Trisilylamine synthesis apparatus and synthesis method

Abstract

Provided are an apparatus and method for synthesizing trisilylamine, which can safely remove solid ammonium chloride in a reactor by thermal decomposition. [Solution] The system comprises a reactor 10 in which a synthesis reaction of trisilylamine takes place, a reaction starting material supply pipe 14 that supplies the reaction starting material to the reactor, a trisilylamine discharge pipe 13 that discharges trisilylamine from the reactor, reactor heating means 14, 19 for heating the reaction space of the reactor, and a gaseous by-product discharge pipe 15 that discharges gaseous by-products from the reactor, wherein the reaction space of the reactor is maintained at a temperature lower than the decomposition temperature of the reaction by-products produced during the synthesis reaction, and the reactor heating means heats the reaction space of the reactor to a temperature equal to or higher than the decomposition temperature after trisilylamine is discharged through the trisilylamine discharge pipe, and the gaseous by-product discharge pipe discharges gaseous by-products, including pyrolysis products of the reaction by-products thermally decomposed by the reactor heating means.

Description

[Technical Field]

[0001] The present invention relates to an apparatus and method for synthesizing trisilylamine, and more particularly to an apparatus and method for synthesizing trisilylamine, which can remove solid ammonium chloride (NH4Cl) generated as a reaction by-product in the synthesis of trisilylamine by thermal decomposition within a reactor. [Background technology]

[0002] Trisilylamine (TSA, N(SiH3)3) is a colorless, spontaneously combustible compound with a melting point of -105.6 °C and a boiling point of +52 °C, and is used in the manufacture of semiconductor devices, for example, as a precursor for the formation of silicon nitride or silicon oxynitride.

[0003] Trisilylamine is generally synthesized from monochlorosilane and ammonia according to the following reaction scheme: 3H3SiCl+4NH3→N(SiH3)3+3NH4Cl

[0004] Ammonium chloride, a by-product produced during the synthesis of such trisilylamine, acts as a catalyst to decompose trisilylamine into silanes and other decomposition products (e.g., silazanes), resulting in a low yield of trisilylamine. Furthermore, ammonium chloride is in a solid state under normal reaction conditions, which can cause problems such as clogging of reactor piping.

[0005] In order to prevent the solid ammonium chloride from clogging the piping in the reactor, conventional synthesis apparatuses periodically remove the solid ammonium chloride using a filter and / or a separate removal means. However, the solid particles of ammonium chloride collected by the filter and / or the separate removal means may contain other by-products of the synthesis reaction, such as flammable silanes (silane, silazane, etc.) and trace amounts of trisilylamine.

[0006] If solid ammonium chloride collected by a filter or other removal means is disposed of as is, flammable substances such as silanes attached to the surface of the solid ammonium chloride particles may be exposed to the atmosphere, which could lead to spontaneous combustion. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention is intended to reduce or solve these problems of the prior art, and has as its object to provide an apparatus and method for synthesizing trisilylamine that can safely remove solid ammonium chloride in a reactor by thermal decomposition. [Means for solving the problem]

[0008] According to one aspect of the present invention, there is provided an apparatus for synthesizing trisilylamine, comprising: a reactor in which a synthesis reaction of trisilylamine takes place; a reaction starting material supply pipe for supplying a reaction starting material to the reactor; a trisilylamine discharge pipe for discharging trisilylamine from the reactor; a reactor heating means for heating the reaction space of the reactor; and a gaseous by-product discharge pipe for discharging gaseous by-products from the reactor, wherein the reaction space of the reactor is maintained at a temperature lower than the decomposition temperature of reaction by-products produced during the synthesis reaction; the reactor heating means heats the reaction space of the reactor to a temperature equal to or higher than the decomposition temperature after trisilylamine is discharged through the trisilylamine discharge pipe; and the gaseous by-product discharge pipe discharges gaseous by-products, including pyrolysis products of the reaction by-products thermally decomposed by the reactor heating means.

[0009] According to another aspect of the present invention, a method for synthesizing trisilylamine includes a reaction starting material inflow step of inflowing a reaction starting material into a reactor, a reaction step of reacting the inflowed reaction starting material to produce trisilylamine and a reaction by-product, a trisilylamine discharge step of discharging trisilylamine from the reactor, a reaction by-product pyrolysis step of thermally decomposing the reaction by-product in the reactor after the trisilylamine discharge step, and a gaseous by-product discharge step of discharging the gaseous by-product obtained in the reaction by-product pyrolysis step from the reactor, wherein the temperature inside the reactor in the reaction step is maintained at a temperature lower than the decomposition temperature of the reaction by-product, and the reaction by-product pyrolysis step includes a step of heating the reaction space of the reactor to a temperature equal to or higher than the decomposition temperature of the reaction by-product. [Effects of the Invention]

[0010] The apparatus for synthesizing trisilylamine according to the present invention can safely remove, by thermal decomposition, solid ammonium chloride that has accumulated in the reactor as a by-product of the trisilylamine synthesis reaction. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram showing a synthesis apparatus according to Example 1 of the present invention. [Figure 2] FIG. 1 is a schematic diagram showing a synthesis device according to Example 2 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. However, the size, material, shape and relative arrangement of components of the synthesis apparatus described below, as well as the process flow and reaction conditions of the synthesis method, may be appropriately changed within the technical scope of the present invention, and the scope of protection of the present invention is not limited to the embodiments described below.

[0013] In the apparatus for synthesizing trisilylamine according to the present invention, trisilylamine is synthesized according to the following reaction formula. 3SiH3X+4NH3→N(SiH3)3+3NH4X(X=Cl,F,Br)

[0014] The reactor of the synthesis apparatus according to one embodiment of the present invention is operated under conditions in which the reaction by-product ammonium halide remains in the reactor, and the reaction product, such as trisilylamine, is discharged and collected outside the reactor substantially free of ammonium halide. After the trisilylamine is discharged, the ammonium halide in the reactor is safely removed by separate thermal decomposition within the reactor.

[0015] That is, in one embodiment of the present invention, the synthesis reaction conditions within the reactor are set so that the ammonium halide by-product of the synthesis reaction remains inside the reactor by accumulating in a solid state at the bottom of the reactor or adhering to the sidewall of the reactor, while the trisilylamine reaction product undergoes phase separation (e.g., liquid or gaseous state) from the ammonium halide by-product. If the trisilylamine reaction product is obtained in a liquid state, it is converted into a gaseous state by heating and then separated, discharged, and collected outside the reactor. After the gaseous trisilylamine is discharged, the solid ammonium halide accumulated within the reactor is decomposed into gaseous ammonia or hydrogen chloride through a separate heating process. This gaseous by-product is then discharged outside the reactor together with the silanes attached to the ammonium halide, and safely removed. Specific embodiments of the present invention will be described in more detail below. [Example]

[0016] Example 1 FIG. 1 is a schematic diagram showing a synthesis apparatus 1 according to a first embodiment of the present invention. The synthesis apparatus 1 and synthesis method according to the first embodiment of the present invention will be described below on the assumption that monochlorosilane and ammonia are used as reaction starting materials, and trisilylamine is produced as a reaction product and ammonium chloride is produced as a reaction by-product. However, the present invention is not limited to this. For example, monofluorosilane, monobromosilane, or monoiodosilane can be used as one of the reaction starting materials instead of monochlorosilane, and other ammonium halides can be produced as reaction by-products depending on which reaction starting material is used.

[0017] The synthesis apparatus 1 according to Example 1 of the present invention comprises a reactor 10 in which a synthesis reaction of trisilylamine takes place, reaction starting material supply pipes 11 and 12 for supplying the reaction starting material to the reactor 10, a trisilylamine discharge pipe 13 for discharging trisilylamine to the outside of the reactor 10, reactor heating means 14 and 19 for heating the reaction space of the reactor 10, and a gaseous byproduct discharge pipe 15 for discharging gaseous byproducts obtained by thermal decomposition of reaction byproducts (e.g., ammonium chloride) by the reactor heating means 14 and 19 to the outside of the reactor 10.

[0018] 1, the reactor heating means includes an inert gas supply pipe 14 for supplying an inert gas to the reactor 10, and an inert gas supply pipe heating means 19 for heating the inert gas supply pipe 14. However, the present invention is not limited thereto, and the reactor heating means may heat the wall of the reactor 10 to heat the reaction space within the reactor 10.

[0019] The reactor 10 according to Example 1 of the present invention is a batch reactor, and predetermined amounts of reaction starting materials, such as monochlorosilane and ammonia, are supplied through reaction starting material supply pipes 11 and 12. Here, the monochlorosilane supply pipe 11 and the ammonia supply pipe 12 independently connect a monochlorosilane supply source (not shown) and an ammonia supply source (not shown) to the reactor 10, respectively. That is, monochlorosilane and ammonia are independently supplied to the reactor 10 so that they do not react before entering the reactor 10. This prevents the reaction starting material supply pipes 11 and 12 from becoming clogged with solid reaction by-products (e.g., ammonium chloride).

[0020] However, the present invention is not limited to this, and monochlorosilane and ammonia may be supplied to the reactor in a mixed state. In this case, it is preferable to heat the supply pipes 11 and 12 of the reaction starting materials and / or the mixer (not shown) to a temperature equal to or higher than the decomposition temperature of ammonium chloride to prevent clogging of the supply pipes of the reaction starting materials due to the reaction between monochlorosilane and ammonia. When a predetermined amount of reaction starting materials has flowed into the reactor 10, the supply pipes 11 and 12 for the reaction starting materials are shut off by valves (not shown).

[0021] The reaction conditions in the reactor 10 in Example 1 of the present invention are set so that (i) trisilylamine as a reaction product is in a liquid state, and (ii) ammonium chloride as a reaction by-product is in a solid state.

[0022] For example, when the pressure condition in the reactor 10 is atmospheric pressure, the temperature (T R ) is maintained at a temperature below 52°C, the boiling point of trisilylamine (T R <52℃). Temperatures below 52℃ (T R ) the equilibrium phase of ammonium chloride is a solid phase, so in Example 1 of the present invention, the synthesis reaction in the reactor 10 is carried out according to the following reaction formula: 3SiH3Cl+4NH3→N(SiH3)3(l)+3NH4Cl(s)

[0023] When the synthesis reaction of trisilylamine is completed, solid ammonium chloride is present in liquid trisilylamine in reactor 10, as shown in FIG.

[0024] In Example 1 of the present invention, once the synthesis reaction of trisilylamine is completed, the interior of reactor 10 is heated to a temperature above 52°C, the boiling point of trisilylamine, in order to separate and discharge trisilylamine. For example, the temperature inside reactor 10 can be increased by introducing inert gas heated to a temperature above 52°C using inert gas supply pipe heating means 19 into reactor 10 through inert gas supply pipe 14. As a result, trisilylamine, which was in a liquid state immediately after the completion of the reaction, changes to a gaseous state.

[0025] Here, the inert gas supplied through the inert gas supply pipe 14 is nitrogen or argon, and is preferably nitrogen. However, the present invention is not limited to this, and other gases that do not react with trisilylamine, etc. (e.g., helium, etc.) may also be used.

[0026] Meanwhile, in the heating step for separating and discharging trisilylamine, the temperature inside the reactor 10 is set to a temperature lower than the decomposition temperature of ammonium chloride, a reaction by-product. As will be described later, ammonium chloride begins to be fully thermally decomposed from 340°C. Therefore, for example, in the heating step for separating and discharging trisilylamine, the temperature inside the reactor 10 preferably satisfies 52°C≦T<340°C. More preferably, the temperature inside the reactor 10 is set to satisfy 52°C≦T≦300°C.

[0027] As a result, trisilylamine as a reaction product vaporizes and fills the internal space of the reactor 10, and ammonium chloride as a reaction by-product in solid form accumulates in the lower part of the interior of the reactor 10 or adheres to the sidewalls. That is, the reaction product and reaction by-product are separated into gaseous and solid forms, respectively.

[0028] In this state, the valve (not shown) of the trisilylamine discharge pipe 13 is opened to discharge the gaseous trisilylamine outside the reactor 10. However, the present invention is not limited to this, and the valve of the trisilylamine discharge pipe 13 may be opened at any time after the heated inert gas begins to be introduced into the reactor 10 in order to separate and discharge the trisilylamine.

[0029] Although not shown in Fig. 1, a filter may be further provided at the inlet of trisilylamine discharge pipe 13 in order to prevent fine solid particles of ammonium chloride from being discharged together with the gaseous trisilylamine in reactor 10. The filter may be a glass frit, a metal frit, a gas-permeable membrane, or the like, but may also be made of other materials as long as they do not react with trisilylamine, etc.

[0030] The trisilylamine discharged to the outside is collected using a collection means such as a condensation trap, as described below.

[0031] In Example 1 of the present invention, the liquid trisilylamine as the reaction product is vaporized and discharged, but the present invention is not limited to this. After the synthesis reaction is complete, trisilylamine is liquid and ammonium chloride is solid, and phase separation has already occurred. Therefore, the liquid trisilylamine can be directly discharged without the heating step for converting trisilylamine to gas. Alternatively, the liquid trisilylamine can be discharged first, and only the trisilylamine remaining at the bottom of the reactor can be converted to gas by heating and then discharged. In this case, it is preferable to install the trisilylamine discharge pipe 13 in an appropriate position so that the liquid trisilylamine can be discharged. Alternatively, a pipe for discharging liquid trisilylamine and a pipe for discharging gaseous trisilylamine can be installed separately.

[0032] Once a sufficient amount of trisilylamine has been separated and discharged from reactor 10, the valve on trisilylamine discharge pipe 13 is closed, and the temperature inside reactor 10 is increased to a temperature above the decomposition temperature of the reaction by-products. For example, an inert gas (such as nitrogen) heated to a temperature above the decomposition temperature of ammonium chloride by inert gas supply pipe heating means 19 is supplied into reactor 10 through inert gas supply pipe 14. The temperature of the inert gas supplied for thermal decomposition of the reaction by-products is set to, for example, 340°C or higher.

[0033] In the present invention, the decomposition temperature of a reaction by-product, for example, ammonium chloride, refers to the temperature at which ammonium chloride is decomposed into gaseous substances such as ammonia and hydrogen chloride. Experiments by the present inventors and others have shown that ammonium chloride is hardly thermally decomposed at a temperature of 300°C, but significant thermal decomposition begins to occur around 340°C.

[0034] The temperature of the inert gas supplied for the thermal decomposition of the reaction by-products is preferably 350°C or higher, more preferably 400°C or higher, and even more preferably 450°C, so that the thermal decomposition of ammonium chloride occurs more quickly. According to experiments conducted by the inventors of the present invention, when the temperature of the supplied inert gas is 350°C, approximately 75% of the reaction by-products are thermally decomposed within one hour, based on their weight; when the temperature is 400°C, approximately 80% are thermally decomposed; and when the temperature is 450°C, more than 90% of the ammonium chloride is decomposed into gaseous form. While thermal decomposition at temperatures higher than 450°C increases the thermal decomposition rate and shortens the thermal decomposition time, from the perspective of balancing thermal decomposition efficiency and energy consumption, the temperature of the inert gas supplied for the thermal decomposition of the reaction by-products is preferably 520°C or lower.

[0035] In this way, by heating the space within reactor 10 to a temperature equal to or higher than the decomposition temperature of ammonium chloride, the solid ammonium chloride remaining within reactor 10 is decomposed into gaseous ammonia, hydrogen chloride, etc. At this time, silane, silazane, and trace amounts of trisilylamine adhering to the solid particles of ammonium chloride also become gaseous.

[0036] When the thermal decomposition of ammonium chloride has progressed sufficiently, a valve (not shown) on the gaseous by-product discharge pipe 15 is opened to discharge gaseous by-products such as ammonia, hydrogen chloride, silane, silazane, and a trace amount of trisilylamine from the reactor 10. As will be described later, the discharged gaseous by-products are removed, for example, through a scrubber (a gaseous by-product treatment means).

[0037] After the gaseous by-products have been sufficiently discharged, an inert gas (e.g., nitrogen) is supplied to the reactor 10 to purge the reaction space in the reactor 10. The temperature of the inert gas during purging is set to a temperature below 52°C, i.e., the temperature of the synthesis reaction (T R ) is preferred.

[0038] After the inert gas purging is completed, the valves of the feed pipes 11 and 12 for the reaction starting materials are opened again to proceed with the synthesis reaction of the next batch. Thereafter, the above-mentioned steps are repeated.

[0039] The synthesis apparatus 1 according to Example 1 of the present invention further includes a condenser 16 as trisilylamine collection means for collecting trisilylamine discharged in a gaseous state to the outside of the reactor 10, and a trisilylamine collection container 17 for storing the condensed trisilylamine.

[0040] Trisilylamine collection container 17 contains a dry ice / isopropyl alcohol (IPA) cooling bath maintained at a temperature of about 20° C. to about −110° C., preferably about −50° C. to about −110° C. However, the present invention is not limited thereto, and other collection means capable of collecting trisilylamine discharged in gaseous form may be used.

[0041] The synthesis apparatus 1 according to the first embodiment of the present invention further includes a scrubber 18 as a means for removing gaseous substances such as ammonia, hydrogen chloride, silane, and silazane that are generated by the thermal decomposition of ammonium chloride and discharged. The scrubber 18 of the present invention may be a scrubber commonly used in the art.

[0042] In Example 1 of the present invention, after the above-described batch process has been performed several times (when a sufficient amount of solid ammonium chloride particles has accumulated at the bottom of the reactor to require removal), the operation of reactor 10 is stopped, and the solid ammonium chloride that has not been thermally decomposed and accumulated in reactor 10 is removed. To this end, the synthesis apparatus according to Example 1 of the present invention may further include a solid reaction by-product collection vessel 101 for collecting and storing the solid ammonium chloride particles. The solid reaction by-product collection vessel 101 for collecting the solid ammonium chloride is connected to the bottom of reactor 10, for example, through a gate valve (not shown).

[0043] During operation of the reactor 10, the gate valve is closed and is opened after a predetermined number of batch processes are completed or between each subsequent batch process to discharge ammonium chloride accumulated in the lower part of the reactor 10 into a solid reaction by-product collection container 101. When the solid reaction by-product collection container 101 is filled with solid ammonium chloride, the solid ammonium chloride is discharged from the solid reaction by-product collection container 101 to the outside and removed.

[0044] The solid ammonium chloride particles collected in the solid reaction by-product collection vessel 101 have undergone at least one thermal decomposition process using a high-temperature inert gas, and therefore other by-products such as silane, silazane, and trace amounts of trisilylamine that may have been attached to the surface of the solid ammonium chloride immediately after the synthesis reaction are safely removed in the scrubber 18 through the thermal decomposition / gaseous by-product discharge process described above. Therefore, even if the solid ammonium chloride is exposed to the atmosphere during the process of discharging the solid ammonium chloride from the solid reaction by-product collection vessel 101, the possibility of spontaneous combustion is greatly reduced because substantially no flammable material remains on the surface of the ammonium chloride solid particles.

[0045] While discharging the solid ammonium chloride from the collection container 101, cleaning of the reactor 10 can be performed at the same time, such as removing ammonium chloride that has not accumulated at the bottom of the reactor 10 but has adhered to the side wall or filter (not shown) of the reactor 10.

[0046] Although the above description has been primarily focused on the case where there is one reactor 10, the present invention is not limited thereto and may include multiple reactors. That is, the reactor 10 of the present invention may include multiple reaction vessels that are connected in parallel to sources of reaction starting materials and can be operated simultaneously or alternately. The multiple reaction vessels may be operated such that while at least one reaction vessel is performing a thermal decomposition process of reaction by-products and / or a process of discharging gaseous by-products resulting from the thermal decomposition, at least one other reaction vessel is performing a trisilylamine synthesis reaction.

[0047] For example, the reactor 10 may have a first reaction vessel and a second reaction vessel, and may be operated such that while the synthesis reaction of trisilylamine proceeds in the first reaction vessel, the reaction by-products are thermally decomposed and / or the gaseous by-products are discharged in the second reaction vessel.

[0048] This can prevent a decrease in the overall operating rate of the synthesis apparatus due to thermal decomposition of reaction by-products between synthesis steps.

[0049] According to the first embodiment of the present invention, the solid ammonium chloride in the reactor 10 is thermally decomposed and removed in a gaseous state together with other by-products (silane, silazane, a trace amount of trisilylamine, etc.). This reduces clogging of pipes and the like caused by solid ammonium chloride and a decrease in the yield of trisilylamine. Furthermore, exposure of spontaneously combustible substances such as silane and silazane to the atmosphere is suppressed, thereby reducing the risk of spontaneous combustion.

[0050] <Example 2> 2 is a schematic diagram illustrating a synthesis apparatus 2 and a synthesis method according to Example 2 of the present invention. Example 2 of the present invention differs from Example 1 of the present invention in that the temperature inside reactor 20 is maintained at a temperature equal to or higher than the boiling point of the reaction product trisilylamine during the synthesis reaction step in reactor 20, and the synthesis reaction is carried out continuously or semi-continuously. Hereinafter, the second embodiment of the present invention will be specifically described, focusing on the differences from the first embodiment.

[0051] In Example 2 of the present invention, reactor 20 is operated under atmospheric pressure, and during the synthesis reaction process, the reaction starting materials, monochlorosilane and ammonia, are continuously supplied through reaction starting material supply pipes 21 and 22. That is, reactor 20 in Example 2 is a continuous or semi-continuous reactor.

[0052] During the synthesis reaction process of trisilylamine, the reaction space of the reactor 20 is maintained at a temperature equal to or higher than the boiling point of the reaction product, trisilylamine, and lower than the decomposition temperature of the reaction by-product, ammonium chloride. For example, the reaction space in the reactor 20 is maintained at a temperature of 52°C or less during the synthesis reaction process. R <340°C. More preferably, the temperature in the reactor 20 is 52°C < T R It is adjusted to satisfy the condition of ≦300°C. That is, the synthesis reaction in Example 2 is carried out according to the following reaction formula. 3SiH3Cl+4NH3→N(SiH3)3(g)+3NH4Cl(s)

[0053] For this purpose, for example, during the synthesis reaction process, an inert gas (e.g., nitrogen) heated by an inert gas supply pipe heating means 29 so as to satisfy the above-mentioned temperature conditions is supplied into the reactor 20 through the inert gas supply pipe 24. However, the present invention is not limited thereto, and the temperature of the reaction space in the reactor 20 may be adjusted by heating the wall of the reactor 20.

[0054] As the synthesis reaction progresses, gaseous trisilylamine is produced, and the produced gaseous trisilylamine is continuously discharged from reactor 20 through trisilylamine discharge pipe 23. In FIG. 2, reaction starting material supply pipes 21 and 22 and trisilylamine discharge pipe 23 are shown connected to the top of reactor 20, but the present invention is not limited thereto, and other arrangements are possible as long as the supply of reaction starting materials from reaction starting material supply pipes 21 and 22 and the discharge of trisilylamine from trisilylamine discharge pipe 23 are smoothly performed. Furthermore, although not shown in FIG. 2, a filter or the like may be provided at the inlet of trisilylamine discharge pipe 23 to prevent fine solid particles of ammonium chloride from being discharged together with the inlet.

[0055] The gaseous trisilylamine discharged from reactor 20 is condensed in condenser 26 and collected in trisilylamine collection vessel 27. Trisilylamine collection vessel 27 may have, for example, a cooling bath of dry ice / isopropyl alcohol (IPA) maintained at a temperature lower than the boiling point of trisilylamine, for example, at a temperature of about 20°C to about -110°C, preferably about -50°C to about -110°C. As the synthesis reaction proceeds, solid ammonium chloride accumulates in reactor 20 as a reaction by-product.

[0056] After the synthesis reaction has proceeded for a predetermined time, the supply of the reaction starting materials and the discharge of gaseous trisilylamine are stopped, and in order to remove the solid ammonium chloride accumulated in the reactor 20 by thermal decomposition, an inert gas (e.g., nitrogen) heated to a temperature equal to or higher than the decomposition temperature of ammonium chloride by an inert gas supply pipe heating means 29 is supplied through the inert gas supply pipe 23.

[0057] The temperature of the inert gas (e.g., nitrogen) supplied for the thermal decomposition of ammonium chloride is 340°C or higher, preferably 350°C or higher, more preferably 400°C or higher, and even more preferably 450°C or higher. However, in order to balance with energy consumption, it is preferable that the temperature be 520°C or lower.

[0058] As the inert gas heated to a temperature equal to or higher than the decomposition temperature of ammonium chloride by the inert gas supply pipe heating means 29 is supplied into the reactor 20, the solid ammonium chloride remaining in the reactor 20 is decomposed into gaseous ammonia and hydrogen chloride, and the silane, silazane, trace amounts of trisilylamine, etc. adhering to the solid particles of ammonium chloride all become gaseous.

[0059] When the thermal decomposition of ammonium chloride has progressed sufficiently, the valve of the gaseous by-product discharge pipe (25) of the reactor 20 is opened, and gaseous by-products such as ammonia, hydrogen chloride, and silane are discharged from the reactor 20 and removed by a scrubber 28.

[0060] In this way, also in Example 2, by removing the solid ammonium chloride in reactor 20 by thermal decomposition with a high-temperature inert gas, it is possible to reduce the clogging of piping and the like by the solid ammonium chloride and the reduction in the yield of trisilylamine, and furthermore, it is possible to safely remove other flammable by-products attached to the solid ammonium chloride.

[0061] After the gaseous by-products have been discharged and removed, an inert gas (e.g., nitrogen) is supplied into the reactor 20 to purge it. The inert gas used for purging is selected from the group consisting of a nitrate, thiamin ... R ), that is, a temperature of 52°C or higher and lower than 340°C. More preferably, it is a temperature of 52°C or higher and 300°C or lower (T R ) is.

[0062] The synthesis apparatus 2 of Example 2 may also further include a solid reaction by-product collection container 202 connected to the bottom of the reactor 20 through a gate valve (not shown) and a gate valve for opening and closing the container, in order to remove solid ammonium chloride that has not been pyrolyzed and remains in the reactor 20. As described above, since substantially all flammable materials are removed from the surface of the solid ammonium chloride that has undergone the pyrolysis process, the risk of spontaneous combustion is significantly reduced even if the ammonium chloride in the solid reaction by-product collection container 202 is exposed to the atmosphere during the process of discharging the ammonium chloride.

[0063] Although the present specification has been described with reference to reactor 10 or reactor 20 being operated under atmospheric pressure, the present invention is not limited thereto and reactor 10 or reactor 20 may be operated under reduced pressure. When reactor 10 or reactor 20 is operated under reduced pressure, the temperature within the reactor may be appropriately changed within the scope of the technical concept of the present invention.

Claims

1. a reactor in which a synthesis reaction of trisilylamine occurs; a supply pipe for a reaction starting material for supplying the reaction starting material to the reactor; a trisilylamine discharge pipe for discharging trisilylamine from the reactor; and a reactor heating means for heating the reaction space of the reactor; a gaseous by-product discharge pipe for discharging gaseous by-products from the reactor; Equipped with The reaction space of the reactor is maintained at a temperature lower than the decomposition temperature of reaction by-products produced during the synthesis reaction; the reactor heating means heats the reaction space of the reactor to a temperature equal to or higher than the decomposition temperature after trisilylamine is discharged through the trisilylamine discharge pipe; The gaseous by-product discharge pipe discharges gaseous by-products including pyrolysis products of the reaction by-products thermally decomposed by the reactor heating means. Trisilylamine synthesis apparatus.

2. 2. The apparatus for synthesizing trisilylamine according to claim 1, wherein the reactor heating means comprises an inert gas supply pipe for supplying the inert gas to the reaction space of the reactor, and an inert gas supply pipe heating means for heating the inert gas supply pipe.

3. 3. The apparatus for synthesizing trisilylamine according to claim 2, wherein the inert gas is nitrogen.

4. 2. The apparatus for synthesizing trisilylamine according to claim 1, further comprising a scrubber connected to an exhaust pipe for the gaseous by-products to treat the gaseous by-products.

5. 2. The apparatus for synthesizing trisilylamine according to claim 1, further comprising: a condenser connected to the trisilylamine discharge pipe for condensing gaseous trisilylamine; and a trisilylamine collection container for collecting condensed trisilylamine.

6. 2. The apparatus for synthesizing trisilylamine according to claim 1, wherein the reactor has a plurality of reaction vessels connected in parallel to sources of reaction starting materials and capable of operating simultaneously or alternately.

7. The reactor comprises a first reaction vessel and a second reaction vessel; 7. The apparatus for synthesizing trisilylamine according to claim 6, wherein the reaction space of at least the second reaction vessel is heated to a temperature equal to or higher than the decomposition temperature while the reaction is carried out in the first reaction vessel.

8. 2. The apparatus for synthesizing trisilylamine according to claim 1, wherein the supply pipes for the reaction starting materials include a supply pipe for monochlorosilane and a supply pipe for ammonia, and the supply pipe for monochlorosilane and the supply pipe for ammonia are each independently connected to the reactor.

9. 2. The apparatus for synthesizing trisilylamine according to claim 1, further comprising: a collection container for solid reaction by-products connected to the reactor and configured to collect solid reaction by-products; and a gate valve configured to open and close the collection container for solid reaction by-products and the reactor.

10. 2. The apparatus for synthesizing trisilylamine according to claim 1, wherein the reactor is a batch reactor.

11. 2. The apparatus for synthesizing trisilylamine according to claim 1, wherein the reactor is a continuous reactor.

12. A reaction starting material flow step of flowing the reaction starting material into a reactor; a reaction step in which the input reaction starting material is reacted to produce trisilylamine and a reaction by-product; a step of discharging trisilylamine from the reactor; a step of thermally decomposing the reaction by-products in the reactor after the step of discharging the trisilylamine; a gaseous by-product discharge step of discharging the gaseous by-product obtained in the pyrolysis step of the reaction by-product from the reactor; Equipped with The temperature in the reactor during the reaction step is maintained at a temperature lower than the decomposition temperature of the reaction by-products; The step of thermally decomposing the reaction by-products includes a step of heating the reaction space of the reactor to a temperature equal to or higher than the decomposition temperature of the reaction by-products. Method for synthesizing trisilylamine.

13. 13. The method for synthesizing trisilylamine according to claim 12, wherein the step of thermally decomposing the reaction by-products comprises the step of introducing into the reactor an inert gas heated to a temperature equal to or higher than the decomposition temperature of the reaction by-products.

14. 14. The method for synthesizing trisilylamine according to claim 13, wherein the inert gas comprises nitrogen.

15. 14. The method for synthesizing trisilylamine according to claim 13, further comprising the step of treating the vented gaseous by-products.

16. 16. The method for synthesizing trisilylamine according to claim 15, wherein the treating step includes a step of removing the gaseous by-products with a scrubber.

17. 14. The method for synthesizing trisilylamine of claim 13, wherein during the reacting step, the reactor is maintained at a temperature below the boiling point of trisilylamine.

18. 18. The method for synthesizing trisilylamine according to claim 17, further comprising the step of heating the reaction space of the reactor to a temperature equal to or higher than the boiling point of trisilylamine after the end of the reaction step and before the step of discharging the trisilylamine.

19. 18. The method for synthesizing trisilylamine according to claim 17, wherein the reacting step is carried out batchwise.

20. 14. The method for synthesizing trisilylamine according to claim 13, wherein during the reacting step, the reactor is maintained at a temperature equal to or greater than the boiling point of trisilylamine.

21. 21. The method for synthesizing trisilylamine according to claim 20, wherein the reaction step is carried out in a continuous or semi-continuous manner.

22. 21. The method for synthesizing trisilylamine according to claim 17 or claim 20, further comprising the step of condensing and collecting the gaseous trisilylamine.

23. 13. The method for synthesizing trisilylamine according to claim 12, further comprising the step of discharging from the reactor any solid reaction by-products that are not pyrolyzed in the pyrolysis step and that have accumulated in the reactor.

24. 13. The method for synthesizing trisilylamine of claim 12, wherein the reaction starting materials include monochlorosilane and ammonia, and the reaction by-products include ammonium chloride.

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