Sublimation of silicon carbide to produce large, device quality single crystals of silicon carbide

• US RE34,861 E
• Filed: 10/09/1990
• Issued: 02/14/1995
• Est. Priority Date: 10/26/1987
• Status: Expired due to Term

• Current Assignee: North Carolina State University (University of North Carolina System)
• Original Assignee: North Carolina State University (University of North Carolina System)
• Inventors: Carter, Calvin H. Jr., Hunter, Charles E., Davis, Robert F.
• Primary Examiner(s): FOURSON III, GEORGE R
• Application Number:
  US07/594,856
• Time in Patent Office: 1,589 Days
• Field of Search: 148/DIG. 148, 156/610, 156/612, 156/614, 156/DIG. 64, 156/DIG. 68, 437/100, 117/105
• US Class Current: 117/86
• CPC Class Codes: C30B 23/00 Single-crystal growth by condensing evaporated or sublimed materials
• CPC Class Codes: C30B 29/36 Carbides
• CPC Class Codes: H01L 33/0054 for devices with an active region comprising only group IV elements
• CPC Class Codes: Y10S 148/021 Continuous process
• CPC Class Codes: Y10S 148/148 Silicon carbide

Abstract

The present invention is a method of forming large device quality single crystals of silicon carbide. The sublimation process is enhanced by maintaining a constant polytype composition in the source materials, selected size distribution in the source materials, by specific preparation of the growth surface and seed crystals, and by controlling the thermal gradient between the source materials and the seed crystal.

Claims

1. A method of reproducibly controlling the growth of large single crystals of the use of impurities as a primary mechanism for controlling polytype growth, and which crystals are suitable for use in producing electrical devices, the method comprising:

introducing a monocrystalline seed crystal of silicon carbide of desired polytype and a silicon carbide source powder into a sublimation system;

raising the temperature of the silicon carbide source powder to a temperature sufficient for the source powder to sublime;

while

elevating the temperature of the growth surface of the seed crystal to a temperature approaching the temperature of the source powder, but lower than the temperature of the source powder and lower than that at which silicon carbide will sublime under the gas pressure conditions of the sublimation system; and

generating and maintaining a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit area per unit time from the source powder to the growth surface of the seed crystal for a time sufficient to produce a desired amount of macroscopic growth of monocrystalline silicon carbide of desired polytype upon the seed crystal.

2. A method according to claim 1 further comprising the step of preparing a polished seed crystal of silicon carbide prior to the step of introducing the seed crystal of silicon carbide into the closed system.

3. A method according to claim 1 wherein the step of introducing a seed single crystal of silicon carbide into a closed system containing silicon carbide source powder further comprises initially segregating the source powder and the seed crystal from one another.

4. A method according to claim 1 wherein the step of raising the temperature of the silicon carbide source powder comprises raising the temperature of the silicon carbide source powder to between about 2250°

and 2350°

centigrade.

5. A method according to claim 1 wherein the step of raising the temperature of the silicon carbide source powder comprises raising the temperature of the silicon carbide source powder to about 2300°

centigrade.

6. A method according to claim 2 wherein the step of elevating the temperature of the seed crystal comprises elevating the temperature of the seed crystal to between about 2150°

and 2250°

centigrade.

7. A method according to claim 2 wherein the step of elevating the temperature of the seed crystal comprises elevating the temperature of the seed crystal to about 2200°

centigrade.

8. A method according to claim 1 wherein the step of introducing a single seed crystal of silicon carbide comprises introducing a seed crystal for which a face corresponding to a low integer Miller index face has been cut to expose a face which is nonperpendicular to an axis normal to the low integer Miller index face which was cut.

9. A method according to claim 1 wherein the step of generating and maintaining a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit time comprises introducing a source powder having a selected composition of polytypes and maintaining the selected composition of polytypes in the source powder substantially constant throughout the growth process.

10. A method according to claim 9 wherein the step of maintaining the originally selected composition of polytypes in the source powder comprises replenishing the source powder during the sublimation process using source powder replenishment having a composition of polytypes which will maintain the originally selected composition of polytypes in the source powder substantially constant in the sublimation system.

11. A method according to claim 1 wherein the step of generating and maintaining a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit area per unit time comprises introducing a source powder having a selected predetermined distribution of surface areas and maintaining the selected distribution of surface areas in the source powder substantially constant throughout the growth process.

12. A method according to claim 11 wherein the step of maintaining the originally selected predetermined distribution of surface areas comprises replenishing the source powder during the sublimation process using source powder replenishment having a distribution of surface areas which will maintain the originally selected distribution of surface areas substantially constant in the source powder in the sublimation system.

13. A method according to claim 1 wherein the step of generating and maintaining a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit area per unit time comprises introducing a source powder having a selected predetermined distribution of particle sizes and maintaining the selected distribution of particle sizes in the source powder substantially constant throughout the growth process.

14. A method according to claim 11 wherein the step of maintaining the originally selected predetermined distribution of particle sizes comprises replenishing the source powder during the sublimation process using source powder replenishment having a distribution of particle sizes which will maintain the originally selected distribution of particle sizes substantially constant in the source powder in the sublimation system.

15. A method according to claim 10, claim 12 or claim 14 wherein the step of replenishing the source powder during the sublimation process comprises feeding silicon carbide to the sublimation system using a screw conveying mechanism.

16. A method according to claim 10, claim 12 or claim 14 wherein the step of replenishing the source powder during the sublimation process comprises feeding silicon carbide to the sublimation system using ultrasonic energy to move silicon carbide powder into the system.

17. A method according to claim 15 wherein the step of increasing the temperature gradient between the seed crystal and the source powder comprises increasing the temperature of the source powder while maintaining the temperature of the growth surface of the seed crystal at the initial lower temperature than the source powder.

18. A method according to claim 15 wherein the step of introducing the thermal gradient commprises introducing a thermal gradient of 20°

centrigrade per centimeter.

19. A method according to claim 15 wherein the step of increasing the thermal gradient comprises increasing the thermal gradient from about 20°

centigrade per centimeter to about 50°

centigrade per centimeter.

20. A method according to claim 15 wherein the steps of raising the temperature of the source powder, introducing a thermal gradient and increasing the thermal gradient comprise using a resistance heating device to raise the temperature, introduce the thermal gradient and increase the thermal gradient.

21. A method according to claim 16 wherein the step of maintaining a fixed thermal gradient between the growth surface of the seed crystal and the source powder comprises providing relative movement between the growth surface of the seed crystal and the source powder as the seed crystal grows while maintaining the source powder at the temperature sufficient for silicon carbide to sublime and the seed crystal at the temperature approaching the temperature of the source powder but lower than the temperature of the source powder and lower than that at which silicon carbide will sublime.

22. A method according to claim 16 wherein the step of maintaining a fixed thermal gradient between the growth surface of the seed crystal and the source powder comprises maintaining a fixed distance between the growth surface of the seed crystal and the source powder as the crystal grows.

23. A method according to claim 16 wherein the step of maintaining a constant thermal gradient between the growth surface of the seed crystal and the source powder comprises independently controlling the source powder and seed crystal temperatures by separately monitoring the temperature of the source powder and the temperature of the seed crystal and separately adjusting the temperature of the source powder and the temperature of the seed crystal.

24. A method according to claim 14 wherein the step of replenishing the source powder during the sublimation process using source powder having a selected distribution of particle sizes comprises introducing silicon carbide powder having the following size distribution as determined by the weight percentage of a sample which will pass through a designated Tyler mesh screen:

space="preserve" listing-type="tabular">______________________________________ Tyler Mesh Screen Weight Percent Passed ______________________________________ 20-40 43% 40-60 19% 60-100 17% Over 100 21% ______________________________________

25. A method according to claim 1 wherein the step of generating and maintaining a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit area per unit time from the source powder to the growth surface of the seed crystal comprises increasing the thermal gradient between the seed crystal and the source powder as the crystal grows and the source powder is used up to thereby maintain an absolute temperature difference between the source powder and seed crystal which continues to be most favorable for crystal growth and to continuously encourage further crystal growth beyond that which would be obtained by maintaining a constant temperature gradient.

26. A method according to claim 1 wherein the step of generating and maintaining a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit area per unit time from the source powder to the growth surface of the seed crystal comprises maintaining a constant thermal gradient as measured between the growth surface of the seed crystal and the source powder as the crystal grows and as the source powder is used up while maintaining the growth surface of the seed crystal and the source powder at their respective different temperatures to thereby maintain a constant growth rate of the single seed crystal and a consistent growth of a single polytype upon the single growth surface of the seed crystal.

27. A method according to claim 1 including the step of rotating the seed crystal as the seed crystal grows and as the source powder is used up to thereby maintain a constant temperature profile across the growth surface of the seed crystal, to dampen the effect of flux variations, and to prevent the growing crystal from becoming attached to undesired mechanical portions of the closed system.

29. A method according to claim 1 wherein the step of generating and maintaining a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit area per unit time from the source powder to the growth surface of the seed crystal further comprises introducing a thermal gradient between the source powder and the seed crystal and then increasing the thermal gradient between the seed crystal and the source powder as the crystal grows and the source powder is used up to thereby maintain an absolute temperature difference between the source powder and seed crystal which continues to be most favorable for crystal growth and to continuously encourage further crystal growth beyond that which would be obtained by maintaining a constant temperature gradient. .Iaddend.

28. A method of reproducibly controlling the growth of large single crystals of a single polytype of silicon carbide independent of the use of impurities as a primary mechanism for controlling polytype growth, and which crystals are suitable for use in producing electical devices, the method comprising:

introducing a monocrystalline seed crystal of silicon carbide of desired polytype and a silicon carbide source powder into a sublimation system, with the source powder having a selected composition of polytypes, a selected predetermined distribution of surface areas, and a selected predetermined distribution of particle sizes;

raising the temperature of the silicon carbide source powder to a temperature sufficient for the source powder to sublime;

while

elevating the temperature of the growth surface of the seed crystal to a temperature approaching the temperature of the source powder, but lower than the temperature of the source powder and lower than that at which silicon carbide will sublime under the gas pressure conditions of the sublimation system; and

maintaining the selected composition of polytypes in the source powder substantially constant throughout the growth process;

while

maintaining the selected distribution of surface areas in the source powder substantially constant throughout the growth process; and

while

maintaining the selected distribution of particle sizes in the source powder substantially constant throughout the growth process, to thereby generate and maintain a substantially constant flow of vaporized Si, Si₂ C, and SiC₂ per unit area per unit time from the source powder to the growth surface of the seed crystal, and all for a time sufficient to produce a desired amount of macroscopic growth of monocrystalline silicon carbide of desired polytype upon the seed crystal. .Iadd.