Process for producing silicon carbide crystals having increased minority carrier lifetimes

• US 7,811,943 B2
• Filed: 02/07/2005
• Issued: 10/12/2010
• Est. Priority Date: 12/22/2004
• Status: Active Grant

• Current Assignee: CREE Incorporated (Wolfspeed, Inc.)
• Original Assignee: CREE Incorporated (Wolfspeed, Inc.)
• Inventors: Carter, Calvin H. Jr., Tsvetkov, Valeri F., Hobgood, Hudson M., Das, Mrinal K., Jenny, Jason R., Malta, David P.
• Primary Examiner(s): Monbleau; Davienne
• Assistant Examiner(s): REAMES, MATTHEW L
• Application Number:
  US11/052,679
• Publication Number:
  US 20060130742A1
• Time in Patent Office: 2,073 Days
• Field of Search: 257/E33.035, 257/E21.054, 257/E31.459, 257/E21.603, 257/E21.695, 257/E21.699, 438/478, 438/758
• US Class Current: 438/758
• CPC Class Codes: C30B 11/003 Heating or cooling of the melt or the crystallised material
• CPC Class Codes: C30B 29/36 Carbides
• CPC Class Codes: C30B 33/02 Heat treatment C30B33/04, C30B33/06 take precedence

Abstract

A process is described for producing silicon carbide crystals having increased minority carrier lifetimes. The process includes the steps of heating and slowly cooling a silicon carbide crystal having a first concentration of minority carrier recombination centers such that the resultant concentration of minority carrier recombination centers is lower than the first concentration.

Claims

1. A process for producing silicon carbide crystals having increased minority carrier lifetimes, comprising:

growing at a growth temperature to form a silicon carbide crystal having a first concentration of minority carrier recombination centers resulting in a first minority carrier lifetime;

heating said silicon carbide crystal to a temperature greater than its growth temperature to dissociate at least some of said recombination centers to decrease the concentration thereof; and

thereafter cooling the heated silicon carbide crystal at a rate sufficiently slow to reduce the recombination of said dissociated recombination centers to provide a silicon carbide crystal having a second concentration of minority carrier recombination centers that is lower than the first concentration thereby providing a material having an increased minority carrier lifetime.

2. The process of claim 1, wherein the heating step comprises heating the silicon carbide crystal to a temperature of at least about 2400°

C. and wherein the process further comprises maintaining said heated silicon carbide crystal at a temperature of at least about 2400°

C. for up to about one hour in an inert ambient atmosphere.

3. The process of claim 2, wherein the heating step comprises heating the silicon carbide crystal to a temperature ranging from about 2400°

C. to about 2700°

C. and wherein the process further comprises maintaining said heated silicon carbide crystal at a temperature ranging from about 2400°

C. to about 2700°

C. for up to about one hour in an inert ambient atmosphere.

4. The process of claim 3, wherein the heating step comprises heating the silicon carbide crystal to a temperature of about 2600°

C. and wherein the process further comprises maintaining said heated silicon carbide crystal at a temperature of about 2600°

C. for up to about one hour in an inert ambient atmosphere.

5. The process of claim 2, wherein the cooling step comprises cooling the heated silicon carbide crystal at a rate of about 2°

C. per minute or less to a temperature of about 1400°

C. to about 1000°

C.

6. The process of claim 5, wherein the cooling step comprises cooling the heated silicon carbide crystal at a rate of about 2°

C. per minute or less to a temperature of about 1200°

C.

7. The process of claim 6, wherein the cooling step further comprises cooling the silicon carbide crystal from about 1200°

C. to about room temperature at a rate from about 2°

C. per minute to about 10°

C. per minute.

8. The process of claim 1, wherein the growing step comprises forming the silicon carbide crystal by a sublimation process to form a bulk silicon carbide single crystal prior to said heating step and wherein the heating step comprises heating the bulk silicon carbide single crystal.

9. The process of claim 1, wherein the growing step comprises forming the silicon carbide crystal by an epitaxial growth process to form an epitaxial silicon carbide layer or layer prior to said heating step and wherein the heating step comprises heating the epitaxial silicon carbide layer or layers.

10. The process of claim 1, wherein the heating step comprises heating a silicon carbide crystal comprising dopant in an amount of about 1×

10¹⁷cm<sup>−

3</sup> or less.

11. The process of claim 1, wherein the heating and cooling steps comprise heating and cooling a silicon carbide crystal under conditions sufficient to provide a silicon carbide crystal exhibiting a minority carrier lifetime of at least about 1 microseconds (μ

s) or greater.

12. The process of claim 11, wherein the heating and cooling steps comprise heating and cooling a silicon carbide crystal under conditions sufficient to provide a silicon carbide crystal exhibiting a minority carrier lifetime of at least about 4 microseconds (μ

s) or greater.

14. A silicon carbide crystal made by the process of claim 1.

15. A semiconductor device comprising a silicon carbide crystal made by the process of claim 1.

16. The device of claim 15, wherein said device is a power device.

17. The device of claim 15, wherein said device is selected from the group consisting of pn diodes, PiN diodes, thyristors, and IGBTs.

23. The process of claim 1, wherein the cooling step comprises cooling the silicon carbide crystal at a rate of about 2°

C. per minute or less.

44. The process of claim 1, wherein the heating and cooling steps comprise heating and cooling a silicon carbide crystal under conditions sufficient to provide a silicon carbide crystal exhibiting a minority carrier lifetime of greater than 5 microseconds (μ

s).

45. The process of claim 1, wherein the heating and cooling steps comprise heating and cooling a silicon carbide crystal under conditions sufficient to provide a silicon carbide crystal exhibiting a minority carrier lifetime of about 20 microseconds (μ

s) or greater.

13. A process for producing silicon carbide crystals having increased minority carrier lifetimes, comprising:

heating a silicon carbide crystal having a first concentration of minority carrier recombination centers resulting in a first minority carrier lifetime and thereafter cooling the heated silicon carbide crystal at a rate sufficiently slow to provide a silicon carbide crystal having a second concentration of minority carrier recombination centers that is lower than the first concentration thereby providing a material having an increased minority carrier lifetime, wherein the heating and cooling steps comprise heating and cooling a silicon carbide crystal under conditions to provide a silicon carbide crystal exhibiting a minority carrier lifetime of at least about 30 microseconds (μ

s).

18. A process for the production of a device comprising a silicon carbide crystal exhibiting increased minority carrier lifetime, comprising:

growing at a growth temperature to form a silicon carbide crystal having a first concentration of minority carrier recombination centers resulting in a first minority carrier lifetime;

heating said silicon carbide crystal to a temperature greater than its growth temperature to dissociate at least some of said recombination centers to decrease the concentration thereof;

thereafter cooling the heated silicon carbide crystal at a rate sufficiently slow to reduce the recombination of said dissociated recombination centers to provide a silicon carbide crystal having a second concentration of minority carrier recombination centers that is lower than the first concentration thereby providing a material having an increased minority carrier lifetime; and

incorporating said silicon carbide crystal into a device.

19. The process of claim 18, wherein the incorporating step comprises incorporating said silicon carbide crystal into a device after said heating and cooling steps.

20. The process of claim 18, wherein the incorporating step comprises incorporating said silicon carbide crystal into a power device.

21. The process of claim 20, wherein the incorporating step comprises incorporating said silicon carbide crystal into a p-n diode.

22. The process of claim 20, wherein the incorporating step comprises incorporating said silicon carbide crystal into a PiN diode.

24. The process of claim 18, wherein the cooling step comprises cooling the silicon carbide crystal at a rate of about 2 °

C. per minute or less.

25. The process of claim 18, wherein the heating step comprises heating the silicon carbide crystal to a temperature of at least about 2400°

C. and wherein the process further comprises maintaining said heated silicon carbide crystal at a temperature of at least about 2400°

C. for up to about one hour in an inert ambient atmosphere.

26. The process of claim 25, wherein the heating step comprises heating the silicon carbide crystal to a temperature ranging from about 2400°

C. to about 2700°

C. and wherein the process further comprises maintaining said heated silicon carbide crystal at a temperature ranging from about 2400°

C. to about 2700°

C. for up to about one hour in an inert ambient atmosphere.

27. The process of claim 26, wherein the heating step comprises heating the silicon carbide crystal to a temperature of about 2600°

C. and wherein the process further comprises maintaining said heated silicon carbide crystal at a temperature of about 2600 °

C. for up to about one hour in an inert ambient atmosphere.

28. The process of claim 25, wherein the cooling step comprises cooling the heated silicon carbide crystal at a rate of about 2°

C. per minute or less to a temperature of about 1400°

C. to about 1000°

C.

29. The process of claim 28, wherein the cooling step comprises cooling the heated silicon carbide crystal at a rate of about 2°

C. per minute or less to a temperature of about 1200°

C.

30. The process of claim 29, wherein the cooling step farther comprises cooling the silicon carbide crystal from about 1200°

C. to about room temperature at a rate from about 2°

C. per minute to about 10°

C. per minute.

31. A process for the production of a device comprising a silicon carbide crystal exhibiting increased minority carrier lifetime comprising heating a silicon carbide crystal having a first concentration of minority carrier recombination centers resulting in a first minority carrier lifetime and thereafter cooling the heated silicon carbide crystal at a rate sufficiently slow to provide a silicon carbide crystal having a second concentration of minority carrier recombination centers that is lower than the first concentration thereby providing a material having an increased minority carrier lifetime, wherein the heating and cooling steps comprise heating and cooling a silicon carbide crystal under conditions to provide a silicon carbide crystal exhibiting a minority carrier lifetime of at least about 30microseconds (μ

s); and

incorporating said silicon carbide crystal into a device.

32. A process for producing silicon carbide crystals having increased minority carrier lifetimes, comprising:

growing at a growth temperature to form a silicon carbide crystal having a first concentration of minority carrier recombination centers resulting in a first minority carrier lifetime;

heating said silicon carbide crystal to a temperature greater than its growth temperature; and

thereafter cooling the heated silicon carbide crystal at a rate of about 2°

C. per minute or less to provide a silicon carbide crystal having a second concentration of minority carrier recombination centers that is lower than the first concentration thereby providing a material having an increased minority carrier lifetime.

33. The process of claim 32, wherein said growing step comprising growing said silicon carbide crystal using sublimation techniques to form a bulk grown silicon carbide single crystal boule and wherein the heating step comprises heating a bulk grown silicon carbide single crystal boule to a temperature higher than the sublimation temperature of silicon carbide.

34. The process of claim 33, wherein the heating step comprises heating a bulk grown silicon carbide single crystal boule to a temperature of at least about 2400 °

C.

35. The process of claim 32, wherein said growing step comprising growing said silicon carbide crystal using chemical vapor deposition techniques to form one or more silicon carbide epitaxial layers and wherein the heating step comprises heating one or more silicon carbide epitaxial layers to a temperature higher than the temperature for epitaxial growth of said silicon carbide epitaxial layers.

36. The process of claim 35, wherein the heating step comprises heating said one or more silicon carbide epitaxial layers to a temperature above about 1600°

C.

37. The process of claim 34, wherein the heating step comprises heating a bulk grown silicon carbide single crystal boule to a temperature of at least about 2600 °

C.

38. A process for producing silicon carbide crystals having increased minority carrier lifetimes, comprising:

growing at a growth temperature to form a silicon carbide crystal having a first concentration of intrinsic defects and a first minority carrier lifetime;

heating said silicon carbide crystal to a temperature that decreases the concentration of intrinsic defects; and

thereafter cooling the heated silicon carbide crystal at a rate sufficiently slow so that the silicon carbide crystal has a second concentration of intrinsic defects that is lower than the first concentration thereby providing a material having an increased minority carrier lifetime.

39. The process of claim 38, wherein:

said heating step comprises heating said silicon carbide crystal having a first concentration of intrinsic defects and a first minority carrier lifetime to a temperature sufficient to dissociate at least some of said intrinsic defects to decrease the concentration thereof; and

said cooling step comprises thereafter cooling the heated silicon carbide crystal at a rate sufficiently slow to reduce recombination of said dissociated intrinsic defects to provide a silicon carbide crystal having a second concentration of intrinsic defects that is lower than the first concentration thereby providing a material having an increased minority carrier lifetime.

40. The process of claim 39, wherein said cooling step is sufficiently slow to allow the silicon carbide crystal to spend sufficient time at a temperature at which the defects are re-annealed.

41. The process of claim 40, wherein the cooling step comprises cooling the silicon carbide crystal at a rate of about 2°

C. per minute or less.

42. The process of claim 41, wherein said growing step comprising growing said silicon carbide crystal using sublimation techniques to form a bulk grown silicon carbide single crystal boule and wherein the heating step comprises heating a bulk grown silicon carbide single crystal boule to a temperature higher than the sublimation temperature of silicon carbide of at least about 2400°

C.

43. The process of claim 41, wherein said growing step comprising growing said silicon carbide crystal using chemical vapor deposition techniques to form one or more silicon carbide epitaxial layers and wherein the heating step comprises heating one or more silicon carbide epitaxial layers to a temperature higher than the temperature for epitaxial growth of said silicon carbide epitaxial layers of above about 1600°

C.