Trichlorosilane purification system and method for producing polycrystalline silicon

Abstract

There is provided trichlorosilane purification technology in which it is unnecessary to discharge large amounts of chlorosilanes oat of the system in the production of high-purity trichlorosilane from a chlorosilane fraction containing hydrocarbons and in which the reaction control can also be easily performed. In the present invention, the step of converting hydrocarbons contained in a chlorosilane fraction into low-boiling materials by thermal decomposition has been provided in the purification system in order to easily separate the hydrocarbons. Thereby, the conversion of hydrocarbons into low-boiling materials by thermal decomposition and the separation are performed in the trichlorosilane purification cycle, and it is unnecessary to discharge large amounts of chlorosilanes out of the system. As a result, the trichlorosilane production efficiency is increased, and the problem of yield reduction of polycrystalline silicon does not arise either.

Claims

1. A trichlorosilane purification system for obtaining semiconductor-grade trichlorosilane from a chlorosilane fraction comprising hydrocarbons, the system comprising: a thermal decomposition reactor for thermally decomposing the hydrocarbons in the chlorosilane fraction to convert the hydrocarbons into materials having a lower boiling point than that of the hydrocarbons; and a distiller for separating trichlorosilane comprised in the chlorosilane fraction transferred from the thermal decomposition reactor from other components, wherein the thermal decomposition reactor can convert at least isopentane, methyltrichlorosilane, and methyldichlorosilane into low-boiling materials.

2. The trichlorosilane purification system according to claim 1, wherein the thermal decomposition reactor can control the pressure during the conversion of hydrocarbons into low-boiling materials in the range of 0.01 to 2 MPa.

3. The trichlorosilane purification system according to claim 1, wherein the thermal decomposition reactor can control the temperature during the conversion of hydrocarbons into low-boiling materials in the range of 300 to 1200 C.

4. The trichlorosilane purification system according to claim 1, wherein the content of iron in an inner wall material of the thermal decomposition reactor is 65% by weight or less.

5. The trichlorosilane purification system according to claim 4, wherein the content of iron in the inner wall material of the thermal decomposition reactor is 50% by weight or less.

6. The trichlorosilane purification system according to claim 1, wherein the purification system comprises a gas line for introducing tetrachlorosilane and hydrogen into the thermal decomposition reactor.

7. The trichlorosilane purification system according to claim 6, wherein the amount of hydrogen ([H.sub.2]) introduced into the thermal decomposition reactor from the gas line can be controlled so that the ratio ([H.sub.2]/[STC]) of the amount of hydrogen ([H.sub.2]) to the amount of tetrachlorosilane ([STC]) will be in the range of 1 to 6.

8. The trichlorosilane purification system according to claim 1, wherein the purification system further comprises: a hydrogenation reactor for reacting hydrogen with tetrachlorosilane in the presence of metallic silicon to obtain crude trichlorosilane; and a gas line for transferring the chlorosilanes comprising hydrocarbons converted into low-boiling materials to the hydrogenation reactor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A is a block diagram of an example of a system in which crude trichlorosilane is distilled and purified to produce high-purity trichlorosilane, and FIG. 1B is a block diagram of an example of a system in which a gas produced in the step of precipitating polycrystalline silicon is distilled and purified to separate high-purity trichlorosilane, and the resulting high-purity trichlorosilane is fed to the step of producing polycrystalline silicon again;

(2) FIG. 2 is a block diagram of an example of a system in which a gas fed from the step of producing crude trichlorosilane is purified, and the purified gas is used as a gas for producing polycrystalline silicon as high-purity trichlorosilane; and a gas discharged from the step of precipitating polycrystalline silicon is purified, and the purified gas is fed and used in the step of precipitating polycrystalline silicon again;

(3) FIG. 3 is a block diagram for describing an embodiment in which the step of producing crude trichlorosilane comprises at least one of a hydrogenation step and a chlorination step;

(4) FIG. 4 is a block diagram for describing an embodiment in which a chlorosilane fraction containing hydrocarbons separated by the purification of crude trichlorosilane is fed to a thermal decomposition step together with tetrachlorosilane and hydrogen, and the resulting chlorosilanes containing thermally-decomposed hydrocarbons are fed to a hydrogenation step in the step of producing crude trichlorosilane; and

(5) FIG. 5 is a block diagram for describing an embodiment in which tetrachlorosilane recovered after a polycrystalline silicon precipitation reaction is fed to a hydrogenation step through a thermal decomposition step.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) Hereinafter, the trichlorosilane purification system according to the present invention will be described with reference to drawings.

(7) Trichlorosilane (TCS) used for the production of polycrystalline silicon and the like is highly purified by distilling and purifying crude trichlorosilane obtained in a reaction accompanied by chlorination of metallic silicon, and the resulting high-purity trichlorosilane is fed to the step of producing polycrystalline silicon. Further, if high-purity trichlorosilane is separated by distilling and purifying a gas produced in the step of precipitating polycrystalline silicon, the high-purity trichlorosilane can be fed to the step of producing polycrystalline silicon again.

(8) However, hydrocarbons by-produced from carbon impurities contained in metallic silicon used as a raw material are incorporated into the crude trichiorosilane as described above. Further, hydrocarbons by-produced from carbon contained in reactor materials and the like are incorporated into a gas produced in the step of precipitating polycrystalline silicon. Among such hydrocarbons, hydrocarbons having about 5 carbon atoms such as isopentane have boiling points close to that of trichiorosilane which is the target, of purification, and the separation of these hydrocarbons from trichiorosilane is not easy. Particularly, the boiling point of isopentane is 27.7 C., which is extremely close to the boiling point of trichiorosilane of 31.8 C.

(9) Thus, these hydrocarbons contained in crude trichiorosilane and in a gas produced in the step of precipitating polycrystalline silicon are gradually concentrated in the trichiorosilane purification process, even if the amounts of these hydrocarbons are very small. As a result, the hydrocarbons will be a hindrance in the high-purity purification of trichiorosilane.

(10) In the present invention, hydrocarbons contained in chlorosilanes are converted to low-boiling materials by thermal decomposition to increase the boiling point difference with trichlorosilane. Thereby, the separation from trichlorosilane is made easy. Alkanes and alkenes each having 1-4 carbon atoms are obtained as a thermal decomposition product of hydrocarbons having 5 carbon atoms, and the boiling point of these thermal decomposition products are lower than that of trichlorosilane. The compound having the highest boiling point among these thermal decomposition products is cis-2-butene having 4 carbon atoms, and since the boiling point of cis-2-butene is 3.7 C., the boiling point difference (about 28 C.) between trichlorosilane and cis-2-butene is sufficiently large from the point of view of separation. Therefore, the present invention aims to convert hydrocarbons contained in chlorosilanes into low-boiling hydrocarbons having 4 or less carbon atoms by thermal decomposition. Thereby, the boiling point difference can be about 28 C. described above or more.

(11) Thus, the trichlorosilane purification system according to the present invention makes it possible to obtain high-purity trichlorosilane from a chlorosilane fraction containing hydrocarbons by providing a thermal decomposition reactor for thermally decomposing hydrocarbons in a chlorosilane fraction to convert the hydrocarbons into low-boiling materials and a distiller for separating trichlorosilane contained in the chlorosilane fraction transferred from the thermal decomposition reactor from other components.

(12) FIG. 1A is a block diagram of an example of a system in which crude trichlorosilane is distilled and purified to produce high-purity trichlorosilane, and FIG. 1B is a block diagram of an example of a system in which a gas produced in the step of precipitating polycrystalline silicon is distilled and purified to separate high-purity trichlorosilane and the resulting high-purity trichlorosilane is fed to the step of producing polycrystalline silicon again.

(13) Chlorosilanes containing hydrocarbons (for example, isopentane, methyltrichlorosilane, and methyldichlorosilane) are fed to the thermal decomposition step (thermal decomposition reactor), and the hydrocarbons are thermally decomposed in the reactor heated to 300 C. to 1200 C. and converted into low-boiling materials. Then, the chlorosilane fraction containing the hydrocarbons converted into low-boiling materials is transferred to the purification step (distiller), and trichlorosilane is separated from other components.

(14) As described above, hydrocarbons having boiling points close to that of trichiorosilane are easily separated from trichiorosilane since the hydrocarbons are converted into low-boiling materials by passing them through the thermal decomposition step, and a high-purity trichiorosilane will be easily formed.

(15) It is preferred that the thermal decomposition reactor used in the present invention can convert at least isopentane, methyltrichlorosilane, and methyldichlorosilane into low-boiling materials. That is because these hydrocarbons have boiling points close to that of trichiorosilane which is the target of purification, and separation of trichiorosilane from these hydrocarbons is not easy by a common technique.

(16) Further, since the thermal decomposition described above is performed, for example, in the pressure range of 0.01 to 2 MPa in the temperature range of in a 300 to 1200 C., it is preferred that the thermal decomposition reactor can control the pressure during the conversion of hydrocarbons into low-boiling materials in the range of 0.01 to 2 MPa.

(17) FIG. 2 is a block diagram of an example of a circulation system in which the steps shown in FIG. 1A and FIG. 1B are combined; a gas fed from the step of producing crude trichlorosilane is purified, and the purified gas is used as a gas for producing polycrystalline silicon as high-purity trichlorosilane; and a gas discharged from the step of precipitating polycrystalline silicon is purified, and the purified gas is fed and used in the step of precipitating polycrystalline silicon again.

(18) Note that the step of producing crude trichlorosilane shown in FIG. 2 may comprise only one of the hydrogenation step (hydrogenation reactor) and the chlorination step (chlorination reactor) or may comprise both of the steps, as in the embodiment shown in FIG. 3. In this case, in the hydrogenation step, metallic silicon, tetrachlorosilane, and hydrogen are fed; hydrogen is reacted with tetrachlorosilane in the presence of metallic silicon to obtain crude trichlorosilane containing trichlorosilane; and there is provided a gas line for transferring the crude trichlorosilane to the thermal decomposition reactor. Further, in the chlorination step, metallic silicon and hydrogen chloride are fed, and crude trichlorosilane containing trichlorosilane is obtained.

(19) Further, as in the embodiment shown in FIG. 4, there may be an embodiment in which a gas line for introducing tetrachlorosilane and hydrogen into a thermal decomposition reactor; a chlorosilane fraction containing hydrocarbons separated by the purification of crude trichlorosilane is fed to the thermal decomposition step together with tetrachlorosilane and hydrogen; and the resulting chlorosilanes containing thermally-decomposed hydrocarbons are fed to a hydrogenation step in the step of producing crude trichlorosilane. Note that, in this case, it is preferred that the amount of hydrogen ([H.sub.2]) introduced into the thermal decomposition reactor from the gas line described above can be controlled so that the ratio ([H.sub.2]/[STC]) of the amount of hydrogen ([H.sub.2]) to the amount of tetrachlorosilane ([STC]) will be in the range of 1 to 6.

(20) Furthermore, as in the embodiment shown in FIG. 5, there may be an embodiment in which tetrachlorosilane recovered after a polycrystalline silicon precipitation reaction is fed to a hydrogenation step through a thermal decomposition step. Note that, also in this case, it is preferred that the amount of hydrogen ([H.sub.2]) introduced into the thermal decomposition reactor from the gas line described above can be controlled so that the ratio ([H.sub.2]/[STC]) of the amount of hydrogen ([H.sub.2]) to the amount of tetrachlorosilane ([STC]) will be in the range of 1 to 6.

EXAMPLES

(21) Hereinafter, in Examples and Comparative Examples, there will be shown specific examples of converting isopentane in a test gas into low-boiling materials by thermal decomposition by the system of the present invention, the test gas being obtained by adding isopentane as a hydrocarbon to a mixed gas of tetrachlorosilane and hydrogen at a predetermined concentration.

Example 1

(22) A test gas (tetrachlorosilane:hydrogen=1:6) to which isopentane was added at a concentration of 5 ppm was passed through a quartz tube under a thermal decomposition temperature condition of 450 to 650 C., and the isopentane concentration in the discharged gas was measured by gas chromatography (FID-GC) using a flame ionization detector to determine the percent decomposition of isopentane.

Example 2

(23) A test gas (tetrachlorosilane:hydrogen=1:6) to which isopentane was added at a concentration of 5 ppm was passed through a quartz tube whose inner wall was covered with pure nickel under a thermal decomposition temperature condition of 450 to 650 C., and the isopentane concentration in the discharged gas was measured by FID-GC to determine the percent decomposition of isopentane.

Example 3

(24) A test gas (tetrachlorosilane:hydrogen=1:6) to which isopentane was added at a concentration of 5 ppm was passed through a quartz tube whose inner wall was covered with SUS316 under a thermal decomposition temperature condition of 450 to 650 C., and the isopentane concentration in the discharged gas was measured by FID-GC to determine the percent decomposition of isopentane.

Example 4

(25) A test gas (tetrachlorosilane:hydrogen=1:6) to which isopentane was added at a concentration of 5 ppm was passed through a quartz tube whose inner wall was covered with pure iron under a thermal decomposition temperature condition of 450 to 650 C., and the isopentane concentration in the discharged gas was measured by FID-GC to determine the percent decomposition of isopentane.

Comparative Example 1

(26) A test gas (tetrachlorosilane:hydrogen=1:6) to which isopentane was added at a concentration of 5 ppm was passed through a quartz tube under a thermal decomposition temperature of room temperature, and the isopentane concentration in the discharged gas was measured by FD-GC to determine the percent decomposition of isopentane.

Comparative Example 2

(27) A test gas (tetrachlorosilane:hydrogen=1:6) to which isopentane was added at a concentration of 5 ppm was passed through a quartz tube whose inner wall was covered with SUS316 under a thermal decomposition temperature of room temperature, and the isopentane concentration in the discharged gas was measured by FID-GC to determine the percent decomposition of isopentane.

(28) The results of Examples 1 to 4 and Comparative Examples 1 to 2 were summarized in Table 1.

(29) TABLE-US-00001 TABLE 1 Percent decomposition of i-C.sub.5H.sub.12 at each temperature (%) Reactor Room inner wall temper- material ature 450 C. 530 C. 600 C. 650 C. Example 1 Quartz 68 82 85 91 Example 2 Nickel 66 80 84 90 Example 3 SUS316 47 68 72 90 Example 4 Iron 43 59 73 91 Comparative Quartz 0 Example 1 Comparative SUS316 0 Example 2

(30) According to the results shown in Table 1, it can be verified that the thermal decomposition of isopentane in chlorosilanes is accelerated with the increase of temperature. Further, it can be verified that the thermal decomposition is easily accelerated with the decrease of iron content in the material of the reactor inner wall surface. Since iron content in SUS316 is about 65% by weight or less, the results shown in Table 1 at least show that the improvement effect of the percent decomposition of i-C.sub.5H.sub.12 is observed when iron content in the inner wall material of the thermal decomposition reactor is 65% by weight or less. Examples of such material include Incoloy (R) 800H, whose iron content is about 45% by weight. When the present inventors performed an experiment in a thermal decomposition reactor using Incoloy (R) 800H as the inner wall material, an improvement in the percent decomposition at 650 C. was observed compared with the results in a thermal decomposition reactor using pare iron or SUS316 as the inner wall material. Consequently, in practical use, it is conceivable that an inner wall material having an iron content of 65% or less will preferably be used, and more preferably, an inner wall material having an iron content of 50% by weight or less will be used.

(31) High-purity trichlorosilane is produced using the system described above, and polycrystalline silicon is produced using the high-purity trichlorosilane as a raw material.

INDUSTRIAL APPLICABILITY

(32) The present invention provides trichlorosilane purification technology in which it is unnecessary to discharge large amounts of chlorosilanes out of the system in the production of high-purity trichlorosilane from a chlorosilane fraction containing hydrocarbons and in which the reaction control can also be easily performed.