FR2955867A1 - Recycling silane comprises injecting a mixture of pure silane/hydrogen in chamber, extracting the mixture, discharging a mixture comprising silane, hydrogen, silicon tetrafluoride and non-zero amount of feed gas and separating - Google Patents

Abstract

Process of recycling silane comprises: (a) injecting a mixture of pure silane/hydrogen (SiH 4/H 2) in a reaction chamber (7) to produce thin films containing silicon; (b) extracting the mixture using a pump (8) providing a feed gas; (c) discharging a mixture comprising at least one silane, H 2, silicon tetrafluoride (SiF 4) and non-zero amount of the feed gas in the pump at a pressure close to atmospheric pressure; and (d) separating SiF 4and mixture of SiH 4/H 2/the feed gas, where at least 50%, preferably 80% of silane from the step (b) is reused after the step (d) for a further step (a).

Description

The present invention relates to a process for recycling gas, in particular silane (SiH4). In the latter context, the first targeted application is the deposition of thin layers of silicon, in particular for the production of photovoltaic cells. However, this system can be used for other applications whose specifications are close. Reducing the cost of solar energy involves reducing the cost of manufacturing photovoltaic cells. For the so-called "thin films" technological sector, especially for the application where silicon is deposited in a thin layer, and more particularly for the micro-crystalline and amorphous silicon solution, the reduction of the consumption of the gases used for the deposits of the active layers contributes to the overall decrease in manufacturing cost. The production of silicon thin films for solar cells requires the sequential deposition of p-doped, undoped and n-doped silicon layers on a substrate. Each silicon deposit is conducted in a chamber in which a method selected from CVD, (including MOCVD, PECVD, ALD, HWCVD, APCVD, VTD ...) or PVD (in particular evaporation and spraying) is performed. The production of photovoltaic cells with thin films of microcrystalline and / or amorphous silicon requires the use of gases such as H2, SiH4, doping gases such as TMB - TriMethyl Bore, PH3 - phosphine, B2H6 - diborane and also N2, argon...

For example, the substrate is located in a first chamber in which a mixture of silane-containing gas, a dopant such as TMB and hydrogen as the carrier gas is provided to form a p-type silicon layer on the substrate. The substrate is then moved to a second chamber in which a mixture of hydrogen gas and silane is provided for the design of an undoped layer. The substrate can then be moved to a third chamber in which a gas mixture comprising hydrogen as a carrier gas, silane and a dopant such as PH3 phosphine is provided for producing an n-doped layer on the substrate. There is an evolution in this type of manufacture of such devices: the substrates on which these deposits are made are becoming larger. Thus, the size of the deposition chambers and the rates of introduction of gases, in particular of hydrogen as a carrier gas must also be increased. In current devices, the gases not used in the deposition chambers are pumped before being treated in order to destroy the hazardous effluents. The quantities of gas required for the deposits of the target active layers are very important. Due to the size of the planned plants and the inherent need for gas due to the nature of the technology, the required flows will reach tens, or even hundreds of m3 per hour for hydrogen. The supply of gas thus becomes problematic for the hydrogen as well as for the silane. The volumes required are a brake on the deployment of these technologies. One way to reduce the cost of supply and logistics of silane (SiH4) and hydrogen (H2) is to recycle these gases as they exit the deposition reactors. However, the gases reintroduced into the reactor must meet the specifications required to obtain good quality layers. The main specifications are as follows: concentrations of H2O, O2 and N2 <1 ppm in SiH4 and H2 to avoid the formation of oxides and / or nitrides; Dopant gas concentrations such as PH3, B2H6, TMB controlled depending on the type and level of doping desired. In addition, powders can form in large amounts during the reaction; their concentration must therefore be related to an acceptable value, that is to say at a sufficiently low level to be compatible, for example: with the mode of operation of the various components in which the gases containing these powders will circulate, and with the intended application (for example the deposition of thin layers for the production of solar cells). These components are for example compressors, adsorption units .... In addition, the SiH4 / H2 ratio and the flow rate of these gases must be controllable.

The literature reveals some characteristics. A recycling of the offgas is for example described in JP58223612A "Apparatus for forming amorphous silicon film". The patent application published in 1983, presents a solution to improve the rate of use of the silane during the deposition of an amorphous silicon film by plasma enhanced CVD (Plasma Enhanced Chemical Vapor Deposition): it is a separating the hydrogen from the gases recovered at the outlet of the deposition reactor and then recycling the silane at the inlet of this same reactor. This document describes a solution where the separation and recycling require in particular the implementation of a cold trap using liquid nitrogen. But it does not address the problem of recycling hydrogen. On the other hand, the process is carried out under vacuum which presents a danger difficult to master perfectly for the handling of silane which is a very violent reducer, so hungry for oxidant such as oxygen in the air that could go into the process for example. In the photovoltaic field, up to now, the solution detailed in patent application JP58223612A commented on above has not been implemented to separate and then recycle the gases used as precursors of thin film deposition. On the other hand, no solution is currently industrialized to recover the silane gas and / or hydrogen and ensure their reuse in the process of deposition of silicon layers. The rejected gases are simply treated and evacuated.

Furthermore, US Pat. No. 5,785,741 "Process and system for separation and recovery of perfluorocompounds gases" presents a solution for the separation of PFC gases for their recycling. This solution can be implemented in the microelectronics industry. Washers, filters, membranes, cold traps and PSA (Pressure Swing Adsorber) are required to achieve recycling of these PFC gases. This solution is interesting but an improved and simplified form of this method is essential to implement other gases (silane and hydrogen for example) and in another field (case of the photovoltaic industry for example). For the separation of the silane from hydrogen, solutions are written in EP 0 644 153 "Silane separation process using a membrane" and "Separation of hydrogen from silane via membranes: a step in the production of ultra-high purity silicon "dealing with the use of a membrane to separate silane from hydrogen used in the manufacture of high purity silicon. This element can be used for the solution developed for the recycling of silane and hydrogen for the application relating to the deposition of amorphous silicon in thin layers. Nevertheless, it is a brick of the technological solution developed to carry out this recycling. On the other hand, membrane separation can not provide high purity gases, which is however indispensable in the applications mentioned above. Finally, in patent EP 0 645 345, there is described a method of membrane separation of a gaseous hydride or a mixture of gaseous hydrides (such as PH3, AsH3, Si2H6), a gaseous medium containing at least argon, helium and / or hydrogen. The proposed solution therefore makes it possible to concentrate, on the one hand, the gaseous hydrides (in this case the gases used for doping in the case of an application for the photovoltaic industry) and to not let through the membrane, the other side also called permeate, the mixture argon, helium and / or hydrogen. Such a separation is carried out with a polyimide or polyaramid polymer membrane.

This problem of silane recycling for the photovoltaic industry is addressed in various documents, in particular patent applications WO2008 / 154293 and WO2009 / 079314. These documents describe a way to implement a silane recycling machine downstream of a solar cell manufacturing process, without addressing the recycling process itself. The patent application WO09112730 discloses a state of the art on silane recycling and details an innovative silane recycling process, one of whose applications is the production of solar cells. Given the specifications to be achieved in terms of the purity of the gases to be recycled at their disposal from the storage reactors, the cryogenic route is preferred for carrying out this recycling. However, this technology can not accept species solidifying at the working temperatures used. This is the case of silicon tetrafluoride (SiF4) which, in addition to being a harmful product at a solidification temperature of 86.8 ° C. to 2.24 bar, can then lead to clogging of the systems in which it passes. The gas is found in a significant quantity in the flows to be treated at the outlet of the deposition reactors (which can reach concentrations of the order of 500 ppm to 2000 ppm or more).

Indeed, following the deposition reaction in the reactor, the latter is cleaned using fluorinated substances (for example NF3 or F2); As a result, the walls of the output circuits of said deposition reactor contain fluorinated products at their surface, the latter reacting with the reaction products from the reactor form SiF4. The protocol for cleaning the reactor after deposition consists of injecting nitrogen trifluoride (NF3) or fluoride (F2) under a plasma which will react with the silane deposited and mainly form the tetrafluorosilane SiF4 gas and several fluorinated by-products (HF , F2). Nevertheless, these fluorinated compounds will partially redeposit after leaving the plasma area of effect especially in the vent lines. During the deposition step, a portion of the injected SiH4 silane fraction that does not decompose will react with these fluorinated compounds and transform into SiF4.

It is therefore necessary to trap SiF4 without retaining SiH4 before sending said stream to the cryogenic portion dedicated to recycling mentioned above. The removal of SiF4 will also have the advantage of avoiding the use of materials compatible with this fluorinated product. The method which is the subject of the present invention can also be used for any other application for which removal of SiF4 is necessary. However, no satisfactory solution has been proposed or implemented so far to efficiently and in an integrated manner the various steps necessary to achieve the recycling of gases used in the manufacture of structures formed in particular of doped silicon films. or not, and deposited in thin layers, from a gas flow containing SiF4. In particular, the documents cited above do not provide answers to this problem. Several ways can be envisaged. The cryogenic trapping path of liquefying or solidifying the SiF4 by cooling, would lead to the trapping of SiF4 but also trapping at least partial SiH4 which is to be avoided according to the problem to be solved above. In addition, it requires the use of cryogenic equipment and the use of a cooling liquid such as liquid nitrogen and therefore all the constraints related to the use of low temperature system. In summary, in order to reduce the consumption of hydrogen and / or silane for the manufacture of systems composed of thin layers of silicon deposited for example by CVD or PVD, such as in particular thin-film photovoltaic silicon cells, the benefits that the solution must provide are, for example: the separation of silicon tetrafluoride from a gaseous effluent (effluent recovered at the outlet of a reactor for depositing thin layers of amorphous silicon); The separation of the powders from a gaseous effluent (effluent recovered at the outlet of an amorphous silicon thin film deposition reactor); The concentration of the silane in a silane / hydrogen mixture; - The separation of the gases to be recycled from the nitrogen used in the pumping unit is in ballast or dilution downstream of (s) the chamber (s); - The separation of the doping gases silane or hydrogen; - The provision of silane and hydrogen gases for reintroduction into the deposition reactor and their reuse for said deposits. One of the difficulties consists in extracting SiF4 from the gas stream without retaining the silane (SiH4) that one seeks to recover elsewhere. In the first application, the composition of the flow from the deposition reactor is of the order of 70% nitrogen (N2), 27.9% hydrogen (H2), 2% silane (SiH4 ) and 0.1% silicon tetrafluoride (SiF4). This composition may vary according to the reactor and the deposit recipe used. One objective is to produce a gas stream comprising a SiF 4 content of less than 10 ppm, or even lower, while keeping a SiH 4 content close to its initial value, 2% in the case cited above.

An object of the present invention is to overcome all or part of the disadvantages of the prior art noted above. In particular, the present invention aims to achieve the selective separation of SiF4 and SiH4 in the gas mixture at the outlet of the reactor in order to recycle the flow of SiH4 by trapping SiF4 in solid form through an adsorbent and regenerating said adsorbent.

To this end, the subject of the invention is a silane recycling process comprising the following successive steps: a) Injection of a pure silane / pure hydrogen mixture (SiH4 / H2) into a reaction chamber (7) to manufacture thin layers containing silicon; b) extraction of the mixture: excess silane not used in step a) / hydrogen (SiH4 / H2), by means of a pump (8) using a feed gas; c) Delivery of said pump (8) at a pressure close to atmospheric pressure, of a mixture comprising at least silane (SiH4), hydrogen (H2), silicon tetrafluoride (SiF4) and a non zero of said feed gas; d) Separation of the silicon tetrafluoride (SiF4) from the silane / hydrogen / feed gas mixture resulting from the mixture resulting from stage c); characterized in that at least 50%, preferably 70%, and more preferably 80% of the silane (SiH4) from step b) is reused after step d) for a new step a). Said feed gas is a heavy gas for driving the hydrogen out of said reaction chamber and satisfactory lubrication of the pump. The feed gas is, for example, nitrogen, argon or 002. Preferably, the feed gas is nitrogen. Pure gas is understood to mean gases comprising less than 100 ppm of impurities, for example less than 100 ppm of nitrogen, or even less than 1 ppm of impurity, for example less than 1 ppm of nitrogen. Dopants as mentioned above are not considered as impurities. The technique of manufacturing thin layer by vacuum metal deposition is a widely used practice. At very low pressure (of the order of a hundredth of Pascal), the vapor molecules of a metal move with very little risk of collision with other molecules. The metal gas is projected onto a substrate without being slowed down by diffusion phenomena and without the risk of oxidation. The layer obtained is thus very pure and very regular. Furthermore, embodiments of the method of the invention may comprise one or more of the following characteristics: - Method as defined above further comprising a step of: e) Separation of the silane (SiH4) from the hydrogen / gas mixture feedstock resulting from the mixture resulting from step d), said silane obtained comprising less than 100 ppm of feed gas, preferably less than 10 ppm of feed gas, preferably less than 1 ppm of gas

- Process as defined above, characterized in that during step d), the silicon tetrafluoride contained in the mixture resulting from step c) is reacted with a solid adsorbent nF2 type, nM, where n = 2 when M is an alkali metal selected from Li, Na, K, Rb, Cs, Fr and n = 1 when M is an alkaline earth metal selected from Be, Mg, Ca, Sr, Ba, Ra. - Method as defined above further comprising a step of regenerating the solid adsorbent by thermal activation at a temperature greater than or equal to 400 ° C under a neutral gas sweep vis-à-vis the reaction of the step d), such as N2, H2, Ar, He. - Process as defined above characterized in that the adsorbent is sodium fluoride (NaF). Indeed, NaF is not soluble in water or hygroscopic, moreover it is one of the least toxic of all fluorides

- Process as defined above, characterized in that the silane stream (SiH4) from step e) contains less than 10 ppm of silicon tetrafluoride (SiF4), and preferably less than 1 ppm.

- Method as defined above further comprising a step of: f) purifying the hydrogen (H2) from step e) such that the feed gas rate in the hydrogen is not greater than 100 ppm, preferably not more than 10 ppm and more preferably not more than 1 ppm; characterized in that at least 50% of the hydrogen (H2) and preferably at least 85% of the hydrogen from step b) is reused after step f) for a new step a).

- Process as defined above, characterized in that said feed gas of the pump (8) is nitrogen (N2). - Process as defined above, characterized in that the mixture resulting from step c) comprises, from 60% to 75% of nitrogen (N 2), from 20% to 35% of hydrogen (H 2), from 1 , 5% to 4% of silane (SiH4) and 0.1% to 0.3% of silicon tetrafluoride (SiF4), preferably 70% of nitrogen (N2), 27.9% of hydrogen (H2 ), 2% silane (SiH4) and 0.1% silicon tetrafluoride (SiF4).

- Process as defined above, characterized in that step e) is carried out by separation and / or cryogenic distillation. - Process as defined above characterized in that step d) comprises introducing the mixture from step c) into a container such as a cartridge, containing said solid adsorbent nF2 type, nM.

15 - Process as defined above, characterized in that several cartridges are placed in parallel so as to regenerate some while the others work.

- Method as defined above, further comprising a step of adsorbing water after compression and before step e). Indeed, among the impurities present in the mixture resulting from step c), water may be present. The adsorption means is for example a PSA or a TSA. The said adsorption means being then present in the apparatus (defined below) implementing the method according to the invention. 25 - Process as defined above, characterized in that the mixture injected in step a) comprises less than 50% of silane (SiH4) in hydrogen (H2) and preferably less than 25%. The process according to the invention can also be used for a mixture injected in step a) containing more than 50% of silane. - Process as defined above, characterized in that the ratio: concentration of silane (SiH4) on hydrogen concentration (H2) is controlled and adjusted if necessary before reinjection, for a new step a), of the silane / hydrogen mixture ( SiH4 / H2) comprising at least silane (SiH4) recycled according to said process. - Method as defined above, characterized in that the manufacture of thin layers in the reaction chamber is made under vacuum.

An essential characteristic of the process according to the invention is the recycling of the silane and, if necessary, hydrogen, carried out otherwise than under vacuum. In fact, silane is a very reactive gas with air so it is very difficult to handle other than using membranes or absorption, but these techniques are not satisfactory when a gas to be recycled requires a purity requirement. . In addition, the handling of silane under vacuum represents a great danger in terms of safety due to the risk of the penetration of air, oxygen or moisture. On the other hand, the fact of implementing a method at a relatively high pressure (at atmospheric pressure or more) optimizes the blocks of the apparatus for carrying out the method according to the invention. The apparatus embodying the process which is the subject of the invention operates at a pressure at least equal to atmospheric pressure, of recycling at least one gas used in a vacuum reaction chamber during a process. deposition apparatus for thin film comprising: - a vacuum pump fed with feed gas; at least one means for purifying the gas mixture sucked by

at least one means for separating the gases from the mixture

at least one means of recycling the separated gases to said reaction chamber. Furthermore, embodiments of the apparatus implementing the method that is the subject of the invention may include one or more of the following features: Apparatus as defined above, further comprising a compression means located downstream purification means and upstream of the separation means. said pump;

purified; 25 - Apparatus as defined above, characterized in that the separation means consists of an apparatus for cryogenic phase separation and / or cryogenic distillation. - Apparatus as defined above, characterized in that said feed gas is nitrogen (N2). Another object of the invention is the use of the apparatus defined above for the implementation of a method defined according to the invention. The invention also relates to a method of depositing a silicon-containing film using at least one recycled gas according to the method defined above.

Preferably, this deposit is made using an SiH4 (precursor) / H2 mixture comprising less than 50% of silane, preferably less than 25%. The recycled gas described in the above process employed in the deposition process according to the invention is either the precursor silane or the precursor silane and hydrogen. The invention relies on the chemical reaction of certain fluorides with SiF4 to form solid complexes. For example, from the properties of hexafluorosilicates it appears that the silicon tetrafluoride is likely to be converted into hexafluorosilicate at room temperature. Thus, when it is desired to remove SiF4 from said fluid stream to be treated, the following chemical adsorption is envisaged: SiF4 (g) + nF2.1zM (s) -Mn [SiF6] (s) With n = 2 if M is a alkali metal: Li, Na, K, Rb, Cs, Fr With n = 1 if M is an alkaline earth metal: Be, Mg, Ca, Sr, Ba, Ra. Other metals may give rise to hexafluorosilicates, but their stability is less. All fluorides of this type are crystalline white solids.

The regeneration of the solid adsorbent bed is obtained by heating and sweeping with a dry and inert gas. A minimum temperature of 400 ° C makes it possible to eliminate 85%, and preferably 90%, of the captured silicon tetrafluoride. The inert gas used may be N 2, H 2, Ar and any inert gas, and preferably N 2. For example, during the regeneration step of the adsorbent bed, when the adsorbent is NaF, the following chemical reaction occurs: Nat [SiF6] heat> SiF4 T + 2NaF.

Two columns in alternating operation are required for continuous operation. In the intended application first, the recycling of the silane, the location of these adsorbent beds is upstream of the cryogenic separation device.

Other features and advantages will appear on reading the description below, made with reference to FIG. 1: FIG. 1 represents a diagram of an example of a recycling circuit able to implement the method that is the subject of the present invention. FIG. 1 shows a recycling circuit (C) comprising a source 1 of silicon precursor, in particular silane gas (SiH4), a source of hydrogen 2. Hydrogen can be used as a carrier gas . The apparatus also includes a source 3 of doping gases such as TMB-TriMethyl Bore, PH3-phosphine, B2H6-diborane for the manufacture of thin films for the above-mentioned applications. Other gases may be used depending on the intended application. The gases from these sources are then injected via the gas lines 4, 5, 6 into the reaction chamber 7 where the deposition of the thin layers takes place. For example, said mixture comprises at most 50% of silane in hydrogen, preferably less than 25% of silane. The concentration of doping elements is generally less than 5% and depends on the desired doping level and the doping efficiency of the precursor used. Thus, the ratio, in concentrations, between H2 and SiH4 is precisely chosen and must be controlled before being introduced into the reaction chamber 7. Once said mixture is injected into the reaction chamber 7, the deposition takes place.

During the deposition, an amount of the silicon precursor, in particular silane, previously introduced up to 85% is not used during the reaction inside the chamber. An object of the present invention being to recycle all or substantially all of this unused amount, the other components of the apparatus are useful for recycling this silane. According to a variant of the process according to the invention, besides the silane, the hydrogen is also recycled. Downstream of the reaction chamber 7, a pump 8 is present. This pump 8 sucks a mixture: excess silane not used in the chamber 7 / hydrogen (SiH4 / H2) through a conduit 9 in which the pressure is a few millibars. Said mixture may further comprise impurities such as, for example, H 2 O, O 2, traces of dopants such as PH 3, B 2 H 6, TMB, particles formed in the reactor resulting from the decomposition of the introduced plasma as well as silicon tetrafluoride (SiF 4) originating from of the reaction of the unreacted SiH4 in the chamber 7 with the fluorinated elements such as NF3 or F2 having served to clean said chamber 7 beforehand and present on the walls of the outlet ducts of the chamber 7. The pump 8 is for example supplied with nitrogen (N2) (used here as "feed gas" as defined above), in particular for these qualities of inerting, lubricating and driving light gases. As a result, at the outlet of the pump 8, a mixture comprising, inter alia, silicon tetrafluoride, nitrogen, silane (generally from 0.01% to 15%) and hydrogen (by 10%). 80%) circulates at a pressure close to atmospheric pressure in a conduit 10. A three-way valve 11 can be installed to direct the mixture to either the pipe 12 for recycling or to the pipe 13 and equipment reprocessing and venting. This makes it possible, for example, to select the mixtures, leaving the reaction chamber 7, to be recycled according to the mixtures injected into the same reaction chamber 7. The valve 11 also allows the mixture to be discharged from the pipe 10 towards line 13 in case of failure of the recycling circuit, so that if the recycling process according to the invention can not operate, the evacuation of the gases from the reaction chamber 7 takes place as in the standard systems of the state of the art. The mixture circulating in the pipe 12 may also include impurities such as those described above. The purity requirements in the applications targeted by the present invention therefore require a maximum elimination of these impurities, that is why a filter 14 can be placed at the end of the conduit 12. Said filter 14 is for example of the separator type. centrifugal effect, inertial and sedimentation separator, electric separator, electrofilter, bag filter, wet separators, scrubber. The position of the filter may be downstream or upstream of a compression means 16 (for example a compressor) depending on the characteristics of said compression means 16. In fact, in the case where the suction force of the compressor is sufficient, the filter can be placed upstream, with however a risk of depression downstream of the filters. If the suction force of the compressor is insufficient, the filters must be placed downstream of the compressor.

The mixture thus filtered flows in a duct 15 to a compression means 16. At the outlet of this compression means 16, the pressure of the mixture comprising at least silane, hydrogen and nitrogen is between 2 bar and 35 bar, preferably between 8 bar and 10 bar. The preferred pressure is that which leads to the best compromise between the size of the equipment of the apparatus (C) according to the invention and the cost of energy to raise the working pressure. Said equipment size being reduced when the pressure is high, but the cost of energy to spend to achieve high pressure is to be considered. 1 bar = 105 Pa. Upstream of the compressor 16, the circuit comprises an adsorption means or trapping reactor 40 comprising for example at least one metal fluoride adsorbent column nF2, nM, where n = 2 when M is an alkali metal selected from Li, Na, K, Rb, Cs, Fr and n = 1 when M is an alkaline earth metal selected from Be, Mg, Ca, Sr, Ba, Ra. The gaseous flow circulating upstream of this adsorption means 40 contains silane, silicon tetrafluoride, hydrogen and nitrogen. Only SiF4 reacts with the adsorbent, according to the reaction balance: SiF4 (g) + nF2.1zM (s) -Mn [SiF6] (s) Preferably, the adsorption means 40 contains at least two columns situated in parallel so that when one column is regenerated, the other serves to adsorb the SiF4 stream.

Thus, the purpose of the present invention is to carry out the selective separation of SiF4 and SiH4 in the gas mixture at the reactor outlet 7 so as to recycle the SiH 4 stream by trapping SiF4 in solid form by means of an adsorbent 40 and regenerating said adsorbent. Several types of adsorption are described below: 1) In the case where the adsorption means, the reactor 40 is a technology type TSA (Temperature swinq adsorption).

The proposed adsorbent is sodium fluoride. : SiF4 (g) + 2NaF (s) Na2SiF6 (s) Na2SiF6 (s) 400 ° C ~ 2NaF (s) + SiF4 (g) The system is composed of at least two cans containing the adsorbent in question. The latter can be used in bulk or deposited on substrate. The typical cycle for one can will be as follows. In a first phase, the gas mixture N2 / H2 / SiH4 / SiF4 is injected into the can. The gas stream will thus pass through the adsorbent feedstock where the reaction between sodium fluoride and SiF4 can take place. The length and section of the can should be calculated so that the gas passage time in this section is sufficient for all SiF4 to react. An N2 / H2 / SiH4 gas stream is thus recovered at the top of the can. In the second phase of the cycle, the injection of N2 / H2 / SiH4 / SiF4 is stopped. A so-called neutral gas flow, for example N2, Ar or H2, is then injected into the can. This is heated to the desired regeneration temperature (eg 400 ° C). At the outlet of the reactor is then recovered the neutral gas loaded with SiF4 released by the adsorbent. This flow of gas is then directed, for example, to reprocessing equipment. When regeneration is complete, the can is cooled and can be reused for adsorption. This type of cycle is used alternately on two cans or more so that there is always a can available for the adsorption phase.

2) When the adsorption means, the reactor 40 is a fluidized bed technology. The gas mixture SiH4 / SiF4 from the filter 14 is injected into the adsorption means 40 containing a first reactor containing a solid charge of adsorbent. For example, the adsorbent is composed of sodium fluoride in bulk or deposited on a substrate. The injection of the gas mixture will be done so as to create a bubble regime: the solid charge is fluidized but not driven by the gas stream. The following reaction will take place: SiF4 (g) + 2NaF (s) Na2SiF6 (s) This first fluidized bed is connected to a second by continuous subtitling of solid at the bottom of the reactor. The solid drive through the connection can be done by fluidization with nitrogen or by a mechanical system of solid displacement. The solid is then fluidized by a stream of nitrogen beyond the minimum fluidization speed to create a riser: the solid is driven by the gas flow in the reactor to its top. In order to regenerate the bed, the walls of the reactor are heated to 400 ° C to promote the decomposition reaction of sodium hexafluoride: Na2SiF6 (s) 400 ° c> 2NaF (s) + SiF4 (g) The gas mixture and solids is then separated by a cyclone: the tetrafluorosilane SiF4 loaded gases are collected for treatment while the solid will be reinjected into the first reactor. To avoid any gas leakage from the cyclone (loaded with SiF4) to the first reactor (loaded with SiH4), the connection between the cyclone and the first reactor will incorporate a siphon whose pressure drop will be sufficient to prevent mixing between the gases. different qualities. 3) When the adsorption means, the reactor 40 is a dense bed technology. The proposed adsorbent is sodium fluoride. It was selected to react with SiF4 and for the reversibility of this reaction: SiF4 (g) + 2NaF (s) Na2SiF6 (s) Na2SiF6 (s) 400 ° c> 2NaF (s) + SiF4 (g) The adsorbent is therefore injected into the reactor inlet and its flow can be ensured by continuous injection or mechanical displacement. It can be used in bulk or deposited on substrate. The gaseous mixture N2 / H2 / SiH4 / SiF4 is injected countercurrently with the flow of solids in the first third of the reactor. The gas flow will thus cross-flow the first third of the reactor, where the reaction between sodium fluoride and SiF4 can take place. The length of this section of the reactor and the rate of injection of the gas will have to be calculated so that the passage time of the gas in this section is sufficient for all the SiF4 to react. An N2 / H2 / SiH4 gas stream is thus recovered at the reactor head. At the level of the injection of the gas to be treated, the dense bed thus consists of a NaF / Na 2 SiF 6 mixture. The second half of the reactor is then heated to 400 ° C to promote the regeneration reaction of the adsorbent. A gaseous stream of nitrogen is also introduced cocurrently with the solid to control the gaseous flow in this second half of the reactor and to prevent the silane released by the regeneration from being able to mix again with the injected gas. A buffer zone between initial gas injection and nitrogen injection may also be considered to maximize this effect. At the outlet of the reactor, the dense bed consists mainly of NaF which can then be injected again at the reactor head and the SiF4 / N2 gas mixture will be collected for treatment.

This means of carrying out the process of the invention is proposed for a horizontal piston flow of the fluidized bed and has also been envisaged for a vertical reactor: the solid would then be injected at the top of the reactor and its flow would be by gravity without necessity. mechanical means or intermediate injection of nitrogen. 4) In the case where the adsorption means, the piezoelectric reactor 40 is a dense multi-etaqe bed technology. In a single dense bed, the gaseous mixture N 2 / H 2 / SiH 4 / SiF 4 is injected simultaneously with the adsorbent at the inlet of the reactor and at the co-current of the flow. The advancement of the solid through the reactor will be ensured by its continuous injection and by gas entrainment. In case of insufficient transport, we can add a mechanical displacement device. The adsorbent may be used in bulk or deposited on a substrate. In a first unheated reactor section, the reaction between NaF and SiF4 will proceed. The length of this section should be calculated to achieve an adsorption efficiency of 100%. The influential parameters will be the solid flow rate, the gas flow rate and the SiF4 content of the gas. An N2 / H2 / SiH4 gas stream is thus recovered at the end of the first section. At this point, the bed therefore consists of a NaF / Na 2 SiF 6 mixture. The second half of the reactor is then heated to 400 ° C to promote the regeneration reaction of the adsorbent. A buffer zone between the start of the heating zone and the outlet of the N 2 / H 2 / SiH 4 mixture is provided in order to avoid reflux of the SiF 4 gas. A gas outlet is also provided at the inlet of the heating zone in order to recover the residual gases and the SiF4 present.

At the outlet of the reactor, the dense bed consists mainly of NaF which can then be injected again at the reactor head and the gas, consisting mainly of SiF4 will be collected for treatment. This approach using a single dense bed requires a very high accuracy of control and design of the reactor so that the reaction zones are well defined. This also implies a less flexibility of the process vis-à-vis gas flow rate variations as well as the SiF4 content of the injected gas. One method to overcome these disadvantages is to adopt a dense double bed process. This configuration simplifies the management of the gas flows in the particle beds and avoids the risk of contamination of the cleaned gas stream. In return, it requires the injection of nitrogen into the second bed to maintain the gas flow and entrainment of the SiF4 released by regeneration of the adsorbent. 5) In the case where the adsorption means, the pore reactor 40 comprises at least one rotating cartridge of adsorbents. The adsorbent cartridge consists of compacted sodium fluoride and is divided into several sections, some heated and others not. The N2 / H2 / SiH4 / SiF4 gas mixture is injected into the unheated sections to adsorb the SiF4 which will react and form Na2SiF6. The purified gas N2 / H2 / SiH4 is thus recovered. The adsorbent may be used in bulk or deposited on a substrate. The principle of the system is to rotate at a given speed around its central axis, which will allow the solid to progressively move from cold areas to heated areas at 400 ° C and return to cold areas. This method proposes to adsorb SiF4 in the cold zone by injecting the gas to be purified parallel to the axis. The solid rotating progressively charges Na2SiF6 and gradually enters the heated zones. Once the optimum adsorbent regeneration temperature reached (estimated at 400 ° C), a preheated nitrogen gas stream is injected parallel to the axis but counter-current to the initial injection to minimize migration of SiF4 in the cartridge. At the exit of this heated zone, the adsorbent gradually returns to the cold adsorption zone while cooling. To optimize this cooling, the speed of rotation of the cartridge is the main parameter. This cooling can also be accelerated by providing for the injection of cold nitrogen into the adsorbent, which would have the advantage of causing traces of SiF4 in the adsorbent. The main dimensioning parameters of this unit will be: ^ The flow rate of the N2 / H2 / SiH4 / SiF4 gas flow and its composition; • The particle size of the solid NaF; • The height of the cartridge; • The rotational speed of the cartridge.

According to a variant of the invention, a buffer capacity 18 can be installed in order to smooth the flow variations of the mixture circulating in the pipe 17 downstream of said compression means 16. The size and the manner of connecting this capacity 16 to the pipe 17 depend on the flows used and the desired operating mode.

According to a variant of the invention, one or more systems for removing impurities may be arranged around the compression module. Indeed, the exact location will eliminate a majority of one or more harmful impurities following the process. The presence of fluorine may cause problems for example corrosion or mechanical strength of the materials present in the apparatus according to the invention. The cost can be as high if the presence of fluorinated compounds requires the use of particularly suitable materials so expensive. The compressor 16 is particularly targeted by these possible problems. Then, an elimination system 19 will preferably be placed upstream of the compression system 16. Of course, in the absence of detrimental impurities, no necessary elimination system is to be added. According to a variant of the invention, a separation means 19 operating for example on the principle of adsorption (for example, PSA, TSA: English, or Pressure or Thermal Swing Absorption) is located downstream of the compression means 16 in the purpose is to adsorb impurities such as for example H 2 O, O 2 or fluorinated or chlorinated compounds. In the conduit 20 at the outlet of the separation means 19, a nitrogen / silane / hydrogen mixture circulates, the pressure being a few bars. One of the objectives of the present invention is to recycle gases, such as silane and hydrogen, pure. Pure gas is understood to mean gases comprising less than 100 ppm of impurities, for example less than 100 ppm of nitrogen, or even less than 1 ppm of impurity, for example less than 1 ppm of nitrogen. These specifications depend on the intended application. Or the recycling at a pressure of a few bars of a gas mixture (silane / hydrogen) comprising less than 100 ppm of nitrogen, preferably less than 1 ppm of nitrogen, resulting from an initial mixture (silane / hydrogen) which can contain up to 90% nitrogen is a technical problem to be solved by the present invention. Therefore, a cryogenic separation device 21 is located downstream of said conduit 20. A cryogenic system 21, allows to condense or even solidify the silane (SiH4) and thus ensures the separation of SiH4. Depending on the separation conditions (pressure and temperature), the condensed silane phase may contain more or less nitrogen and other heavy products. Further purification of the silane (distillation column or TSA for example) may be considered according to the required specifications. In particular, obtaining a nitrogen content of less than 1 ppm can be efficiently obtained using a distillation column 23 which is fed by the condensed mixture into the separator 21 and flowing in the pipe 22. For example, the distillation column 23 may be configured to allow removal of the so-called light impurities through the pipe 25 and the so-called heavy impurities via the pipe 26. The silane having the desired purity is then recovered in the pipe 24. There are various methods to reinject the purified SiH4 into the reactor. Either directly by directly returning the flow into the SiH4 distribution system, or by passing buffer capacity or even filling bottles. Preferably, the solution according to the invention uses buffer capacities (27) which make it possible to adapt the output streams of the column to the gas demand of the distribution system. In particular, a system implementing two buffering capacitors in parallel makes it possible to fill one capacity while the other is emptying and thus to have a total decoupling between the output flow of the column and the flow requested by the control system. distribution. The filling of these capacities can for example be done by cryo-filling, a mode well known in the field of gases produced by cryogenic routes.

According to a variant of the invention, the silane thus recycled and purified is reinjected into the pipe 4 via the pipe 28. The mixture N2 / H2 standing out a few bars, from the separation step performed by the system 21, through a conduit 29 can then be separated by means of a membrane 30 to allow the hydrogen H2 to be recycled if necessary. Indeed, the distillation of the hydrogen / nitrogen mixture is not very easy because of the very low temperatures required. Obtaining pure hydrogen with less than 100 ppm of nitrogen, or even less than 1 ppm of nitrogen, is conventionally obtained using systems based on adsorption (PSA, cryogenic adsorption, etc.). However, to be fully operational, these types of equipment require an input stream with limited nitrogen levels (less than about 20% for a PSA or less than 5000 ppm for a cryo-adsorption system). The use of a membrane makes it possible, at a lower cost, to deplete the nitrogen mixture so as to match the specifications of a possible purification system downstream. The nitrogen resulting from the separation with pure hydrogen is preferably removed from the system (C) by means of, for example, a vent 31. Part of the nitrogen resulting from this separation can also be used by recycling to supply the pump 8, by means of a recycling conduit 32. The reuse of nitrogen is probably not financially relevant because of the low cost of nitrogen. It will therefore be preferable to put the nitrogen in the vent 31 rather than to recycle it to the vacuum pump 8 of the reaction chamber 7. At the outlet of the membrane 30 through which the purified hydrogen circulates, the hydrogen leaving the the membrane can be used for the regeneration of the separation system 19 via a pipe not shown in Figure 1 or also be reinjected (recycled) in the reaction chamber 7 via a pipe 33 after further purification if necessary. This additional purification can be done, for example by PSA or by cryoadsoprtion according to the required purity specifications. According to a variant of the invention, the hydrogen flowing in the pipe 33 is compressed using a compression means 34 and then conveyed to the purification system 36 via the pipe 35. The fact of compressing the gas makes it possible to optimize purification. For example, when using a PSA, the operating pressure of the order of 25 bar.

The hydrogen thus recycled and purified can be, for example reinjected into line 5 using line 37. According to a variant of the invention, one or more capacities 38 can be used to store hydrogen and thus decoupling the flow of recycled hydrogen from the flow required by the application. According to another variant of the invention, the recycled hydrogen can be reinjected into the hydrogen source capacity 2. According to a variant of the invention, the composition of the recycled gas streams can be controlled by a suitable system ( FTIR, katharometer ...) connected either on the pipes 28 and / or 37, or on the capacitors 27 and / or 38. The different quantities measured can thus be sent back to a supervision system which can act on the flow rates of the fresh gases injected to control the process. Another method for controlling the quality of the recycled gases is to take a sample of said gases on the lines 28 and / or 37 or in the capacities 27 and / or 38, and then perform an ex-situ analysis of these samples.

According to one embodiment of the invention, the apparatus comprises reservoirs or mixing chambers (not shown in FIG. 1). These chambers are intended to mix the recycled gases with pure gases from, for example, sources 1 and 2. These types of mixtures make it possible, for example, to damp the fluctuations in the quality of the composition of the recycled gases to be mixed before being reinjected into the reaction chamber 7. In order that the silane / hydrogen mixture is injected into the reaction chamber 7 in the same proportions as the silane / hydrogen mixture circulating in the conduits 4 and 5 containing the gases from the sources 1 and 2, the ratio of silane to hydrogen in concentrations is checked before injection into the reaction chamber 7. According to one variant, the cryogenic separation system 21 comprises exchangers making it possible to reduce the temperature of the mixture. These exchangers are designed and sized to optimize the energy balance. The principle is based on the liquefaction of the silane. To do this, the temperature of the gas containing the silane to be liquefied is conducted at a temperature below the liquefaction temperature (bubble temperature) of the silane using cooled exchangers using extended nitrogen for example. Indeed, it makes it easy to modulate this temperature. Other cold sources are usable. Then, when the silane is in the majority in liquid form, it is necessary to separate the drops of the waste gas. A separation pot is then used, possibly equipped with one or more drop recovery systems in order to recover a maximum of drops. Part of the nitrogen contained in the gas is liquefied and / or solubilized in the liquid silane. However, it is necessary to recycle a silane product of high purity, it is therefore preferable to purify this nitrogen / silane mixture (mainly). Preferably a distillation column of which one of the outlets will consist of high purity silane will be used.

Such cryogenic separation systems make it possible to implement the method according to the invention in a continuous manner.

Claims (12)

REVENDICATIONS1. A silane recycling process comprising the following successive steps: a) Injecting a pure silane / pure hydrogen mixture (SiH4 / H2) into a reaction chamber (7) to make silicon-containing thin layers; b) extraction of the mixture: excess silane not used in step a) / hydrogen (SiH4 / H2), by means of a pump (8) using a feed gas; c) Delivery of said pump (8) at a pressure close to atmospheric pressure, of a mixture comprising at least silane (SiH4), hydrogen (H2), silicon tetrafluoride (SiF4) and a non zero of said feed gas; d) Separation of the silicon tetrafluoride (SiF4) from the silane / hydrogen / feed gas mixture resulting from the mixture resulting from step c); characterized in that at least 50%, preferably 70%, and more preferably 80% of the silane (SiH4) from step b) is reused after step d) for a new step a). 20 2. The process for recycling silane and hydrogen according to claim 1, further comprising a step of: e) separating the silane (SiH4) from the hydrogen / gas mixture obtained from the mixture resulting from step d), said obtained silane comprising less than 100 ppm feed gas, preferably less than 10 ppm feed gas, preferably less than 1 ppm gas. 3. Process for recycling silane and hydrogen using the process as defined in one of claims 1 or 2, characterized in that during step d), the silicon tetrafluoride contained in the mixture from of step c) reacts with a nF2 solid adsorbent, nM, where n = 2 when M is an alkali metal selected from Li, Na, K, Rb, Cs, Fr and n = 1 when M is a metal alkaline earth selected from Be, Mg, Ca, Sr, Ba, Ra. 10 4. The method of claim 3 further comprising a step of regenerating the solid adsorbent by thermal activation at a temperature greater than or equal to 400 ° C, under a purge of a neutral gas vis-à-vis the reaction of the step d), such as N 2, H 2, Ar, He. 5. Method according to one of claims 3 or 4 characterized in that the adsorbent is sodium fluoride (NaF). 6. Method according to one of claims 2 to 5, characterized in that the silane stream (SiH4) from step e) contains less than 10 ppm of silicon tetrafluoride (SiF4), and preferably less than 1 ppm. 7. Method according to one of claims 1 to 6 further comprising a step of: f) Purification of hydrogen (H2) from step e) such as the rate of feed gas in hydrogen is not more than 100 ppm, preferably not more than 10 ppm and more preferably not greater than 1 ppm; characterized in that at least 50% of the hydrogen (H2) and preferably at least 85% of the hydrogen from step b) is reused after step 20 f) for a new step a). 8. Method according to one of claims 1 to 7, characterized in that said feed gas pump (8) is nitrogen (N2). 25 9. Process according to claim 8, characterized in that the mixture resulting from stage c) comprises, from 60% to 75% of nitrogen (N2), from 20% to 35% of hydrogen (H2), from 1.5% to 4% of silane (SiH4) and 100 ppm to 0.3% of silicon tetrafluoride (SiF4), preferably 70% of nitrogen (N2), 27.9% of hydrogen (H2), 2% silane (SiH4) and 0.1% silicon tetrafluoride (SiF4). 30 10. Process according to any one of claims 2 to 9, characterized in that step e) is carried out by separation and / or cryogenic distillation. 5 11. Method according to one of claims 3 to 10 characterized in that step d) comprises introducing the mixture from step c) into a container (40) such as a cartridge or one or more fluidized reactors containing said nF2, nM solid adsorbent. 12. The method of claim 11, characterized in that the container (40) contains several cartridges placed in parallel so as to regenerate one while the other adsorb SiF4. 10