Method of forming a group III-nitride crystalline film on a patterned substrate by hydride vapor phase epitaxy (HVPE)

• US 8,507,304 B2
• Filed: 07/15/2010
• Issued: 08/13/2013
• Est. Priority Date: 07/17/2009
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Kryliouk, Olga, Melnik, Yuriy, Kojiri, Hidehiro, Ishikawa, Tetsuya
• Primary Examiner(s): LUKE, DANIEL M
• Application Number:
  US12/837,390
• Publication Number:
  US 20110012109A1
• Time in Patent Office: 1,125 Days
• Field of Search: 438/481, 438/489, 438/44, 438/504, 257E21112-113, 257/E21.108, 117/97, 117/101
• US Class Current: 438/44
• CPC Class Codes: H01L 21/0237 Materials
• CPC Class Codes: H01L 21/0242 Crystalline insulating materials
• CPC Class Codes: H01L 21/0243 Surface structure
• CPC Class Codes: H01L 21/02433 Crystal orientation
• CPC Class Codes: H01L 21/02439 Materials
• CPC Class Codes: H01L 21/02458 Nitrides
• CPC Class Codes: H01L 21/02488 Insulating materials
• CPC Class Codes: H01L 21/0254 Nitrides
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 21/02639 Preparation of substrate for selective deposition
• CPC Class Codes: H01L 21/02647 Lateral overgrowth
• CPC Class Codes: H01L 29/04 characterised by their crystalline structure, e.g. polycrystalline, cubic or particular orientation of crystalline planes characterised by physical imperfections H01L29/30
• CPC Class Codes: H01L 29/045 by their particular orientation of crystalline planes
• CPC Class Codes: H01L 33/007 comprising nitride compounds
• CPC Class Codes: H01L 33/12 with a stress relaxation structure, e.g. buffer layer
• CPC Class Codes: H01L 33/16 with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous
• CPC Class Codes: H01L 33/22 Roughened surfaces, e.g. at the interface between epitaxial layers

Abstract

A method of depositing a high quality low defect single crystalline Group III-Nitride film. A patterned substrate having a plurality of features with inclined sidewalls separated by spaces is provided. A Group III-Nitride film is deposited by a hydride vapor phase epitaxy (HVPE) process over the patterned substrate. The HVPE deposition process forms a Group III-Nitride film having a first crystal orientation in the spaces between features and a second different crystal orientation on the inclined sidewalls. The first crystal orientation in the spaces subsequently overgrows the second crystal orientation on the sidewalls and in the process turns over and terminates treading dislocations formed in the first crystal orientation.

Claims

1. A method of depositing a Group III-Nitride film comprising:

providing a patterned substrate having a plurality of spaced apart features separated by a space, wherein said plurality of features have inclined sidewalls;

growing a Group III-Nitride film by hydride vapor phase epitaxy (HVPE) on said patterned substrate such that a portion of said Group III-Nitride film is grown with a first crystal orientation having a first growth rate in said space between said features and such that a portion of said Group III-Nitride film is grown with a second crystal orientation having a second growth rate on said inclined sidewalls; and

growing said Group III-Nitride film such that said portion of said Group III-Nitride film having said first crystal orientation grows from said space between said features laterally over said portion of said Group III-Nitride film having said second crystal orientation.

2. The method of claim 1 wherein said first growth rate is greater than said second growth rate.

3. The method of claim 1 wherein said portion of said Group III-Nitride film having said second crystal orientation on said inclined sidewalls is a micro/nanocrystalline film.

4. The method of claim 3 wherein said micro/nanocrystalline film is a columnar micro/nanocrystalline film having a plurality of aligned nanocrystals situated substantially perpendicular to the inclined sidewalls of said features.

5. The method of claim 1 wherein a plurality of voids are formed between said portion of said Group III-Nitride film having said first crystal orientation and said portion of said Group III-Nitride film having said second crystal orientation.

6. The method of claim 1 wherein said portion of said Group III-Nitride film having said second crystal orientation is formed to a thickness between 0.1-1.0 microns.

7. The method of claim 1 wherein said Group III-Nitride film is formed by HVPE utilizing at least two growth steps such that a first growth step uses a first set of process conditions which forms said portion of said Group III-Nitride film having said first crystal orientation with a first lateral growth rate and wherein a second growth step uses a second set of process conditions which forms said portion of said Group III-Nitride film having said first crystal orientation with a second lateral growth rate wherein said second lateral growth rate is greater than said first lateral growth rate.

8. The method of claim 7 wherein at least one of a deposition pressure, a deposition temperature and a Cl₂ flow rate over a Group-III source is changed from said first growth step to said second growth step so that said second lateral growth rate is greater than said first lateral growth rate.

9. The method of claim 1 wherein said inclined sidewalls of said features are inclined at an angle between 30°

-60°

from said substrate.

10. The method of claim 9 wherein said features comprise cone shaped features.

11. The method of claim 1 wherein said patterned substrate is selected from the group consisting of a silicon substrate, a sapphire substrate, a silicon carbide substrate, a silicon on diamond substrate, a quartz substrate, a glass substrate, a zinc oxide substrate, a magnesium oxide substrate and a lithium aluminum oxide substrate.

12. The method of claim 11 wherein said patterned substrate is a sapphire substrate.

13. The method of claim 12 wherein said sapphire substrate is a sapphire substrate with an off-cut angle from the c-plane between 0.35°

-0.8°

.

14. The method of claim 1 further comprising forming a low temperature aluminum nitride buffer layer between said Group III-Nitride film and said patterned substrate.

15. A method of depositing a Group III-Nitride film comprising:

providing a patterned substrate having a plurality of spaced apart features separated by a space, wherein said plurality of features have inclined sidewalls;

growing a Group III-Nitride film by hydride vapor phase epitaxy (HVPE) on said patterned substrate such that a portion of said Group III-Nitride film is grown with a first crystal orientation having a first growth rate in said space between said features and such that a portion of said Group III-Nitride film is grown with a second crystal orientation having a second growth rate and is a micro/nanocrystalline film on said inclined sidewalls; and

growing said Group III-Nitride film such that said portion of said Group III-Nitride film having said first crystal orientation grows laterally over said portion of said Group III-Nitride film having said second crystal orientation.

16. The method of claim 15 wherein said first growth rate is greater than said second growth rate.

17. The method of claim 15 wherein said micro/nanocrystalline film is a columnar micro/nanocrystalline film having a plurality of aligned nanocrystals situated substantially perpendicular to the inclined sidewalls of said features.

18. The method of claim 15 wherein a plurality of voids are formed between said portion of said Group III-Nitride film having said first crystal orientation and said portion of said Group III-Nitride film having said second crystal orientation.

19. The method of claim 15 wherein said portion of said Group III-Nitride film having said second crystal orientation is formed to a thickness between 0.1-1.0 microns.

20. The method of claim 15 wherein said Group III-Nitride film is formed by HVPE utilizing at least two growth steps such that a first growth step uses a first set of process conditions which forms said portion of said Group III-Nitride film having said first crystal orientation with a first lateral growth rate and wherein a second growth step uses a second set of process conditions which forms said portion of said Group III-Nitride film having said first crystal orientation with a second lateral growth rate wherein said second lateral growth rate is greater than said first lateral growth rate.

21. The method of claim 20 wherein at least one of a deposition pressure, a deposition temperature and a Cl₂ flow rate over a Group-III source is changed from said first growth step to said second growth step so that said second lateral growth rate is greater than said first lateral growth rate.

22. The method of claim 15 wherein said inclined sidewalls of said features are inclined at an angle between 30°

-60°

from said substrate.

23. The method of claim 22 wherein said features comprise cone shaped features.

24. The method of claim 15 wherein said patterned substrate is selected from the group consisting of a silicon substrate, a sapphire substrate, a silicon carbide substrate, a silicon on diamond substrate, a quartz substrate, a glass substrate, a zinc oxide substrate, a magnesium oxide substrate and a lithium aluminum oxide substrate.

25. The method of claim 24 wherein said patterned substrate is a sapphire substrate.

26. The method of claim 25 wherein said sapphire substrate is a sapphire substrate with an off-cut angle from the c-plane between 0.35°

-0.8°

.

27. The method of claim 15 further comprising forming a low temperature aluminum nitride buffer layer between said Group III-Nitride film and said patterned substrate.