Patent Application
20110274926
This invention relates to a polycrystalline silicon rod obtained by depositing polycrystalline silicon, by the chemical vapor-phase deposition method, on a silicon core member arranged in a reaction vessel in an erected manner. More specifically, the invention relates to a polycrystalline silicon rod used for the recharging in the floating zone method (FZ method) or the Czochralski method (CZ method).
A variety of processes have heretofore been known for producing silicon that is used as a starting material of semiconductors or wafers for solar power generation, and some of them have already been put into practice on industrial scales. For instance, one of them is a process called Siemens process in which silicon core members are provided in a reaction chamber in a bell jar, are heated by flowing an electric current thereto to a temperature at which silicon deposits and in this state, a gas of a silane compound such as trichlorosilane (SiHCl3) or monosilane (SiH4) is fed into the reaction chamber so that silicon deposits on the silicon core members by the chemical vapor-phase deposition method. This process has a feature in that polycrystalline silicon of a high purity is obtained in the form of rods, and has been put into practice as the most general process (see patent documents 1, 2).
The silicon core members have a Π(pie)-shape, each of which comprising a pair of core wires held by the electrodes and erecting on the electrodes, and a bridging wire connecting the upper ends of the core wires together. The polycrystalline silicon rods deposited on the surfaces of the silicon core members have their corners gradually rounded as the silicon deposits and grows on the surfaces of the silicon core members and are, therefore, obtained in an inverse U-shape as a whole. The polycrystalline silicon rods of such a shape are taken out, usually, with some of their portions being cut off. Besides, the straight body portions deposited and grown on the core wires erected on the electrodes are cut away from the bridge portion connected to the upper ends thereof, and are used as a starting material of single crystal silicon. Further, the shape of the polycrystalline silicon that is used differs depending upon the method of single crystallization. For example, the Czochralski method (CZ method) uses the polycrystalline silicon of the shape of amass while the floating zone method (FZ method) uses it in the form of a rod. Moreover, the CZ method often conducts the recharging in which the polycrystalline silicon rods are directly melted in the silicon melt that is obtained by heating and melting the mass of polycrystalline silicon. The polycrystalline silicon rod used for the above object is, therefore, called polycrystalline silicon for recharging.
To use the polycrystalline silicon rods in the form of rods as in the above FZ method or the CZ method, it becomes necessary to transfer the silicon rods. However, the polycrystalline silicon rods obtained by the Siemens method, usually, have a large diameter with their straight body portions being nearly of a uniform cylindrical shape to maintain productivity of silicon. Namely, the polycrystalline silicon rods cannot be easily transferred in their own shape. As means for transferring the silicon rods, therefore, it has been attempted to form a small slit along the whole circumferences of the silicon rods by using an outer circumference cutter made of diamond, wind a wire or the like round the slit to hold the silicon rods, and lift up the silicon rods to transfer them.
To form the slit along the whole circumferences of the silicon rods, however, a special device is necessary for cutting the surfaces of the rods while rotating the rods thus accompanied by a problem of complex transfer operation.
It is, therefore, an object of the present invention to provide a polycrystalline silicon rod used for the recharging in the FZ method or the CZ method, the straight body portions of the obtained polycrystalline silicon rod assuming an easily transferable shape and excelling in transferability without the need of machining for transfer, as well as an apparatus for producing the same.
To solve the above problems, the present inventors have conducted a keen study and have discovered the fact that a diameter profile can be formed in the straight body portions of the silicon rod in the lengthwise direction thereof, i.e., a minimum diameter portion and a maximum diameter portion can be formed in the straight body portions in producing the polycrystalline silicon rod by the Siemens method.
It was, further, discovered that by utilizing the diameter profile formed in the straight body portions, the polycrystalline silicon rods of such a shape can be transferred by using a crane or the like by being simply hooked by a lifting hook without conducting any special machining for shaping, and the present invention was thus completed.
That is, according to the present invention, there is provided a polycrystalline silicon rod obtained by depositing and growing silicon, by the chemical vapor-phase deposition method, on a silicon core member which includes a pair of silicon core wires erected on electrodes and a bridging wire connecting upper ends of the silicon core wires, the polycrystalline silicon rod having straight body portions deposited and grown on the core wires and a bridging portion deposited on the bridging wire;
wherein the straight body portions of the silicon rod have a diameter profile in a lengthwise direction thereof, and a minimum diameter in the straight body portions is adjusted to be 60 to 95% of a maximum diameter thereof.
In the present invention, the straight body portions of the silicon rod do not necessarily assume a perfectly circular shape in plane cross section but often assume an oval shape or a shape close thereto. Therefore, if a maximum diameter in the plane cross section is denoted by A and a minimum diameter by B, then the diameter of the straight body portions of the silicon rod stands for a value calculated according to the following formula,
Diameter of the straight body portions=((A2+B2)/2)1/2.
In the polycrystalline silicon rod of the present invention, further, it is desired that:
(1) A recessed portion is formed in a portion of the straight body portions close to the electrodes, and the deepest portion in the recessed portion is a portion having the minimum diameter;
(2) The straight body portions and the bridging portion are cut apart in a manner of retaining the recessed portions so as to be used for the transfer; and
(3) The diameter of the straight body portion is gradually increasing from an upper side toward a lower side;
from the standpoint of easy transfer by using lifting hooks.
According to the present invention, further, there is provided an apparatus for producing a polycrystalline silicon rod, including a bottom plate holding a pair of electrodes; a Π-shaped silicon core member which comprises a pair of silicon core wires and a bridging wire connecting the upper ends of the silicon core wires, lower ends of the silicon core wires being held and erected on the pair of electrodes; and a bell jar covering the bottom plate so as to contain the silicon core member therein; wherein a gas feed pipe and a gas discharge pipe extends, through the bottom plate, into a reaction chamber formed by the bell jar and the bottom plate, characterized in that;
wherein a gas ejection nozzle is provided at an end portion of the gas feed pipe, and side ejection ports are formed in the gas ejection nozzle so as to eject gas in a transverse direction in parallel with an upper surface of the bottom plate.
In the above production apparatus, it is desired that (4) an upper ejection port is formed together with the side ejection ports in the gas ejection nozzle so as to eject the gas in the upper direction perpendicular to the upper surface of the bottom plate.
The polycrystalline silicon rod obtained according to the present invention has an inverse U-shape like those produced by the known processes and has a distinguished feature in that its straight body portions have a diameter profile in the lengthwise direction thereof or, in other words, have a minimum diameter portion and a maximum diameter portion. That is, if the straight body portions are cut apart from the bridge portion continuous thereto, then by utilizing the diameter profile, the polycrystalline silicon rod of the invention can be hanged down by using a lifting hook without the need of conducting any special machining for shaping, and can be transferred by using a crane or the like so as to be used for the recharging in the FZ method or the CZ method.
As described above, the polycrystalline silicon rod of the present invention has very excellent transportability in its straight body portions.
Further, the silicon rods of the above shape can be easily produced by using a production apparatus having specifically a structure in which the reaction gas is ejected in the transverse directions from the gas feed pipe that is extending into the reaction chamber in the bell jar. Namely, in the production apparatus of the above structure, the temperature becomes low at portions of the straight body portions of the silicon rod to where the reaction gas is blown. As a result, the deposition and growth of silicon are delayed at the portions to where the reaction gas is blown, and a recessed portion (the deepest portion becomes the minimum diameter portion) is formed in the above portions.
Immediately after the production, the polycrystalline silicon rod of the invention has an inverse U-shape with two straight body portions. The upper ends of the straight body portions are connected to each other via a bridge portion, and the lower ends thereof are connected to the electrodes arranged in the production apparatus that will be described later. This structure is the same as that of the conventional polycrystalline silicon rods. As described above, however, the present invention has a novel feature in regard to that a diameter profile is formed in the straight body portions.
Referring to
That is, in the present invention, a diameter profile is formed in the straight body portion 50 and, therefore, a minimum diameter portion and a maximum diameter portion are formed accompanying the diameter profile.
In
Referring to
That is, by utilizing the diameter profile, the straight body portion 50 that has been cut as described above can be transferred being hooked by using a lifting hook 60 of a crane as shown in
There is no particular limitation on the position L of the recessed portion 51 from the lower end portion of the straight body portion 50 in the shape of
Further, the straight body portion 50 having a diameter profile as shown in
There is no particular limitation on the lifting hook used for transferring the polycrystalline silicon rods of the present invention, and there can be used a known lifting hook that has been used for transferring the polycrystalline silicon rods. As the lifting hook, there can be concretely exemplified those lifting hooks having, as shown in
In the present invention, there is no particular limitation on the form of diameter profile of the straight body portion 50 described above. For example, the position of the minimum diameter portion 53 is not limited to the positions shown in
Contrary to the above, further, the shape of
Among the shapes of the polycrystalline silicon rods of the present invention described above, the shapes of
In the present invention, further, the diameter of the minimum diameter portion 53 should be in a range of 60 to 95% of the maximum diameter. That is, if the minimum diameter is larger than the above range, the difference between the minimum diameter and the maximum diameter becomes so small that the polycrystalline silicon rod cannot be easily hooked by the lifting hook 60 and the transferability decreases. If the minimum diameter is smaller than the above range, on the other hand, there is no change in the transferability of the polycrystalline silicon rod of
With the polycrystalline silicon rod of the shape of
Further, referring to
In this embodiment, the upper and lower portions of the recessed portion 51 are substantially of a cylindrical shape. The silicon rod, however, is obtained by a chemical reaction but not by a mechanical method. Therefore, the diameters thereof tend to fluctuate and, particularly, tend to greatly fluctuate toward the upper portion and the lower end portion of the silicon rod. Therefore, the width W of the recessed portion 51 can be accurately calculated desirably by, for example, drawing a sheathing line (tangential line) Y along the outer circumferential surface of the rod and calculating the width W of the recessed portion 51 with the sheathing line Y as a reference.
The polycrystalline silicon rod of the invention having the straight body portions 50 of the above-mentioned shape is produced by establishing a deposition rate profile for the diameter profile of the straight body portions 50 of the rod being produced. The method of production will now be described.
Referring to
In the past, the bridging portion was made of graphite. Nowadays, however, the bridging portion is chiefly made of silicon from the standpoint of obtaining polycrystalline silicon rods of a high purity.
Referring to
It is also allowable to cover the outer surface of the bell jar 5 or the bottom plate 3 with a cooling jacket (not shown) so that the inner wall of the reaction chamber A can be easily cooled.
A gas feed pipe 15 and gas discharge pipes 17 are inserted in the thus formed reaction chamber A via the bottom plate 3. A predetermined reaction gas is fed into the reaction chamber A through the gas feed pipe 15, and unreacted gas and gases of by-produced compounds are discharged from the reaction chamber A through the gas discharge pipes 17.
By using the above silicon production apparatus 1, the polycrystalline silicon rods are produced as described below.
That is, the temperature of the silicon core members 9 is elevated to be higher than a temperature at which silicon deposits by flowing an electric current into the silicon core members 9 via the electrodes 7. When the chlorosilane gas is a trichlorosilane as will be described later, the temperature at which silicon deposits is not lower than about 900° C. In order for the silicon to be quickly deposited on the silicon core members 9, however, the electric current is, usually, flown into the silicon core members 9 so as to maintain a temperature of about 1000 to about 1100° C.
Simultaneously with the start of flowing electric current to the silicon core members 9 or at a moment when the temperature of the silicon core members 9 has reached a temperature higher than the temperature at which the silicon deposits, the chlorosilane gas and a carrier gas are fed as the reaction gas into the reaction chamber A to form silicon. As the chlorosilane gas, use is made of such a chlorosilane gas as trichlorosilane (hereinafter abbreviated as TCS) or dichlorosilane alone, or a plurality of chlorosilane gases as a mixed gas. Usually, the TCS gas is preferably used. As the carrier gas, further, use is made, in many cases, of a reducing hydrogen gas.
The silicon (Si) formed by feeding the reaction gas deposits on the silicon core members 9. By continuing the reaction, the silicon grows on the silicon core members 9 and, finally, silicon rods X comprising the polycrystalline silicon are obtained.
In a stage when the polycrystalline silicon rods X of a predetermined thickness are obtained as described above, the reaction is terminated, flow of electric current to the silicon core members 9 is interrupted, the chlorosilane gas, hydrogen gas, by-produced silicon tetrachloride and hydrogen chloride are discharged from the reaction chamber A, the interior of the reaction chamber A is purged with a safe gas, the bell jar 5 is opened, and the polycrystalline silicon rods X are taken out.
The thus formed polycrystalline silicon rods X have their corners gradually rounded as they deposit on the silicon core members 9 and, therefore, have an inverse U-shape as a whole with two straight body portions 50 which are coupled at the lower ends thereof to the electrodes 7 and are connected at the upper ends thereof to a bridging portion 65 that is coupling the two straight body portions 50 together.
In the present invention, the straight body portions 50 formed as described above have a diameter profile in the lengthwise direction thereof and have a shape shown in, for example,
Though the mechanism of depositing silicon on the silicon core member and on the surfaces of the polycrystalline silicon rod has not been clarified yet, it is considered that the deposition varies depending upon the temperature on the surfaces of the polycrystalline silicon rod and the concentration of the reaction species formed from the chlorosilane present near the surfaces. Therefore, the rate of depositing silicon on the surfaces of the polycrystalline silicon rod can be adjusted by adjusting the feeding rate and flow rate of the chlorosilane gas fed into the reaction chamber A and the temperature of the chlorosilane gas.
To form the polycrystalline silicon rod X having straight body portions of the shape shown in
That is, the ejection nozzle 20 is provided with side ejection ports 20a for blowing the reaction gas in the transverse direction in parallel with the upper surface of the bottom plate 3, and the reaction gas is blown from the side ejection ports 20a directly onto portions where the recessed portions are to be formed in the straight body portions 50 of the polycrystalline silicon rod X (silicon core member 9 in the early stage of the reaction). That is, since the reaction gas fed from the gas feed pipe 15 has a temperature lower than the temperature on the surfaces of the polycrystalline silicon rod X, the surfaces of the polycrystalline silicon rod X are locally cooled by the blow of the reaction gas making it possible to greatly lower the rate of silicon deposition at the portions to where the reaction gas is blown and, therefore, to quickly form the recessed portions.
As will be understood from the above description, further, the ejection nozzle 20 (particularly, side ejection ports 20a) is located at a position higher than the upper ends of the electrodes 7, as a matter of course.
It is desired that the ejection nozzle 20 is provided at its upper end surface with an upper ejection port 20b for blowing the gas upward perpendicularly to the upper surface of the bottom plate 3 in addition to the side ejection ports 20a. This nozzle 20 enables the reaction gas to be blown in the transverse direction and upward simultaneously. Namely, with the structure which blows the reaction gas in the transverse direction only, the concentration of the reaction gas decreases in the upper part of the reaction chamber A and, as a result, the upper portion of the obtained silicon rod X assumes a popcorn shape which often becomes brittle. To avoid such an inconvenience, it is desired to employ the structure which blows the reaction gas upward, too.
In the embodiment of
There is no particular limitation on the materials of the gas feed pipe 15 and the nozzle 20 provided they do not contaminate the reaction gas that is fed; i.e., the materials may be, for example, silicon, silicon carbide, graphite or graphite of which the surfaces are coated with silicon.
Referring to
There is no particular limitation on the temperature of the reaction gas blown from the gas feed pipe 15 (nozzle 20) onto the silicon core members 9 under a condition where the polycrystalline silicon rods X of the shape of
Further, there is no particular limitation on the rate of feeding the reaction gas provided the surfaces of the polycrystalline silicon rods X can be locally cooled at portions where the recessed portions are to be formed and the rate of silicon deposition can be locally decreased. Namely, the rate of feeding the reaction gas may be suitably determined by taking into consideration the size of the bell jar 5, the number of the silicon core members 9 to be installed, the size of the polycrystalline silicon rods X to be formed, and the reaction time for depositing silicon. Generally, to maintain a predetermined rate of deposition, the flow rate of the reaction gas is, in many cases, increased accompanying the progress of the deposition reaction. For example, when the silicon of a maximum diameter of 110 to 120 mm is to be obtained and if the nozzle 20 is provided with the side ejection ports 20a of a diameter of 5 mm, the flow rate of the reaction gas blown from the side ejection ports 20a will be sufficient if it is about 10 to 30 m/s in terms of the linear velocity just before the end of the silicon deposition reaction (i.e., at the time when the polycrystalline silicon rods X have grown to a maximum diameter of 120 mm).
Upon adjusting the flow rate ratio (A/B) of the flow rate (A) of the reaction gas blown out from the side ejection ports 20a and the flow rate (B) of the reaction gas blown out from the upper ejection port 20b, further, the width W of the recessed portion 51 formed in the silicon rod X can be adjusted. That is, the larger the value of the flow rate ratio (A/B), the smaller the width W of the recessed portion 51, and the smaller the value of the flow rate ratio (A/B), the larger the width W of the recessed portion 51. Therefore, by utilizing this, i.e., by suitably varying the flow rate ratio (A/B), the width W of the recessed portion 51 can be increased or decreased.
Further, to form the polycrystalline silicon rods X having straight body portions of the shape shown in
That is, upon being fed into the reaction chamber A from the gas feed pipe 15, the reaction gas rises in the Z-direction in
In order to form the polycrystalline silicon rods X having straight body portions of the shape shown in
Further, from the standpoint of increasing the rate of silicon deposition near the surfaces of the lower end portions of the straight body portions 50 of the polycrystalline silicon rods X, it is desired that the reaction gas fed into the reaction chamber A has a high temperature. However, the reaction gas of too high temperatures is not desirable causing such troubles as contamination from the pipes, decreased purity of the product and deteriorating the pipes. Therefore, when the TCS is used as the chlorosilane gas, it is desired that the temperature of the reaction gas is set in a range of room temperature to 500° C. and, particularly, in a range of 200 to 350° C.
As for the shape of the gas feed port 15 for forming the polycrystalline silicon rods X having straight body portions of the shape of
As another means for forming the polycrystalline silicon rods X having straight body portions of the shape shown in
<Treatment after the Deposition Reaction>
The silicon rod X having a diameter profile thus formed in the straight body portions 50 thereof is separated away from the electrodes 7 in a customary manner by cutting the vicinities of the lower end portions of the straight body portions 50, is separated away from the bridging portion 65 by cutting the upper end portions of the straight body portions 50, and is lifted up by using the lifting hooks 60 that meet the shape of the straight body portions as shown in
The straight body portions cut from the polycrystalline silicon rod of the invention can be easily transferred without the need of machining for shaping, making it possible to greatly decrease the amount of work needed for the transfer.
The invention will now be more concretely described by way of Examples to which only, however, the invention is in no way limited.
Polycrystalline silicon rods were produced by using the production apparatus shown in
Here, the nozzle 20 having an upper ejection port and four side ejection ports was attached to an end portion of the gas feed pipe 15. The diameter of the upper ejection port (inner diameter at the end portion of the nozzle 20) was 20 mm and the diameters of the four side ejection ports were 5 mm each.
The end position of the nozzle 20 was set to a height of 400 mm from the bottom plate, and the positions of the four side ejection ports were set to a height of 300 mm each from the bottom plate 3.
Further, Π-shaped silicon core members 9 made of a fine rod of a square of 8 mm and a height of 2.2 m were erected on the electrodes 7 on the bottom plate 3.
The distance d between the gas feed pipe 15 (nozzle 20) and the silicon core members 9 was set to be 200 mm.
An electric current was flown to the silicon core members 9 via the electrodes 7. At a moment when the temperature has reached 1000° C. on the surfaces of the silicon core members 9, the reaction gas of TCS and hydrogen mixed in advance at a ratio of 1:5 and heated at 25° C. was fed from the gas feed pipe 15 through the nozzle 20.
Here, the amount of feeding the gas was so adjusted that the amount of the TCS gas that was fed was maintained to be 0.09±0.01 mols/cm2·h per the surface area of the silicon rod accompanying an increase in the diameter of the silicon rods deposited on the surfaces of the silicon core members 9, and the silicon deposition reaction was conducted until the straight body portions have gained a maximum diameter of 120 mm.
The reaction gas fed from the gas feed port 15 possessed a linear velocity of about 18 m/s just before the end of the reaction.
After the end of the reaction, the reaction gas was no longer fed, no electric current was supplied to the silicon core members 9, the straight body portions 50 were cut at the vicinities of the lower end portions thereof and were separated from the electrodes 7. Further, the straight body portions 50 were cut at the upper end portions thereof and were separated from the bridging portion 65, and the polycrystalline silicon rods of a length of 2 m were taken out; i.e., there were obtained the polycrystalline silicon rods having the recessed portion 51 formed near the lower ends of the straight body portions 50.
The minimum diameter portion was located 20 cm over the lower end of the polycrystalline silicon rod, and possessed a minimum diameter of 109 mm (91% of the maximum diameter). Further, the recessed portion was 150 mm wide.
The obtained polycrystalline silicon rods could be transferred without any problem being hooked at their recessed portions by using the lifting hooks.
Polycrystalline silicon rods were produced in the same manner as in Example 1 but setting the diameter of the upper ejection port of the nozzle 20 (inner diameter at the end portion of the nozzle 20) and the diameters of the four side ejection ports to be as shown in Table 1. The minimum diameters and the widths of the recessed portions were as shown in Table 1.
Silicon rods were produced by using the production apparatus shown in
Here, the inner diameter of the gas feed pipe 15 was set to be 40 mm, nozzle 20 was not provided, and the Π-shaped silicon core members 9 made of a fine rod of a square of 8 mm and a height of 2.2 m were erected on the electrodes 7.
Like in Example 1, an electric current was flown into the silicon core members 9 and at a moment when the temperature reached 1000° C. on the surfaces of the silicon core members 9, the reaction gas of TCS and hydrogen mixed in advance at a ratio of 1:5 and heated at 200° C. was fed from the gas feed pipe 15.
The amount of feeding the reaction gas was so adjusted that the amount of the TCS gas that was fed was maintained to be 0.04±0.005 mols/cm2·h per the surface area of the silicon rod accompanying an increase in the diameter of the silicon rod, and the silicon deposition reaction was conducted until a maximum diameter was 110 mm.
The reaction gas fed from the gas feed port 15 possessed a linear velocity of about 18 m/s just before the end of the reaction.
After the end of the reaction, the polycrystalline silicon rods of a length of 2 m were taken out in the same manner as in Example 1; i.e., there were obtained the polycrystalline silicon rods of the shape shown in
The minimum diameter portion was the upper end portion of the straight body portion 50, and possessed a minimum diameter of 88 mm (80% of the maximum diameter).
The obtained silicon rods could be transferred without any problem being so hooked by using the lifting hooks that the maximum diameter portions were on the upper side.
The silicon deposition reaction was conducted in the same manner as in Example 2 but so feeding the reaction gas that the amount of the TCS gas that was fed was 0.03±0.005 mols/cm2·h per the surface area of the silicon rod.
After the end of the reaction, the polycrystalline silicon rods of a length of 2 m were taken out in the same manner as in Example 2; i.e., there were obtained the polycrystalline silicon rods of the shape shown in
The minimum diameter portion was the upper end portion of the straight body portion 50, and possessed a minimum diameter of 79 mm (72% of the maximum diameter).
The obtained silicon rods could be transferred without any problem being so hooked by using the lifting hooks that the maximum diameter portions were on the upper side.
The silicon deposition reaction was conducted in the same manner as in Example 2 but so feeding the reaction gas that the amount of the TCS gas that was fed was 0.09±0.005 mols/cm2·h per the surface area of the silicon rod.
After the end of the reaction, the polycrystalline silicon rods of a length of 2 m were taken out in the same manner as in Example 2 to find that the minimum diameter was 108 mm (98% of the maximum diameter). The outer surfaces of the silicon rods had been tapered and tilted without any recessed portion.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2009-046498 | Feb 2009 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2010/052760 | 2/23/2010 | WO | 00 | 7/8/2011 |
