EP0648865A1 - 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
EP0648865A1
EP0648865A1 EP94401974A EP94401974A EP0648865A1 EP 0648865 A1 EP0648865 A1 EP 0648865A1 EP 94401974 A EP94401974 A EP 94401974A EP 94401974 A EP94401974 A EP 94401974A EP 0648865 A1 EP0648865 A1 EP 0648865A1
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EP
European Patent Office
Prior art keywords
cathode
arsine
membrane
ions
hydrogen
Prior art date
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Granted
Application number
EP94401974A
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English (en)
French (fr)
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EP0648865B1 (de
Inventor
Pascal Bouard
Philippe Labrune
Panayotis Cocolios
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Publication of EP0648865A1 publication Critical patent/EP0648865A1/de
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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 (AsH3) by electrolytic means.
  • Gas hydrides are a key point in the semiconductor industry. We can thus cite the example of silane used as a precursor for the manufacture of silicon substrates or for the production of silica deposits, or even the example of arsine as a source of arsenic for doping semi- conductive or for the growth of epitaxial layers of GaAsP.
  • arsine is not without posing safety problems linked to the highly toxic nature of this gas, justifying its handling under very careful conditions (use of hoods, etc.), both in terms of its production. than its storage or its transport in the form of bottles containing a generally reduced concentration of 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 As2O3) in an acid medium (sulfuric acid) in which is also sulphate of potassium (K2SO4)
  • 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 proposes a process for generating arsine by electrolytic route from an electrochemical cell where a cathode supplied with H+ and AsO2 ⁇ ions are arranged, where two competing reactions producing respectively produce arsine and hydrogen gas, and an anode, where a reaction source of H+ ions takes place, in which the ratio of H+ / As concentrations to the cathode is controlled and kept constant.
  • the reaction source of H+ ions can 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 mixture gas 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 As2O3 (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 As2O3 (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 As2O3 saturator avoids the use of sodium salts, but also constitutes a kind of buffer capacity which ensures a regular and constant concentration of AsO2 ⁇ ions in the medium supplying the cathode.
  • the acid medium used in the composition of the mixtures supplying the two compartments may include phosphoric, perchloric, or preferably sulfuric acid.
  • 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 area of the order of 70 cm2. 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 is carried out, downstream of the generator, of separation of the hydrogen / arsine mixture produced at the cathode, by treating this mixture on a membrane module, making it possible to obtain at the outlet (or rejection) of modulates a higher arsine concentration than in the arsine / hydrogen mixture treated at the entrance to the module, but also to obtain a high stability of this concentration.
  • An assembly of one or more semi-permeable membranes mounted in series or in parallel, having good separation properties of arsine with respect to a carrier gas (selectivity), will advantageously be used to carry out this concentration step. This is the case for membranes of the polyimide or polyaramide (aromatic polyimide) type.
  • this low pressure is compensated for by carrying out, on the permeate side of the membrane, a vacuum drawing or else a scanning with using a "tool" gas, so as to lower the partial pressure of the 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 104 Pa to 5 x 105 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 comme will be used as the "tool" gas.
  • the mixture produced at the cathode undergoes at least one drying operation, on a device such as a refrigerant (for example with Peltier effect), or else a molecular sieve, or a combination of these two means, and where appropriate, at least one filtering operation on a particle filter.
  • a device such as a refrigerant (for example with Peltier effect), or else a molecular sieve, or a combination of these two means, and where appropriate, at least one filtering operation on a particle filter.
  • 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 AsO2 ⁇ ions, where two competing reactions take place, producing respectively arsine and hydrogen gas, and at least one anode. , where a reaction source of H+ ions takes place; a cationic membrane separating the electrochemical cell into two compartments, anodic and cathodic; and to supply the cathode compartment with H+ and AsO2 ⁇ ions, a saturator constituted by a reserve of As2O3, which is swept away by an acid solution.
  • the source reaction of H+ ions at the anode is the electrolysis of water, the anode compartment is then supplied with an acid solution.
  • the source reaction 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 storage tank for the acid solution supplying the cathode compartment.
  • the saturator is located inside the storage tank for the acid solution supplying the cathode compartment, within this acid solution.
  • a material will be used for the cathode which favors the arsine formation reaction to the detriment of the hydrogen formation reaction, such as copper on which a deposit of bismuth, lead, or thallium or cadmium has been carried out.
  • a material such as titanium on which a deposit of ruthenium oxide or iridium was deposited, or an electrode of the carbon felt type, for example (conventional electrolysis or gas electrode) will be used, as the case may be .
  • the device comprises, downstream of the electrochemical cell, 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 allowing the permeate side of the membrane to be evacuated, 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 SF6.
  • 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 SF6.
  • the device comprises, upstream of the membrane module, at least one device for drying the mixture produced at the cathode, such as a refrigerant, for example with Peltier effect, or else 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
  • Figure 2 illustrates the performance obtained using a generator such as that described above, using a current density (relative to the electrode surface) of 500A / m2.
  • 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 / m2 (m2 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 a H+ / As ratio close to 1. It can be seen, in the range [200 A / m2, 1500 A / m2] of current density an increasing flow of arsine, from around 25 l / h / m2 to around 225 l / h / m2.
  • An electrochemical cell 12 such as that described in FIG. 1 is recognized in FIG. 4.
  • the compartment of the cell 12 is supplied with acid solution stored in the tank 4, via line 5 which here also incorporates a flow sensor 13.
  • the tank 4 includes means for discharging the oxygen produced at the anode to a vent 14, via a valve 15 if necessary, and a pressure sensor 16.
  • the cell compartment 12 is supplied with AsO2 ⁇ ions by the storage tank 10, via line 17 which includes a flow sensor 18.
  • the reserve of As2O3 (saturator 8) is here included in the storage 10, within the acid liquid 19, continuously swept by it, to allow the continuous dissolution of the compound As2O3 in the solution, leading to its saturation in AsO2 ⁇ ions.
  • the cathode container 10 includes means for evacuating gas to a vent 20, via a valve 21 if necessary. This evacuation is in particular used during the purging operations of the system.
  • an inlet 22 of inert gas such as nitrogen
  • inert gas such as nitrogen
  • This nitrogen inlet is particularly used to carry out storage purge cycles, 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 a large part of its humidity.
  • 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 module exchange surface of approximately 0.25 m2.
  • 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 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 on a particulate filter 38.
  • a vent 40 is provided 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 from the valves for the liquid circuit (such as valves 41, 42 etc.), and for the gas pipeline (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)
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

Publications (2)

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

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EP94401974A Expired - Lifetime EP0648865B1 (de) 1993-09-17 1994-09-06 Verfahren und Vorrichtung zur elektrolytischen Herstellung von Arsin

Country Status (6)

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

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
DE69422367T2 (de) 2000-08-24
DE69422367D1 (de) 2000-02-03
FR2710043B1 (fr) 1995-10-13
JPH07180076A (ja) 1995-07-18
US5425857A (en) 1995-06-20
EP0648865B1 (de) 1999-12-29
FR2710043A1 (fr) 1995-03-24
TW285780B (de) 1996-09-11

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