here also to separate the gases produced, at the bubbling stage.
  • the invention provides a process for generating arsine electrolytically from an electrochemical cell where a cathode supplied with H + and AsO 2 - ions is arranged, where two competing reactions occur, respectively producing l arsine and hydrogen gas, and an anode, where an H + ion source reaction takes place, in which the ratio of H + / As concentrations to the cathode is controlled and kept constant, so as to produce a mixture H 2 + AsH 3 in proportions of between 50% and 95% of AsH 3 according to the H + / As ratio applied.
  • the reaction source of H + ions may for example consist of the electrolysis of water (in the case of a conventional plane anode supplied with acid solution) or also by the oxidation of hydrogen (supply of gaseous hydrogen d '' a gas diffusion electrode).
  • This second type of electrode having a very large specific surface generally has catalyst particles (platinum type) at the gas / liquid interface on which the hydrogen will oxidize to H + ions, and on the gas side is treated so as to be made hydrophobic.
  • the Applicant has indeed highlighted the key role of the H + / As ratio at the cathode, and its influence on the yield of arsine obtained (concentration of arsine in the gas mixture obtained at the cathode).
  • Each cell geometry corresponds to an optimum of the H + / As ratio to be respected and maintained.
  • the conversion rate is understood to mean, according to the invention, the ratio: (As e -As s ) / As e , where As e represents the concentration of arsenic in the fluid supplying the cathode compartment, and As s this same concentration in the outlet fluid which is recycled to the storage tank supplying the cathode compartment.
  • the reserve of As 2 O 3 (saturator) is located in the circuit between the cathode compartment and the storage of acid solution which comes to sweep the saturator.
  • the reserve of As 2 O 3 (saturator) is located in the circuit inside the storage of acid solution, within this solution, thus ensuring close contact between this solution and the walls of the saturator.
  • a material such as that sold under the name NAFION R is suitable for the preparation of such a membrane.
  • the use of the As 2 O 3 saturator makes it possible to avoid the use of sodium salts, but also constitutes a kind of buffer capacity which ensures a regular and constant concentration of AsO 2 ions - in the medium supplying the cathode.
  • the acid medium used in the composition of the mixtures feeding the two compartments may contain phosphoric, perchloric acid, or preferably sulfuric.
  • the electrodes used for the implementation of the invention are advantageously made up as follows: at the cathode, a material promoting the formation of arsine to the detriment of the competing reaction of hydrogen formation, advantageously a material such as copper on which a deposit of bismuth, lead, or thallium or cadmium was carried out, with an electrode surface of the order of 70 cm 2 . At the anode, a material such as titanium on which a deposit of ruthenium oxide or iridium was deposited, or an electrode, for example of the felt type, will be used, depending on the case (conventional electrolysis or gas electrode). carbon.
  • a step of downstream of the generator is carried out. separation of the hydrogen / arsine mixture produced at the cathode, by treating this mixture on a membrane module, making it possible to obtain a concentration of arsine higher than in the arsine / hydrogen mixture treated at the entrance to the module, but also to obtain a high stability of this concentration.
  • this low pressure is compensated for by performing, on the permeate side of the membrane, vacuum drawing or even sweeping using a "tool" gas, so as to lower the partial pressure of hydrogen (which we want to separate from arsine) on the permeate side.
  • Low pressure is understood to mean, according to the invention, a pressure lying in the range 10 4 Pa to 5 ⁇ 10 5 Pa absolute.
  • a gas other than that which it is desired to separate, and moreover having a low permeation of the permeate towards the interior of the membrane, so as to prevent this gas "tool” does not pollute the interior of the membrane and therefore does not affect the result obtained at the output of the module.
  • nitrogen, or even SF 6 will be used as the "tool" gas.
  • the mixture produced at the cathode undergoes at least one drying operation, on a device such than a refrigerant (for example Peltier effect), or a molecular sieve, or a combination of these two means, and where appropriate, at least one filtering operation on a particle filter.
  • a refrigerant for example Peltier effect
  • a molecular sieve for example a molecular sieve
  • Another object of the invention is to propose a device for implementing the method according to the invention.
  • the device comprises at least one electrochemical cell where at least one cathode is placed, supplied with H + and AsO 2 - ions, where two competing reactions take place, producing respectively arsine and hydrogen gas, and at least one anode, where an H + ion source reaction takes place; a cathionic membrane separating the electrochemical cell into two compartments, anodic and cathodic; and to supply the cathode compartment with H + and AsO 2 - ions, a saturator constituted by a reserve of As 2 O 3 , which is swept away by an acid solution.
  • This device is according to the characteristic of claim 10.
  • the reaction source of H + ions at the anode is the electrolysis of water, the anode compartment is then supplied with an acid solution.
  • the reaction source of H - ions at the anode is the oxidation of hydrogen and we are then in the presence of a gas diffusion electrode supplied with hydrogen gas.
  • the saturator is located between the electrochemical cell and the tank for storing the acid solution supplying the cathode compartment.
  • the saturator is located inside the tank. storage of the acid solution supplying the cathode compartment, within this solution acid.
  • a material promoting the reaction of the cathode will be used. arsine formation at the expense of the hydrogen formation reaction such as copper on which has been deposited with bismuth, lead, or thallium or cadmium.
  • a material such as conventional (conventional electrolysis or gas electrode) will be used titanium on which a deposit of ruthenium oxide or iridium has been carried out, or an electrode for example of the carbon felt type.
  • the device comprises, downstream of the cell electrochemical, a membrane module, on which the arsine / hydrogen mixture produced at the cathode undergoes a separation step, so as to obtain, at the module output, a higher arsine concentration than in the initial mixture.
  • the membrane module is connected to means for carrying out a vacuum on the permeate side of the membrane, so as to bring the pressure on the permeate side to a value of the order of 1 to 100 Pa (primary vacuum).
  • the membrane module is connected to a gas source, making it possible to carry out a scanning of the permeate side of the membrane, using this gas, which advantageously will have according to the invention low permeation of the permeate towards the inside of the membrane, such as nitrogen or SF 6 .
  • the device comprises, upstream of the module membrane, at least one device for drying the mixture produced at the cathode, such as a refrigerant for example with Peltier effect, or a molecular sieve, or a combination of these two means, and where appropriate, at least one particle filter.
  • a refrigerant for example with Peltier effect
  • a molecular sieve or a combination of these two means
  • FIG. 2 illustrates the performance obtained using a generator such as that described above, using a current density (relative to the electrode surface) of 500 A / m 2 .
  • the observed evolution confirms the existence of an optimum for the H + / As ratio, close to 1 for this cell geometry, giving rise to the production at cathode 7 of an arsine / hydrogen mixture containing 95% of arsine, with a flow rate of 50 l / h / m 2 (m 2 of electrode).
  • the performances decrease rapidly around the optimum value.
  • FIG. 3 illustrates, under these same cell and electrode conditions, the influence of the current density on the flow of arsine produced at cathode 7, this for an H + / As ratio close to 1. It can be seen, in the range [200 A / m 2 , 1500 A / m 2 ] of current density an increasing flow of arsine, from approximately 25 l / h / m 2 to approximately 225 l / h / m 2 .
  • Tray 4 has means for discharging the oxygen produced at the anode to a vent 14, via a valve 15 if required, and a pressure sensor 16.
  • the cell compartment 12 is supplied with AsO 2 ions - by the storage tank 10, via line 17 which includes a flow sensor 18.
  • the reserve of As 2 O 3 (saturator 8) is included here in storage 10, within the acid liquid 19, continuously swept by it, to allow the continuous dissolution of the compound As 2 O 3 in the solution, leading to its saturation with AsO 2 - ions.
  • the cathode container 10 includes means for evacuating gas to a vent 20, via a valve 21 if necessary. This evacuation is used in particular during operations purge system.
  • an inlet 22 of inert gas such as nitrogen
  • inert gas such as nitrogen
  • This nitrogen inlet is particularly used for perform purge cycles of the storage, at the start of the installation, but also to purge the downstream of the installation via a line 48 derived from line 25.
  • the tank 10 also includes a pressure sensor 26, and a temperature sensor 28.
  • the arsine / hydrogen mixture produced at the cathode of cell 12 is first treated on a refrigerant 27 (the temperature of which is controlled by a sensor 29), so as to purify the mixture in question of much of its moisture.
  • the mixture undergoes a second purification of water on a molecular sieve 30, before passing over a particle filter 31.
  • the mixture then approaches a semi-permeable membrane module 32 of the type with hollow fibers, the active layer of which is a polyaramide (aromatic polyimide) offering a total exchange surface of the module of approximately 0.25 m 2 .
  • the installation allows the permeate side of the membrane to be evacuated by a line 35, at a pressure of the order of 10 Pa absolute (primary vacuum).
  • the mixture enriched in arsine, at the outlet (rejection) of the membrane, is then directed via a line 46 comprising a non-return valve 33 to a buffer capacity 34 from which the mixture is directed, via a line 47 comprising a pressure sensor 36, to the reactor 39 using arsine.
  • the mixture is filtered through a particle filter 38.
  • a vent 40 is planned if necessary at the end of the line 47.
  • valves of two types All along the route there are valves of two types, depending on the fluids transported valves for the liquid circuit (such as valves 41, 42 etc.), and for the gas pipe (such as valves 43, 44, 45 etc.).
  • the application of this installation made it possible to obtain, at the outlet of the cathode compartment, concentrations of arsine in hydrogen varying from 50% to 95%, according to the H + / As ratio applied (as illustrated in FIG. 2), with a flow rate of the mixture leaving the cell of at least 3 l / h.
  • the drying stage consisting of the refrigerant 27 and a molecular sieve 30, makes it possible to obtain a mixture almost free of water, any additional drying which can be carried out on the membrane 30.
  • the essential objective of the membrane is to concentrate the arsine in the mixture obtained at the membrane outlet.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (20)

  1. Verfahren zur Herstellung von Arsin auf elektrolytischem Wege aus einer elektrochemischen Zelle (12), in der eine Kathode (7), die mit H+- und AsO2 --Ionen gespeist wird und an der zwei Konkurrenzreaktionen ablaufen, bei denen sich Arsin bzw. gasförmiger Wasserstoff bildet, und eine Anode (3), an der eine Reaktion abläuft, die H+-Ionen liefert, angeordnet sind, dadurch gekennzeichnet, daß man das H+/As-Konzentrationsverhältnis an der Kathode (7) derart kontrolliert und konstant hält, daß sich je nach verwendetem H+/As-Verhältnis eine Mischung aus H2 und AsH3 mit 50% bis 95% AsH3 bildet.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das H+/As-Verhältnis dadurch kontrolliert, daß man:
    a) die elektrochemische Zelle mit Hilfe einer kationischen Membran (11) in zwei Kammern, nämlich eine Anodenkammer und eine Kathodenkammer, unterteilt, was die Beherrschung des Materialstroms im Inneren der Zelle ermöglicht;
    b) sicherstellt, daß das Kathodenkammerspeisefluid so schnell zirkuliert, daß der Arsenumsatz an der Kathode unter 10% liegt;
    c) die Kathode mit H+- und AsO2 --Ionen aus einem As2O3-Vorrat (8), der mit einer sauren Lösung (19) gespült wird, speist.
  3. Verfahren zur Herstellung von Arsin auf elektrolytischem Wege nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Kathode (7) aus einem Material gefertigt ist, das die Arsinbildungsreaktion auf Kosten der Wasserstoffbildungsreaktion begünstigt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Kathode (7) aus Blei oder aus Kupfer mit Bismut-, Blei-, Thallium- oder Cadmiumüberzug besteht.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man das H+/As-Verhältnis zwischen 0,7 und 1,5, vorzugsweise zwischen 0,75 und 1,25, hält.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man das an der Kathode (7) gebildete Gemisch aus Wasserstoff und Arsin abschließend über ein Membranmodul (32) so trennt, daß man am Modulausgang eine höhere Arsinkonzentration als im Gemisch erhält.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man auf der Permeatseite der Membran Vakuum anlegt.
  8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß man die Membran permeatseitig mit einem Gas, das das Permeat nur wenig in Richtung des Membraninneren permeiert, wie Stickstoff oder SF6, spült.
  9. Verfahren nach einem der Ansprüche 6, 7 oder 8, dadurch gekennzeichnet, daß man das an der Kathode (7) gebildete Gemisch vor dessen Eintreffen am Membranmodul (32) mindestens einer Trockung in einer Vorrichtung wie einem Peltier-Kühler (27) oder einem Molekularsieb (30) oder einer Kombination dieser beiden Mittel und gegebenenfalls mindestens einer Filtration über einen Partikelfilter (31) unterwirft.
  10. Vorrichtung zur Herstellung von Arsin auf elektrolytischen Wege, insbesondere für die Durchführung des Verfahrens nach einem der Ansprüche 1 bis 9, mit:
    einer elektrochemischen Zelle (12), in der eine Kathode (7), die sich in Berührung mit einem H+- und AsO2 --Ionen enthaltenden Elektrolyt befindet und an der zwei Konkurrenzreaktionen ablaufen, bei denen sich Arsin bzw. gasförmiger Wasserstoff bildet, und eine Anode (3), an der eine Reaktion abläuft, die H+-Ionen liefert, angeordnet sind, wobei das H+/As-Konzentrationsverhältnis an der Kathode konstant gehalten wird, damit man am Ausgang der Kathodenkammer je nach verwendetem H+/As-Verhältnis Konzentrationen von Arsin in Wasserstoff von 50% bis 95% erhält;
    einer kationischen Membran (11), die die elektrochemische Zelle in zwei Kammern, nämlich eine Anodenkammer und eine Kathodenkammer, unterteilt; und
    Einrichtungen zur Speisung der Kathodenkammer mit H+- und AsO2 --Ionen mit einem Sättiger (8), bei dem es sich um einen As2O3-Vorrat, der mit einer sauren Lösung (19) gespült wird, handelt.
  11. Vorrichtung nach Anspruch 10, dadurch gekennzeichnet, daß der Sättiger (8) zwischen der elektrochemischen Zelle (12) und dem Speicherbehälter (10) für die die Kathodenkammer speisende saure Lösung (19) angeordnet ist.
  12. Vorrichtung nach Anspruch 10, dadurch gekennzeichnet, daß der Sättiger (8) im Inneren des Speicherbehälters (10) für die die Kathodenkammer speisende saure Lösung in der sauren Lösung (19) angeordnet ist.
  13. Vorrichtung nach einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, daß die Kathode (7) aus einem Material gefertigt ist, das die Arsinbildungsreaktion auf Kosten der Wasserstoffbildungsreaktion begünstigt.
  14. Vorrichtung nach Anspruch 13, dadurch gekennzeichnet, daß die Kathode (7) aus Blei oder aus Kupfer mit Bismut-, Blei-, Thallium- oder Cadmiumüberzug besteht.
  15. Vorrichtung nach einem der Ansprüche 10 bis 14, dadurch gekennzeichnet, daß sie ein der elektrochemischen Zelle nachgeschaltetes Membranmodul (32) enthält, über das das an der Kathode (7) gebildete Gemisch aus Wasserstoff und Arsin so getrennt wird, daß man am Modulausgang eine höhere Arsinkonzentration als im Gemisch erhält.
  16. Vorrichtung nach Anspruch 15, dadurch gekennzeichnet, daß das Membranmodul mit Einrichtungen zum Anlegen von Vakuum auf der Permeatseite der Membran verbunden ist.
  17. Vorrichtung nach Anspruch 15, dadurch gekennzeichnet, daß das Membranmodul mit einer Quelle eines Gases, die die permeatseitige Spülung der Membran mit dem Gas, das das Permeat nur wenig in Richtung des Membraninneren permeiert, wie Stickstoff oder SF6, ermöglicht, verbunden ist.
  18. Vorrichtung nach einem der Ansprüche 15 bis 17, dadurch gekennzeichnet, daß sie vor dem Membranmodul mindestens eine Vorrichtung zur Trocknung des an der Kathode gebildeten Gemischs und gegebenenfalls mindestens einen Partikelfilter (31) enthält.
  19. Vorrichtung nach einem der Ansprüche 10 bis 18, dadurch gekennzeichnet, daß die Anodenkammer eine mit einer sauren Lösung gespeiste Flächenelektrode aufweist, an der Wasserelektrolyse stattfindet.
  20. Vorrichtung nach einem der Ansprüche 10 bis 18, dadurch gekennzeichnet, daß die Anodenkammer eine mit Wasserstoff gespeiste Gasdiffusionselektrode aufweist, an der Wasserstoffoxidation stattfindet.
EP94401974A 1993-09-17 1994-09-06 Verfahren und Vorrichtung zur elektrolytischen Herstellung von Arsin Expired - Lifetime EP0648865B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9311082A FR2710043B1 (fr) 1993-09-17 1993-09-17 Procédé et dispositif de génération d'arsine par voie électrolytique.
FR9311082 1993-09-17

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EP0648865A1 EP0648865A1 (de) 1995-04-19
EP0648865B1 true EP0648865B1 (de) 1999-12-29

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US (1) US5425857A (de)
EP (1) EP0648865B1 (de)
JP (1) JPH07180076A (de)
DE (1) DE69422367T2 (de)
FR (1) FR2710043B1 (de)
TW (1) TW285780B (de)

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JP3889813B2 (ja) * 1995-12-06 2007-03-07 エレクトロン・トランスファー・テクノロジーズ・インコーポレーテッド 半導体加工用の水素化物ガスを一定組成で供給するための方法と装置
US6080297A (en) * 1996-12-06 2000-06-27 Electron Transfer Technologies, Inc. Method and apparatus for constant composition delivery of hydride gases for semiconductor processing
US6277342B1 (en) 1999-08-23 2001-08-21 Air Products And Chemicals, Inc. Storage and safe delivery of hazardous specialty gases by acid/base reactions with ionic polymers
US8021536B2 (en) * 2006-04-13 2011-09-20 Air Products And Chemical, Inc. Method and apparatus for achieving maximum yield in the electrolytic preparation of group IV and V hydrides
US20090159454A1 (en) 2007-12-20 2009-06-25 Air Products And Chemicals, Inc. Divided electrochemical cell and low cost high purity hydride gas production process
TWI421601B (zh) 2008-04-25 2014-01-01 Au Optronics Corp 適用雷射切割技術之顯示面板及其母板
US8361303B2 (en) * 2010-09-02 2013-01-29 Air Products And Chemicals, Inc. Electrodes for electrolytic germane process
GB201015022D0 (en) 2010-09-09 2010-10-20 Johnson Matthey Plc Metal passivation
CN110950382B (zh) * 2018-09-26 2022-03-15 紫石能源有限公司 砷烷的制备方法
CN111378979B (zh) * 2018-12-29 2022-03-15 紫石能源有限公司 砷纳米颗粒及其制备方法、电解制砷烷的系统和方法
CN114438534A (zh) * 2022-01-05 2022-05-06 飞马牧场(上海)信息咨询服务有限公司 一种高纯气体制备装置及制备方法

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US4178224A (en) * 1978-01-19 1979-12-11 Texas Instruments Incorporated Apparatus for generation and control of dopant and reactive gases
SU962335A1 (ru) * 1980-03-24 1982-09-30 Казахский Ордена Трудового Красного Знамени Государственный Университет Им.С.М.Кирова Электролизер дл получени летучих гидридов
US5158656A (en) * 1991-03-22 1992-10-27 Electron Transfer Technologies, Inc. Method and apparatus for the electrolytic preparation of group IV and V hydrides

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DE69422367T2 (de) 2000-08-24
DE69422367D1 (de) 2000-02-03
FR2710043B1 (fr) 1995-10-13
EP0648865A1 (de) 1995-04-19
JPH07180076A (ja) 1995-07-18
US5425857A (en) 1995-06-20
FR2710043A1 (fr) 1995-03-24
TW285780B (de) 1996-09-11

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