Fluidized bed reactor and method for producing granular polysilicon

Abstract

The fluidized bed process for preparing polysilicon by chemical vapor deposition is improved by positioning at least one Laval nozzle upstream from a gas inlet into the reactor.

Claims

1. In a fluidized bed reactor for producing granular polysilicon, having an inner reactor tube for a fluidized bed of granular polysilicon, the inner reactor tube having a reactor base with openings for entry of fluidizing gas and reaction gas, a heater for heating the fluidized bed of polysilicon, a silicon particle feed, an opening above the fluidized bed for removing offgas, and an opening in the inner reactor tube for removing a granular silicon product, the improvement comprising: at least two reaction gas openings in the reactor base, each of the at least two reaction gas openings fed by a Laval nozzle positioned outside of the reactor tube and upstream of the at least two reaction gas openings, the Laval nozzle suitable for expanding supercritically at least one mass stream of reaction gas, the at least two reaction gas openings comprising a gas distributor, a valve, a hole in the reactor base, or a nozzle, wherein the intake pressure of the Laval nozzle is controlled by gas quantity regulation.

2. The fluidized bed reactor of claim 1, wherein each reaction gas opening in the reactor base is fed by a respective Laval nozzle.

3. The fluidized bed reactor of claim 1, wherein two or more reaction gas openings in the reactor base form a reaction gas opening group, and the reaction gas opening group is commonly fed by a single Laval nozzle located upstream from the reaction gas opening group.

4. The fluidized bed reactor of claim 3, wherein two or more reaction gas opening groups are present, each group fed by a respective Laval nozzle.

5. The fluidized bed reactor of claim 1, wherein more than two reaction gas openings are present, each reaction gas opening fed by a respective Laval nozzle, and wherein two or more of the reaction gas openings together with their individual respective Laval nozzles constitute a reaction gas group, the Laval nozzles of which are in turn fed by a common Laval nozzle located upstream of the reaction gas openings and respective Laval nozzles.

6. The fluidized bed reactor of claim 1, wherein at least one opening in the reactor base for fluidizing gas is preceded upstream by a Laval nozzle.

7. The fluidized bed reactor of claim 2, wherein at least one opening in the reactor base for fluidizing gas is preceded upstream by a Laval nozzle.

8. The fluidized bed reactor of claim 3, wherein at least one opening in the reactor base for fluidizing gas is preceded upstream by a Laval nozzle.

9. A method for the production of granular polysilicon, comprising feeding a fluidizing gas and a mass stream of a silicon-containing gas into a fluidized bed of granular polysilicon contained within an inner reaction tube of a fluidized bed reactor while maintaining the temperature of the fluidized bed at between 850 C. and 1200 C. whereby silicon is deposited on granules in the fluidized bed in polycrystalline form, continuously adding silicon seed particles to the reactor, and continuously withdrawing a granular polysilicon product, wherein the silicon-containing reaction gas is fed to at least two reaction gas openings in a reactor base of the inner reaction tube, the at least two reaction gas openings preceded upstream by at least one Laval nozzle which supercritically expands the mass stream of silicon-containing reaction gas.

10. The method of claim 9, wherein the fluidizing gas comprises H.sub.2 and the silicon-containing reaction gas comprises trichlorosilane.

11. A method for the production of granular polysilicon, comprising feeding a fluidizing gas and a mass stream of a silicon-containing gas into a fluidized bed of granular polysilicon contained within an inner reaction tube of a fluidized bed reactor of claim 1, while maintaining the temperature of the fluidized bed at between 850 C. and 1200 C. whereby silicon is deposited on granules in the fluidized bed in polycrystalline form, continuously adding silicon seed particles to the reactor, and continuously withdrawing a granular polysilicon product, wherein the silicon-containing reaction gas is fed to at least two reaction gas openings in a reactor base of the inner reaction tube, the at least two reaction gas openings preceded upstream by at least one Laval nozzle which supercritically expands the mass stream of silicon-containing reaction gas.

12. A method for the production of granular polysilicon, comprising feeding a fluidizing gas and a mass stream of a silicon-containing gas into a fluidized bed of granular polysilicon contained within an inner reaction tube of a fluidized bed reactor of claim 2, while maintaining the temperature of the fluidized bed at between 850 C. and 1200 C. whereby silicon is deposited on granules in the fluidized bed in polycrystalline form, continuously adding silicon seed particles to the reactor, and continuously withdrawing a granular polysilicon product, wherein the silicon-containing reaction gas is fed to at least two reaction gas openings in a reactor base of the inner reaction tube, the at least two reaction gas openings preceded upstream by at least one Laval nozzle which supercritically expands the mass stream of silicon-containing reaction gas.

13. A method for the production of granular polysilicon, comprising feeding a fluidizing gas and a mass stream of a silicon-containing gas into a fluidized bed of granular polysilicon contained within an inner reaction tube of a fluidized bed reactor of claim 3, while maintaining the temperature of the fluidized bed at between 850 C. and 1200 C. whereby silicon is deposited on granules in the fluidized bed in polycrystalline form, continuously adding silicon seed particles to the reactor, and continuously withdrawing a granular polysilicon product, wherein the silicon-containing reaction gas is fed to at least two reaction gas openings in a reactor base of the inner reaction tube, the at least two reaction gas openings preceded upstream by at least one Laval nozzle which supercritically expands the mass stream of silicon-containing reaction gas.

14. A method for the production of granular polysilicon, comprising feeding a fluidizing gas and a mass stream of a silicon-containing gas into a fluidized bed of granular polysilicon contained within an inner reaction tube of a fluidized bed reactor of claim 4, while maintaining the temperature of the fluidized bed at between 850 C. and 1200 C. whereby silicon is deposited on granules in the fluidized bed in polycrystalline form, continuously adding silicon seed particles to the reactor, and continuously withdrawing a granular polysilicon product, wherein the silicon-containing reaction gas is fed to at least two reaction gas openings in a reactor base of the inner reaction tube, the at least two reaction gas openings preceded upstream by at least one Laval nozzle which supercritically expands the mass stream of silicon-containing reaction gas.

15. A method for the production of granular polysilicon, comprising feeding a fluidizing gas and a mass stream of a silicon-containing gas into a fluidized bed of granular polysilicon contained within an inner reaction tube of a fluidized bed reactor of claim 5, while maintaining the temperature of the fluidized bed at between 850 C. and 1200 C. whereby silicon is deposited on granules in the fluidized bed in polycrystalline form, continuously adding silicon seed particles to the reactor, and continuously withdrawing a granular polysilicon product, wherein the silicon-containing reaction gas is fed to at least two reaction gas openings in a reactor base of the inner reaction tube, the at least two reaction gas openings preceded upstream by at least one Laval nozzle which supercritically expands the mass stream of silicon-containing reaction gas.

16. A method for the production of granular polysilicon, comprising feeding a fluidizing gas and a mass stream of a silicon-containing gas into a fluidized bed of granular polysilicon contained within an inner reaction tube of a fluidized bed reactor of claim 6, while maintaining the temperature of the fluidized bed at between 850 C. and 1200 C. whereby silicon is deposited on granules in the fluidized bed in polycrystalline form, continuously adding silicon seed particles to the reactor, and continuously withdrawing a granular polysilicon product, wherein the silicon-containing reaction gas is fed to at least two reaction gas openings in a reactor base of the inner reaction tube, the at least two reaction gas openings preceded upstream by at least one Laval nozzle which supercritically expands the mass stream of silicon-containing reaction gas.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows one embodiment of the invention having an opening a Laval nozzle situated upstream.

(2) FIG. 2 shows one embodiment of the invention having two or more openings each having a Laval nozzle situated upstream.

(3) FIG. 3 shows one embodiment of the invention having one or more groups of openings, of which each group has at least two openings. A Laval nozzle is situated upstream of each group.

(4) FIG. 4 shows one embodiment of the invention having two or more openings, wherein a Laval nozzle is situated upstream of each opening and which are combined to form one or more groups each having Laval nozzles situated upstream.

(5) FIG. 5 shows one embodiment of the invention having one or more gas distributor devices each having two or more openings. A Laval nozzle is situated upstream of each gas distributor device.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) Preferably, the fluidized bed reactor comprises at least two openings in the reactor base each having a Laval nozzle situated upstream.

(7) Preferably, the fluidized bed reactor comprises at least one group of openings in the reactor base, comprising at least two openings, wherein a Laval nozzle is situated upstream of the at least one group of openings in each case.

(8) Preferably, the fluidized bed reactor comprises at least one group of openings in the reactor base, comprising in each case at least two openings, wherein in each case one Laval nozzle is situated upstream of each opening, in such a manner that at least one group of Laval nozzles comprising in each case at least two Laval nozzles results, wherein in each case one Laval nozzle is connected upstream of each at least one group of Laval nozzles.

(9) Preferably, the at least one opening in the reactor base upstream of which a Laval nozzle is situated is a gas distributor device.

(10) Preferably, the at least one opening in the reactor base upstream of which a Laval nozzle is situated is a hole in the base plate, a valve, or a nozzle.

(11) The object is also achieved by a method for producing granular polysilicon in a device according to the invention or in a device according to any one of the abovementioned preferred embodiments, which comprises fluidizing silicon particles by means of a fluidizing gas in a fluidized bed which is heated via a heating device to a temperature of 850-1200 C., addition of a silicon-containing reaction gas and deposition of silicon on the silicon particles.

(12) The invention also relates to a method for producing granular polysilicon in a fluidized bed reactor, which comprises fluidizing silicon particles by means of a fluidizing gas that is fed via at least one opening in the reactor base of the fluidized bed reactor in a fluidized bed which is heated via a heating device to a temperature of 850-1200 C., addition of a silicon-containing reaction gas which is fed via at least one opening in the reactor base of the fluidized bed reactor, and deposition of silicon on the silicon particles, wherein at least one mass stream of fluidizing gas or reaction gas that is fed is expanded supercritically.

(13) The fluidizing gas is preferably H.sub.2 and the silicon-containing reaction gas is preferably TCS.

(14) Preferably, a Laval nozzle is situated upstream of at least one of the openings in the reactor base in order to expand supercritically the at least one mass stream that is fed, by overpressure prevailing in the Laval nozzle.

(15) For uniform distribution of gas mass streams in fluidized beds, perforated plates having nozzle geometries, nozzle plates, valve plates or occasionally porous plates having a defined pressure drop can also be used. The pressure and mass stream fluctuations on the supply side induced by pressure fluctuations of the fluidized bed are greatly damped by the pressure drop of the gas distributor. Furthermore, circular apertures can be used in the gas feed conduits in case the pressure drop of the gas inlet openings is not sufficient.

(16) A uniform distribution of one or more gas mass streams fed to a fluidized bed over time and all inlet openings is not ensured in the present invention via a gas distributor plate alone via the pressure drop thereof, but via Laval nozzles, which are preferably operated at a supercritical pressure ratio.

(17) In certain fluidized bed applications, for reasons of structural, process-related or quality grounds, it is not possible to ensure the required pressure drop for gas uniform distribution via the gas distributor plate or the valves or nozzles used.

(18) Laval nozzles situated upstream have the advantage that they can be used for such applications for harmonization of the gas mass streams that are fed in terms of time and location, without intervening in the geometry of the fluidized bed apparatuses, gas distributor plates, nozzles or valves.

(19) The uniform distribution of at least one of the gas mass streams fed to the fluidized bed proceeds via a Laval nozzle situated upstream.

(20) In Laval nozzles, a defined pressure drop is generated by cross section constriction and subsequent expansion. If the pressure difference between entry side and exit side increases above a certain ratio (critical pressure ratio), the fluid in the Laval nozzle is accelerated to the speed of sound in the narrowest cross section and supersonic speed on the exit side. In supercritical flow, the mass stream remains constant at constant nozzle intake pressure, i.e. pressure variations on the exit side of the Laval nozzle that are coupled to the fluidized bed apparatus do not have an effect on the mass stream passing through.

(21) In the arrangement of the Laval nozzles and openings (for example holes in the base plates, valves or nozzles), various possibilities result which are illustrated hereinafter with reference to FIGS. 1-5.

LIST OF REFERENCE SIGNS USED

(22) 1 Fluidized bed 2 Opening for feed of a gas mass stream to the fluidized bed 3 Laval nozzle 4 Feed gas mass stream 5 Offgas mass stream 6 Other gas mass streams fed 7 Gas distributor (having a plurality of openings)

EXAMPLES

(23) The examples hereinafter show that the gas mass stream flowing through the Laval nozzles is dependent on the inlet pressure, the nozzle diameter, the gas composition, the temperature and the number of nozzles.

(24) The pressure p_out should preferably be selected in such a manner that a supercritical state prevails in the Laval nozzle:

(25) $\left(\frac{p_{\mathrm{out}}}{p_{\mathrm{in}}}\right)<{\left(\frac{p_{\mathrm{out}}}{p_{\mathrm{in}}}\right)}_{\mathrm{crit}}$

(26) The critical pressure ratio may be calculated as follows

(27) ${\left(\frac{p_{\mathrm{out}}}{p_{\mathrm{in}}}\right)}_{\mathrm{crit}}={\left(\frac{2}{+1}\right)}^{\frac{}{+1}}$

(28) In this case is the isentropic coefficient of the gas which is flowing through the nozzle.

(29) The mass stream which flows through an opening having the narrowest open cross sectional area A may be calculated as follows:

(30) $\stackrel{.}{m}=A.Math.\sqrt{2.Math.p_{\mathrm{in}}.Math.{}_{\mathrm{in}}}.Math.{\left(\frac{2}{+1}\right)}^{\left(\frac{1}{-1}\right)}.Math.\sqrt{\frac{}{+1}}$
.sub.in here is the density of the gas on the gas entry side (pressure side).

(31) Example 1 is the reference case. The parameters of the reference case and also of the further examples may be found in Table 1.

(32) In Example 2, the nozzle cross section was increased. A larger nozzle cross section for the same intake pressure means more mass stream passing through, which, however, does not have an effect on p_out.

(33) In Example 3, the gas composition was changed by the Laval nozzle. It is found that the mass stream depends greatly on the gas composition, wherein gases having a lower molar mass require a lower pressure downstream of the Laval nozzle and a smaller mass stream can be passed through.

(34) In Example 4, the temperature was increased. This causes a decrease in the gas density and thereby likewise decreases the mass stream.

(35) Also, lowering the intake pressure of the Laval nozzle leads to a lower gas mass stream being able to flow through the nozzle.

(36) TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- ple 1 ple 2 ple 3 ple 4 ple 5 Smallest di- 0.01 0.024 0.01 0.01 0.01 ameter of Laval nozzle [m] x_H.sub.2 [mol %] 50 50 95 50 50 x_HCl 0 0 5 0 0 [mol %] x_TCS 50 50 0 50 50 [mol %] T_in [K] 500 500 500 900 500 (p_out/ 0.572 0.572 0.529 0.575 0.572 p_in)_crit [] p_in [bar] 10.00 10.00 10.00 10.00 5.00 p_out [bar] <5.72 <5.725 <5.29 <5.75 <2.86 Mass stream 701 4036 174 520 350 through_indi- vidual nozzle [kg/h] n_nozzles 3 3 3 3 3 Total mass 2103 12108 522 1560 1050 stream

(37) Example 6 is based on the arrangement of FIG. 4, in which four openings each have one Laval nozzle, each two Laval nozzles are combined to form a group and in addition one further Laval nozzle is connected upstream of each group.

(38) The pressure ratios and geometries shown in Table 2 result.

(39) TABLE-US-00002 TABLE 2 Example 6 Smallest diameter of Laval 0.01 nozzle upstream of group [m] Smallest diameter of Laval 0.0092 nozzle upstream of opening [m] x_H.sub.2 [mol %] 50 x_HCl [mol %] 0 x_TCS [mol %] 50 T_in [K] 500 p_in [bar] 15 p_center [bar] <8.572 p_out [bar] <4.889 Total mass stream [kg/h] 2102 Mass stream per group [kg/h] 1051 Mass stream per_opening [kg/h] 525