JP5579634B2 - Reactor for producing polycrystalline silicon and method for producing polycrystalline silicon - Google Patents

Description

  The present invention relates to a technique for producing polycrystalline silicon, and more particularly to a technique for effectively suppressing metal contamination and shape abnormality due to metal chloride and silicon powder generated during a precipitation reaction.

  Polycrystalline silicon is used as a raw material for a single crystal silicon substrate for manufacturing semiconductor devices and a substrate for manufacturing solar cells. A Siemens method is known as a method for producing polycrystalline silicon. The Siemens method is a method in which a source gas containing chlorosilane is brought into contact with a heated silicon core wire, and thereby polycrystalline silicon is vapor-phase grown on the surface of the silicon core wire by a CVD method to obtain a silicon rod.

  When the polycrystalline silicon is vapor-phase grown by the Siemens method, two silicon core wires in the vertical direction and one horizontal direction are assembled in a torii type in the reactor of the vapor phase growth apparatus. Then, both ends of the torii type silicon core wire are fixed to a pair of metal electrodes disposed on the reactor bottom plate via a pair of core wire holders. A raw material gas supply port for causing a reaction and a reaction exhaust gas exhaust port are also disposed on the bottom plate. Such a configuration is disclosed in, for example, Japanese Patent Publication No. 37-18861 (Patent Document 1).

  Generally, dozens of torii type silicon core wires fixed to a pair of metal electrodes arranged on a bottom plate are provided in a reaction furnace and arranged in a multi-ring manner. The bottom plate is also provided with a suitable number of source gas supply nozzles and reaction gas exhaust ports, which are arranged to optimize the gas flow in the furnace. Such a configuration of the bottom plate is disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-241120 (Patent Document 2), Japanese Patent Application Laid-Open No. 2006-206387 (Patent Document 3), and Japanese Patent Application Laid-Open No. 2009-107886 (Patent Document 4). There are also mentioned techniques for improving the shape of the polycrystalline silicon rod in the horizontal cross-sectional direction and suppressing the occurrence of unevenness on the surface.

  In order to deposit polycrystalline silicon by the Siemens method, a current is passed through the silicon core wire, the silicon core wire is heated to a temperature range of 900 ° C. or higher and 1200 ° C. or lower, and a source gas (for example, a mixed gas of trichlorosilane and hydrogen) is used. Supply into the reactor. Polycrystalline silicon is vapor-grown (deposited) on the silicon core wire by decomposition of the raw material gas, and a polycrystalline silicon rod having a desired diameter is formed in an inverted U shape. Usually, the process from the setting of the silicon core wire in the reactor to the removal of the polycrystalline silicon rod is carried out in a batch manner.

  By the way, when chlorosilane is used as a raw material gas, it is known that a metal which is a structural material of a reaction furnace reacts with a chlorine content in chlorosilane, and a metal chloride is generated in the reaction furnace. Although the reactor is cleaned after the end of one batch, the metal chloride once adhered in the reactor is not completely removed even in this cleaning, and remains in the reactor as a trace amount of metal chloride. .

  Metal chlorides generally have a lower sublimation temperature and are more easily gasified than pure metals. For this reason, if the furnace gas temperature becomes a certain temperature or more during the precipitation reaction of polycrystalline silicon, the residual metal chloride in the furnace is sublimated and gasified. Since this gasified metal chloride is taken into the polycrystalline silicon, it causes heavy metal contamination of the polycrystalline silicon. In particular, when the in-furnace gas temperature is 350 ° C. or higher, the above phenomenon becomes remarkable.

  Further, when the furnace gas temperature becomes a certain temperature or higher, powdery silicon is generated by the thermal decomposition reaction of silane gas. When this silicon powder floats in the reactor and comes into contact with the inner wall or bottom plate of the reactor, heavy metals adhere to it, and if it adheres to the surface of the polycrystalline silicon rod, the polycrystalline silicon rod is contaminated with heavy metal or the surface is contaminated. The quality of the polycrystalline silicon is deteriorated by generating protrusions.

  Furthermore, if the precipitation reaction is continued while maintaining the surface temperature of the polycrystalline silicon rod at a high temperature above a certain temperature, the following disadvantages will occur due to the diameter of the polycrystalline silicon rod becoming larger in the latter stage of the precipitation reaction step. Also occurs. In order to improve the productivity of polycrystalline silicon, it is desirable to increase the reaction rate by increasing the surface temperature of the polycrystalline silicon rod during the precipitation reaction as much as possible. In general, the surface temperature of the polycrystalline silicon rod during the precipitation reaction is about 900 to 1200 ° C. If the precipitation reaction is continued at such a relatively high temperature, the polycrystalline silicon rod is formed later in the precipitation reaction step. The diameter of will increase. When the surface area at this temperature increases, convective heat transfer and radiant heat transfer in the furnace become more prominent, which creates a gas stagnation area and a local temperature rise area in the furnace, which promotes the generation of silicon powder. Result. Conversely, if the surface temperature of the polycrystalline silicon rod during the precipitation reaction is lowered in order to suppress heavy metal contamination caused by metal chloride and the generation of silicon powder, the precipitation rate will decrease and the productivity will also decrease. End up.

Japanese Patent Publication No. 37-18861 JP 2002-241120 A JP 2006-206387 A JP 2009-107886 A

  As described above, in the conventional polycrystalline silicon manufacturing technology, when trying to improve the productivity by increasing the deposition rate of polycrystalline silicon, the quality deteriorates due to heavy metal contamination caused by metal chloride and generation of silicon powder. On the other hand, there is a problem that productivity of polycrystalline silicon is inevitably lowered when it is attempted to suppress heavy metal contamination caused by metal chloride and generation of silicon powder.

  The present inventors have made several attempts so far to suppress heavy metal contamination caused by metal chloride and generation of silicon powder. Specifically, (i) a method of lowering the gas temperature in the furnace by lowering the temperature of the cooling water for cooling the inner wall of the furnace, and (ii) the supply amount of the reaction gas as the diameter of the polycrystalline silicon rod increases. A method of keeping the supply amount of the raw material gas per unit surface area of the polycrystalline silicon rod constant by increasing the amount of (ii) a method of precipitating by lowering the reaction temperature, and (iv) a method of lowering the silane concentration in the raw material gas. .

  However, the above methods (i) and (ii) require a new function to be added to the production facility, leading to an increase in the production cost of polycrystalline silicon. In addition, the methods (iii) and (iv) also cause an increase in manufacturing cost due to a decrease in the deposition rate of polycrystalline silicon.

  The present invention has been made in view of the above-described problems, and the object of the present invention is to suppress the occurrence of heavy metal contamination and silicon powder caused by metal chlorides without reducing productivity. To provide technology.

In order to solve the above-described problems, a reactor for producing polycrystalline silicon according to the present invention comprises:
A reactor for producing polycrystalline silicon by a Siemens method, wherein the bottom plate of the reactor includes at least a pair of core wire holders for holding a silicon core wire, and a plurality of nozzles for supplying a source gas, A part of the gas blowing part of the raw material gas supply nozzle is provided at a predetermined height (H> 0) with respect to the upper end of the core wire holder, and the remaining part of the raw material gas supply nozzle has the gas blowing part as the core wire holder. It is characterized by being provided below the upper end of the.

  Further, a reactor for producing polycrystalline silicon according to another aspect of the present invention is a reactor for producing polycrystalline silicon by a Siemens method, and at least a pair of silicon core wires are held on the bottom plate of the reactor. The core wire holder and a plurality of nozzles for supplying the source gas, the gas outlets of the plurality of source gas supply nozzles are provided below the upper end of the core wire holder, and the plurality of source gas supplies It has a control part which adjusts some gas blowing parts of a nozzle to predetermined height (H> 0) on the basis of the upper end of the core wire holder.

  For example, the predetermined height of the gas blowing portion is a value exceeding 1/3 of the vertical length of the silicon core wire, or a value exceeding 50 cm based on the upper end of the core wire holder.

  The reactor for producing polycrystalline silicon according to the present invention is provided with a raw material gas supply system for supplying gases having different trichlorosilane / hydrogen ratios to the gas blowing portion at the predetermined height and the other gas blowing portions. It is good.

  Preferably, the source gas supply system supplies a gas having a hydrogen ratio larger than that of the other gas blowing section to the gas blowing section at the predetermined height.

  More preferably, the source gas supply system supplies the gas having a large hydrogen ratio at a temperature of 100 ° C. or lower.

  The method for producing polycrystalline silicon according to the present invention uses the above-described reactor for producing polycrystalline silicon according to the present invention, and deposits polycrystalline silicon by setting the predetermined height so that the furnace temperature is uniform. .

  According to the raw material gas supply nozzle provided in the present invention, a local increase in the furnace gas temperature can be suppressed. Moreover, even if the diameter of the silicon rod is increased, the downflow from the upper part to the lower part in the furnace can be promoted.

  For this reason, not only the average gas temperature in a reaction furnace falls, but the gas residence in a furnace is suppressed and the production | generation of the silicon powder by thermal decomposition can be suppressed.

  Thus, the present invention provides a technique for producing polycrystalline silicon that can suppress heavy metal contamination caused by metal chloride and generation of silicon powder without reducing productivity.

It is a schematic sectional drawing which shows the structural example of the reaction furnace for polycrystalline silicon manufacture of this invention. It is a schematic sectional drawing which shows the other structural example of the reactor for polycrystalline silicon manufacture of this invention. It is a schematic sectional drawing which shows the other structural example of the reactor for polycrystalline silicon manufacture of this invention. It is a schematic sectional drawing which shows the structural example of the conventional reactor for polycrystalline silicon manufacture.

  Embodiments of the present invention will be described below with reference to the drawings.

  1 to 3 are schematic sectional views showing an example of the structure of a reactor for producing polycrystalline silicon according to the present invention. FIG. 4 is a diagram showing a conventional polycrystalline silicon production in which a raw material gas is supplied only by a nozzle 3 described later. It is a schematic sectional drawing which shows the structural example of the reactor for water. In these drawings, the same reference numerals are assigned to the same components.

  The reactor 100 is sealed inside by a bottom plate 1 and a bell jar 10, and a silicon core wire 5 assembled in a torii form is disposed in the sealed space, and polycrystalline silicon 6 is deposited on the surface of the silicon core wire 5. A silicon rod is obtained. On the bottom plate 1, a core wire holder 8, a metal electrode 2, an insulator 7, and a bell jar 10 for controlling the surface temperature of the core wire to 900 to 1200 ° C. by applying an alternating current or a direct current from both ends of the torii type silicon core wire 5. Nozzles 3 and 3a for supplying the raw material gas inside and a reaction exhaust gas port 4 for discharging the reacted gas to the outside of the bell jar 10 are installed. Hydrogen gas and silicon source gas (generally trichlorosilane gas) are supplied from the source gas supply nozzles 3 and 3a. In the figure, only one pair of silicon core wires 5 is shown, but a plurality of pairs are generally arranged.

  From the gas outlets of the nozzles 3, 3 a, the raw material gas whose flow rate and flow rate are controlled is supplied by the raw material gas supply system 20. 1 and FIG. 2 is provided with a nozzle 3 having a blower outlet above the upper surface of the bottom plate 1 and a blower outlet at a predetermined height with respect to the upper end of the core wire holder 8. The nozzle 3a is provided. The configuration shown in FIGS. 1 and 2 is different only in the arrangement position of the source gas supply nozzle 3a.

  Since the nozzles 3 and 3a are installed in a high-temperature reactor, the material is preferably ceramics that does not cause heavy metal contamination even at high temperatures, such as silicon nitride or carbon. In particular, silicon nitride containing no carbon source is a suitable nozzle material.

  In addition to the nozzle 3 having an outlet near the upper surface of the bottom plate 1 as in the reaction furnace 100 of the embodiment shown in FIG. 3, the control unit 9 controls the upper end of the core wire holder 8 to a predetermined height. It is good also as a structure provided with the nozzle 3a which can adjust the position of a blower outlet. In these drawings, three nozzles are shown, but the number of nozzles is not limited to three. In FIG. 3, the source gas supply system 20 is not shown.

  That is, the first aspect of the reactor for producing polycrystalline silicon according to the present invention is a reactor 100 for producing polycrystalline silicon by the Siemens method, and a silicon core wire is attached to the bottom plate 1 of the reactor 100. At least one pair of core wire holders 8 for holding 5 and at least one nozzle 3a for supplying source gas are provided, and the gas blowing portion of the nozzle 3a has a predetermined height with respect to the upper end of the core wire holder 8. It has the structure provided.

  The second aspect of the reactor for producing polycrystalline silicon according to the present invention is a reactor 100 for producing polycrystalline silicon by the Siemens method, and a silicon core wire is attached to the bottom plate 1 of the reactor 100. At least one pair of core wire holders 8 for holding 5 and a nozzle 3a for supplying a raw material gas are provided, and the gas blowing portion of the nozzle 3a is set at a predetermined height with respect to the upper end of the core wire holder 8. It has the structure provided with the control part 9 adjusted to.

  The “predetermined height” (H) of the gas blowing portion of the source gas supply nozzle 3a is always a positive value (H> 0) in order to obtain a function described later. For example, the length of the silicon core wire 5 in the vertical direction It is a value exceeding 1/3 of (height). The “predetermined height” is a value exceeding 50 cm, for example.

  That is, the reactor for producing polycrystalline silicon according to the present invention is different from the conventional type in that the gas outlet is provided with the nozzle 3a which is at the “predetermined height” or whose position is adjusted. In the present invention, the reason why the gas blowing portion of the nozzle 3a is set to the “predetermined height” is due to the examination of the experimental results conducted by the present inventors. For example, according to experiments conducted by the present inventors, in the case of a general reaction furnace, the region close to the average gas temperature in the furnace is at a height exceeding 50 cm with respect to the upper end of the core wire holder 8.

  As already described, when the polycrystalline silicon 6 is deposited on the silicon core wire 5 and the diameter of the silicon rods is increased, the radiation between the silicon rods becomes remarkable. The gas temperature in the reaction furnace increases due to radiation, and the metal chloride generated in the furnace is sublimated and gasified. In particular, in a reactor designed with a final diameter of about 120 mm as the final diameter of the silicon rod, the average gas temperature in the furnace at the end of the reaction process when the diameter of the silicon rod exceeds about 80 mm is 350 ° C. or more. Therefore, the gasified metal chloride causes the polycrystalline silicon to be contaminated with heavy metals.

  In addition, if the diameter of the silicon rod becomes larger than about 80 mm in the reaction furnace, the flow of the upper gas of the reaction furnace is deteriorated, and the tendency of generating a gas retention portion is increased. Further, since radiation between the silicon rods becomes remarkable, the temperature of the gas staying between the silicon rods is partially increased, and the thermal decomposition reaction in the region is actively promoted to generate silicon powder.

  According to the study by the present inventors, the generation of silicon powder becomes significant as the chlorosilane concentration in the feed gas increases. When trichlorosilane is used as the source gas, silicon powder is generated when the concentration of trichlorosilane in the feed gas becomes 25% or more.

  In the present invention, by providing the nozzle 3a for supplying the raw material gas from the above-mentioned “predetermined height”, the region where the gas temperature is likely to rise such as the region near the center in the furnace or the upper region. In addition, by supplying relatively low temperature gas efficiently, the temperature distribution in the furnace is made uniform and the occurrence of heavy metal contamination and silicon powder caused by metal chlorides is suppressed without reducing productivity. To do.

  For example, after starting the precipitation reaction of polycrystalline silicon, when the diameter of the silicon rod exceeds 80 mm, the gas composition supplied from the nozzle 3a is switched, and the gas supplied from the other nozzle 3 is trichlorosilane / hydrogen. A relatively low temperature gas having a different ratio is supplied from the nozzle 3a. According to the study by the present inventors, since the gas temperature is likely to be high in the furnace region above the “predetermined height” and the gas is liable to be retained, heavy metal contamination due to metal chloride and generation of silicon powder are caused. However, the temperature distribution in the furnace is made uniform by efficiently cooling the region.

  Here, the relatively low temperature gas supplied from the nozzle 3a is preferably a gas having a larger hydrogen ratio than the gas supplied from the nozzle 3 in order to suppress the supply of the silicon source, and only hydrogen gas. It may be. The temperature of the gas having a large hydrogen ratio is set to 100 ° C. or less, for example.

  When such gas supply is performed, the silicon concentration in the reaction gas in the region where the gas temperature is high in the furnace is relatively lowered, and the generation of silicon powder due to the thermal decomposition reaction is suppressed.

  It is preferable to switch the trichlorosilane concentration in the gas supplied from the other nozzles 3 in accordance with the switching of the gas composition supplied from the nozzle 3a. This is because the silicon source supplied into the furnace from the nozzle 3 a is suppressed by switching the gas composition, and therefore, the silicon source that compensates for this is supplied from the other nozzle 3.

  When such a raw material gas is supplied, the average gas temperature in the furnace is lowered, and the gasification of the metal chloride is suppressed. Even if the diameter of the silicon rod is large, the gas sent to the upper region of the furnace promotes the downflow from the upper part of the furnace to the lower part, and the gas retention in the furnace is eliminated, resulting in local gas Temperature rise is less likely to occur, and generation of silicon powder is suppressed.

  The gas supply from the nozzle 3a as described above may be performed from the beginning of the precipitation reaction. However, if the supply of trichlorosilane to the upper region in the furnace is suppressed while the diameter of the silicon rod is small, the polycrystalline silicon is precipitated. The speed is reduced and productivity is worsened.

  The results of Examples 1 and 2 and Comparative Examples 1 and 2 are shown below. In the production of these polycrystalline silicon, in Examples 1 and 2, a reactor having only one nozzle 3a at the center of the bottom plate as shown in FIG. 1 was used, and the gas blowing part of the nozzle 3a was a core wire. The holder was positioned at a height of 80 cm with respect to the upper end of the holder. On the other hand, in Comparative Examples 1 and 2, as shown in FIG. 4, a reactor provided with only the nozzle 3 was used.

  In Example 1, a raw material gas having a trichlorosilane concentration of 25% and a mixed gas of trichlorosilane gas and hydrogen gas (60 ° C.) at the initial stage of the precipitation reaction is supplied from the nozzle 3a. When it reached 80 mm, the supply was switched to supply of only hydrogen gas (60 ° C.), and an amount of hydrogen gas corresponding to 25% of the total hydrogen gas supplied into the furnace was supplied from the nozzle 3a.

  In Example 2, a raw material gas having a trichlorosilane concentration of 25% and a mixed gas of trichlorosilane gas and hydrogen gas (60 ° C.) was supplied from the beginning to the end of the precipitation reaction.

  On the other hand, the gas supplied from the nozzle 3 in Comparative Example 1 and Comparative Example 2 is a mixed gas of trichlorosilane gas and hydrogen gas (60 ° C.), respectively, and is a raw material gas having a trichlorosilane concentration of 15% and 25%. .

  In these Examples 1 and 2 and Comparative Examples 1 and 2, the reaction temperature is 1100 ° C., the final diameter of polycrystalline silicon is 120 mmφ, and the core wire length is 180 cm.

  The results are shown in Table 1. The “heavy metal concentration” in the table is a value obtained by measuring the total of six kinds of metals of Na, Cr, Fe, Ni, Cu, and Zn by ICP-MS. “In-furnace powder generation amount” and “surface protrusion generation” are the results of visually confirming the amount of silicon powder present on the bottom plate and the surface of the polycrystalline silicon rod after the reaction batch, respectively.

  In Comparative Example 2, both generation of powder in the furnace and generation of surface protrusions are recognized, and the heavy metal in the polycrystalline silicon is also at a high value. In Comparative Example 1, neither generation of powder in the furnace nor generation of surface protrusions is observed, but it cannot be said that the heavy metal in the polycrystalline silicon is sufficiently low.

  On the other hand, in both Examples 1 and 2, in addition to the fact that neither furnace powder generation nor surface protrusion generation is observed, the heavy metal in the polycrystalline silicon has a sufficiently low value. Yes.

  As described above, according to the reactor according to the present invention, even when the diameter of polycrystalline silicon is increased, the gas temperature in the furnace is made uniform, which is higher than that of the conventional structure. Generation of heavy metal contamination and silicon powder due to sublimation of objects is effectively suppressed.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing technique of the polycrystalline silicon which can suppress generation | occurrence | production of the heavy metal contamination resulting from a metal chloride and silicon powder, without reducing productivity is provided.

DESCRIPTION OF SYMBOLS 1 Bottom plate 2 Metal electrode 3, 3a Raw material gas supply nozzle 4 Reaction exhaust gas port 5 Silicon core wire 6 Polycrystalline silicon 7 Insulator 8 Core wire holder 9 Control part 10 of nozzle outlet position Berja 20 Raw material gas supply system 100 Reactor

Claims (8)

A reactor for producing polycrystalline silicon by the Siemens method,
The bottom plate of the reactor includes at least a pair of core wire holders for holding a silicon core wire, and a plurality of nozzles for supplying a raw material gas,
A part of the plurality of source gas supply nozzles is provided at a predetermined height (H> 0) with respect to the upper end of the core wire holder, and the remaining source gas supply nozzles have the gas outlets A reactor for producing polycrystalline silicon, wherein the reactor is provided below the upper end of the core wire holder. A reactor for producing polycrystalline silicon by the Siemens method,
The bottom plate of the reactor includes at least a pair of core wire holders for holding a silicon core wire, and a plurality of nozzles for supplying a raw material gas,
Gas outlets of the plurality of source gas supply nozzles are provided below the upper end of the core wire holder, and
A polycrystalline silicon production comprising a control unit for adjusting a part of the plurality of source gas supply nozzles to a predetermined height (H> 0) with respect to an upper end of the core wire holder Reactor.   3. The reactor for producing polycrystalline silicon according to claim 1, wherein the predetermined height of the gas blowing portion is a value exceeding 1/3 of the vertical length of the silicon core wire.   The reactor for producing polycrystalline silicon according to claim 1 or 2, wherein the predetermined height of the gas blowing section is a value exceeding 50 cm.   5. The raw material gas supply system for supplying a gas having a different trichlorosilane / hydrogen ratio to the gas blowing portion at the predetermined height and the other gas blowing portions, respectively. 6. Reactor for producing polycrystalline silicon.   6. The reactor for producing polycrystalline silicon according to claim 5, wherein the source gas supply system supplies a gas having a hydrogen ratio larger than that of the other gas blowing section to the gas blowing section at the predetermined height.   The reactor for producing polycrystalline silicon according to claim 6, wherein the source gas supply system supplies the gas having a large hydrogen ratio at a temperature of 100 ° C. or less.   A polycrystalline for producing polycrystalline silicon using the reactor for producing polycrystalline silicon according to any one of claims 1 to 7, wherein the predetermined height is set so that the temperature in the furnace becomes uniform. Silicon manufacturing method.

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