Production of polycrystalline silicon by the thermal decomposition of silane in a fluidized bed reactor
View Patent ↗Processes for producing polycrystalline silicon by thermal decomposition of silane are disclosed. The processes generally involve thermal decomposition of silane in a fluidized bed reactor operated at reaction conditions that result in a high rate of productivity relative to conventional production processes.
1. A process for producing polycrystalline silicon by the thermal decomposition of silane in a fluidized bed reactor having a reaction chamber, the reaction chamber having a core region, a peripheral region and a cross-section through which feed gases pass, the fluidized bed reactor producing at least about 100 kg/hr of polycrystalline silicon per square meter of reaction chamber cross-section, the process comprising:
introducing a first feed gas comprising silane into the core region of the reaction chamber, the reaction chamber containing silicon particles and the first feed gas containing less than about 80% by volume silane, wherein the temperature of the first feed gas is less than about 300° C. prior to entry into the reaction chamber; and wherein silane thermally decomposes in the reaction chamber to deposit an amount of silicon on the silicon particles; and
introducing a second feed gas into the peripheral region of the reaction chamber, wherein the concentration of silane in the first feed gas exceeds the concentration in the second feed gas, wherein the temperature of the second feed gas is at least about 350° C. to about 600° C. prior to entry into the reaction chamber, the overall concentration of silane in the feed gases fed into the reaction chamber being less than about 15% by volume, the pressure in the reaction chamber being at least 15 bar.
2. The process as set forth in claim 1 wherein the reaction chamber comprises an annular wall and has a circular cross-section having a center and a radius R, wherein the core region extends from the center to at least about 0.6R and the peripheral region extends from the core region to the annular wall.
3. The process as set forth in claim 1 wherein the temperature of the second feed gas is at least about 450° C.
4. The process as set forth in claim 1 wherein a spent gas is withdrawn from the fluidized bed reactor, the pressure of the spent gas being at least 15 bar.
5. The process as set forth in claim 1 wherein the concentration by volume of silane in the first feed gas is at least about 50% greater than the concentration by volume of silane in the second feed gas.
6. The process as set forth in claim 1 wherein at least about 75% of the silane introduced into the fluidized bed reactor is introduced through the core region.
7. The process as set forth in claim 1 wherein particulate polycrystalline silicon is withdrawn from the fluidized bed reactor, the Sauter mean diameter of the particulate polycrystalline silicon being from about 600 μm to about 2000 μm.
8. The process as set forth in claim 1 wherein the average residence time of gas introduced into the reaction chamber is less than about 20 seconds.
9. The process as set forth in claim 1 wherein at least about 150 kg/hr of silicon deposits on the silicon particles per square meter of reaction chamber cross-section.
10. The process as set forth in claim 1 wherein the second feed gas comprises less than about 5% by volume silane.
11. The process as set forth in claim 1 wherein the first feed gas comprises less than about 60% by volume silane.
12. The process as set forth in claim 1 wherein the overall concentration of silane in feed gases introduced into the reaction chamber is less than about 12% by volume.
13. The process as set forth in claim 1 wherein the reaction chamber is not partitioned into separate portions.
14. The process as set forth in claim 1 wherein the fluidized bed reactor comprises an annular inner chamber formed between a reaction chamber wall and an outer shell, the process comprising maintaining a pressure in the inner chamber at least about 1.1 bar below the pressure within the reaction chamber.
15. The process as set forth in claim 1 wherein the reaction chamber is heated to at least about 500° C.
16. The process as set forth in claim 1 wherein particulate polycrystalline silicon is withdrawn from the fluidized bed reactor, the Sauter mean diameter of the particulate polycrystalline silicon being from about 800 μm to about 1300 μm.
17. A process for producing polycrystalline silicon by the thermal decomposition of silane in a fluidized bed reactor having a reaction chamber, the reaction chamber having a core region, a peripheral region and a cross-section through which feed gases pass, the fluidized bed reactor producing at least about 100 kg/hr of polycrystalline silicon per square meter of reaction chamber cross-section, the process comprising:
introducing a first feed gas comprising silane into the core region of the reaction chamber, the reaction chamber containing silicon particles and the first feed gas containing less than about 80% by volume silane; wherein silane thermally decomposes in the reaction chamber to deposit an amount of silicon on the silicon particles; and
introducing a second feed gas into the peripheral region of the reaction chamber, wherein the second feed gas consists of compounds other than silane, the overall concentration of silane in the reaction chamber being less than about 15% by volume, the pressure in the reaction chamber being at least about 20 bar.
18. The process as set forth in claim 17 wherein the second feed gas consists of one or more compounds selected from the group consisting of silicon tetrachloride, hydrogen, argon and helium.
19. A process for producing polycrystalline silicon by the thermal decomposition of silane in a fluidized bed reactor having a reaction chamber and a distributor for distributing gases into the reaction chamber, the reaction chamber having a core region, a peripheral region and a cross-section through which feed gases pass, the fluidized bed reactor producing at least about 100 kg/hr of polycrystalline silicon per square meter of reaction chamber cross-section, the process comprising:
introducing a first feed gas comprising silane into the distributor to distribute the first feed gas into the core region of the reaction chamber, the reaction chamber containing silicon particles, the first feed gas containing less than about 80% by volume silane and the temperature of the first feed gas being less than about 400° C. prior to introduction into the distributor; wherein silane thermally decomposes in the reaction chamber to deposit an amount of silicon on the silicon particles; and
introducing a second feed gas into the distributor to distribute the second feed gas into the peripheral region of the reaction chamber, wherein the peripheral region is not separately partitioned from the core region, wherein the concentration of silane in the first feed gas exceeds the concentration in the second feed gas, the temperature of the second feed gas is at least about 350° C. and to about 600° C. prior to entry into the reaction chamber, and the pressure in the reaction chamber being at least 15 bar.
20. The process as set forth in claim 19 wherein the reaction chamber comprises an annular wall and has a circular cross-section having a center and a radius R, wherein the core region extends from the center to at least about 0.8R and the peripheral region extends from the core region to the annular wall.
21. The process as set forth in claim 19 wherein the temperature of the first feed gas is less than about 200° C. prior to entry into the distributor.
22. The process as set forth in claim 19 wherein the temperature of the second feed gas is at least about 450° C. prior to entry into the distributor.
23. The process as set forth in claim 19 wherein a spent gas is withdrawn from the fluidized bed reactor, the pressure of the spent gas being at least 15 bar.
24. The process as set forth in claim 19 wherein the concentration by volume of silane in the first feed gas is at least about 100% greater than the concentration by volume of silane in the second feed gas.
25. The process as set forth in claim 19 wherein at least about 75% of the silane introduced into the fluidized bed reactor is introduced through the core region.
26. The process as set forth in claim 19 wherein particulate polycrystalline silicon is withdrawn from the fluidized bed reactor, the Sauter mean diameter of the particulate polycrystalline silicon being from about 600 μm to about 2000 μm.
27. The process as set forth in claim 19 wherein the average residence time of gas introduced into the reaction chamber is less than about 4 seconds.
28. The process as set forth in claim 19 wherein at least about 3000 kg/hr of silicon deposits on the silicon particles per square meter of reaction chamber cross-section.
29. The process as set forth in claim 19 wherein the second feed gas comprises less than about 5% by volume silane.
30. The process as set forth in claim 19 wherein the first feed gas comprises less than about 60% by volume silane.
31. The process as set forth in claim 19 wherein the overall concentration of silane in feed gases introduced into the reaction chamber is less than about 20% by volume.
32. The process as set forth in claim 19 wherein the fluidized bed reactor comprises an annular inner chamber formed between a reaction chamber wall and an outer shell, the process comprising maintaining a pressure in the inner chamber at least about 10 bar below the pressure within the reaction chamber.
33. The process as set forth in claim 19 wherein reaction chamber is heated to at least about 650° C.
34. A process for producing polycrystalline silicon by the thermal decomposition of silane in a fluidized bed reactor having a reaction chamber and a distributor for distributing gases into the reaction chamber, the reaction chamber having a core region, a peripheral region and a cross-section through which feed gases pass, the fluidized bed reactor producing at least about 100 kg/hr of polycrystalline silicon per square meter of reaction chamber cross-section, the process comprising:
introducing a first feed gas comprising silane into the distributor to distribute the first feed gas into the core region of the reaction chamber, the reaction chamber containing silicon particles, the first feed gas containing less than about 80% by volume silane and the temperature of the first feed gas being less than about 400° C. prior to introduction into the distributor; wherein silane thermally decomposes in the reaction chamber to deposit an amount of silicon on the silicon particles; and
introducing a second feed gas into the distributor to distribute the second feed gas into the peripheral region of the reaction chamber, wherein the peripheral region is not separately partitioned from the core region, wherein the second feed gas consists of compounds other than silane, and the temperature of the second feed gas is at least about 350° C. and to about 600° C. prior to introduction into the reaction chamber, and further wherein the pressure in the reaction chamber is at least 15 bar.
35. The process as set forth in claim 34 wherein the second feed gas consists of one or more compounds selected from the group consisting of silicon tetrachloride, hydrogen, argon and helium.