Nucleation of aluminum nitride on a silicon substrate using an ammonia preflow

• US 9,617,656 B2
• Filed: 07/07/2014
• Issued: 04/11/2017
• Est. Priority Date: 07/25/2011
• Status: Active Grant

• Current Assignee: Samsung Electronics Co. Ltd.
• Original Assignee: Toshiba Corporation
• Inventors: Ramer, Jeff, Fenwick, William E.
• Primary Examiner(s): Chen, Bret
• Application Number:
  US14/325,195
• Publication Number:
  US 20140318443A1
• Time in Patent Office: 1,009 Days
• CPC Class Codes: C30B 25/10 Heating of the reaction chamber or the substrate
• CPC Class Codes: C30B 25/14 Feed and outlet means for the gases; Modifying the flow of the reactive gases
• CPC Class Codes: C30B 25/183 being provided with a buffer layer, e.g. a lattice matching layer
• CPC Class Codes: C30B 25/186 being specially pre-treated by, e.g. chemical or physical means
• CPC Class Codes: C30B 29/406 Gallium nitride
• CPC Class Codes: H01L 21/02381 Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/02458 Nitrides
• CPC Class Codes: H01L 21/02502 consisting of two layers
• 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 29/2003 Nitride compounds
• CPC Class Codes: H01L 33/0066 with a substrate not being a III-V compound
• CPC Class Codes: H01L 33/0075 comprising nitride compounds

Abstract

A method of making an aluminum nitride (AlN) buffer layer over a silicon wafer for a light emitting diode (LED) includes preflowing a first amount of ammonia that is sufficient to deposit nitrogen atoms on the surface of a silicon wafer without forming SiNx, before flowing trimethylaluminum and then a subsequent amount of ammonia through the chamber.

Claims

1. A method performed in sequential order comprising:

(a) first, heating a substrate of silicon (Si) in a chamber, wherein the chamber'"'"'s temperature is above 950°

C.;

(b) second, changing the chamber'"'"'s temperature from the above 950°

C. to a second temperature and flowing hydrogen (H₂) into the chamber;

(c) third, forming a layer on the substrate of Si having no nitride (N) at least by;

changing the chamber'"'"'s temperature from the second temperature to a third temperature, and

flowing a first amount of ammonia (NH₃) into the chamber while the hydrogen is still flowing into the chamber, wherein the first amount of ammonia is less than 0.01% by volume of the hydrogen flowing into the chamber

(d) fourth, flowing trimethylaluminum (Al₂(CH₃)₆) into the chamber while the hydrogen is still flowing into the chamber; and

(e) fifth, changing the chamber'"'"'s temperature from the third temperature to a fourth temperature and flowing a subsequent amount of ammonia into the chamber while the trimethylaluminum is still flowing into the chamber, wherein the subsequent amount of ammonia is greater than 0.002% by volume of the hydrogen flowing into the chamber,

wherein the first temperature, second temperature, and third temperature are different from each other.

2. The method of claim 1, wherein the flowing the first amount of ammonia into the chamber is performed for between thirty seconds to three minutes.

3. The method of claim 1, wherein the substrate is a wafer having a surface, and wherein the first amount of ammonia does not exceed 0.006 cubic centimeters per minute over each square centimeter of the surface of the substrate.

4. The method of claim 1, wherein the substrate is a wafer having a surface, and wherein the flowing the hydrogen into the chamber is performed by flowing between 106 and 118 cubic centimeters of hydrogen per minute over each square centimeter of the surface of the substrate.

5. The method of claim 1, wherein the flowing the trimethylaluminum into the chamber is performed for between ten to twenty minutes.

6. The method of claim 1, wherein trimethylaluminum flows into the chamber in an amount of about ninety micromoles per minute.

7. The method of claim 1, wherein the second temperature in the chamber during the flowing of hydrogen in (b) is above 1100°

C., and wherein the third temperature in the chamber during the flowing of the first amount of ammonia in (c) is between 1000°

C. and 1050°

C.

8. The method of claim 1, wherein the third temperature in the chamber during the flowing of the first amount of ammonia in (c) is the same as the fourth temperature in the chamber during the flowing of the subsequent amount of ammonia in (e).

9. The method of claim 1, further comprising:

(f) increasing the flow of the trimethylaluminum at a fifth temperature.

10. The method of claim 9, wherein the third temperature in the chamber during the flowing of the first amount of ammonia in (c) is the same as the fourth temperature in the chamber during the flowing of the subsequent amount of ammonia in (e), and lower than the fifth temperature in the chamber during the increased flow of the trimethylaluminum in (f).

11. A method, performed in sequential order, of manufacturing a semiconductor device, the method comprising:

first, providing a silicon substrate in a chamber;

second, cleaning a surface of the silicon substrate with a flow of hydrogen in the chamber;

third, forming a layer on the substrate of Si having no nitride (N) at least by flowing a first amount of ammonia in the chamber while the hydrogen is still flowing into the chamber, wherein the first amount of ammonia forms nitrogen-silicon bonds without forming SiN_x at the surface of the silicon substrate;

fourth, flowing trimethylaluminum (Al₂(CH₃)₆) in into the chamber while the hydrogen is still flowing into the chamber; and

fifth, flowing a second amount of ammonia into the chamber, wherein the second amount of ammonia is greater than 0.002% by volume of the hydrogen flowing into the chamber.

12. The method of claim 11, wherein the first amount of ammonia is less than 0.01% by volume of the hydrogen flowing in the chamber.

13. The method of claim 11, wherein the second amount of ammonia is greater than 0.002% by volume of the hydrogen flowing in the chamber.

14. The method of claim 11, wherein the second amount of ammonia is less than 5% of the total amount of hydrogen, ammonia, and trimethylaluminum simultaneously flowing in the chamber.

15. The method of claim 11, wherein the flow of hydrogen in the chamber is 180 to 200 liters/min.

16. The method of claim 11, wherein a temperature in the chamber during the flowing of the first amount ammonia and second amount of ammonia is between 1000°

C. and 1050°

C., and a temperature in the chamber during the flowing of the trimethylaluminum is 1120°

C.

17. The method of claim 11, wherein the trimethylaluminum is about 90 micromoles per minute.