Method for growing p-type III-V compound material utilizing HVPE techniques

• US 6,555,452 B2
• Filed: 05/17/2001
• Issued: 04/29/2003
• Est. Priority Date: 11/18/1997
• Status: Expired due to Term

• Current Assignee: Kyma Technologies, Inc.
• Original Assignee: Technologies And Devices International Inc.
• Inventors: Vassilevski, Konstantin V., Dmitriev, Vladimir A., Melnik, Yuri V., Nikolaev, Audrey E.
• Primary Examiner(s): Cuneo, Kamand
• Assistant Examiner(s): Sarkar, Asok Kumar
• Application Number:
  US09/861,011
• Publication Number:
  US 20020028565A1
• Time in Patent Office: 712 Days
• Field of Search: 117/952, 117/953, 257/76, 257/77, 257/79, 257/94, 257/101-103, 438/46, 438/47, 438/479, 438/495, 438/505, 438/508, 438/518, 438/519, 438/542, 438/546, 438/565, 438/914, 438/919, 438/925, 438/930
• US Class Current: 438/565
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/40 AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
• CPC Class Codes: C30B 29/403 AIII-nitrides
• CPC Class Codes: C30B 29/406 Gallium nitride
• CPC Class Codes: H01L 21/0237 Materials
• CPC Class Codes: H01L 21/02378 Silicon carbide
• CPC Class Codes: H01L 21/02458 Nitrides
• CPC Class Codes: H01L 21/02505 consisting of more than two layers
• CPC Class Codes: H01L 21/0254 Nitrides
• CPC Class Codes: H01L 21/02543 Phosphides
• CPC Class Codes: H01L 21/02546 Arsenides
• CPC Class Codes: H01L 21/02579 P-type
• CPC Class Codes: H01L 21/0259 Microstructure
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 31/0304 including, apart from doping materials or other impurities, only AIIIBV compounds
• CPC Class Codes: H01L 31/105 the potential barrier being of the PIN type
• CPC Class Codes: H01L 33/007 comprising nitride compounds
• CPC Class Codes: Y02E 10/544 Solar cells from Group III-V materials
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product

Abstract

A method for fabricating p-type, i-type, and n-type III-V compound materials using HVPE techniques is provided. If desired, these materials can be grown directly onto the surface of a substrate without the inclusion of a low temperature buffer layer. By growing multiple layers of differing conductivity, a variety of different device structures can be fabricated including simple p-n homojunction and heterojunction structures as well as more complex structures in which the p-n junction, either homojunction or heterojunction, is interposed between a pair of wide band gap material layers. The provided method can also be used to fabricate a device in which a non-continuous quantum dot layer is grown within the p-n junction. The quantum dot layer is comprised of a plurality of quantum dot regions, each of which is typically between approximately 20 and 30 Angstroms per axis. The quantum dot layer is preferably comprised of Al_xB_yIn_zGa_1-x-y-zN, InGaN_1-a-bP_aAs_b, or Al_xB_yIn_zGa_1-x-y-zN_1-a-bP_aAs_b.

Claims

1. A method of growing a p-type III-V material utilizing HVPE techniques, the method comprising the steps of:

locating at least one Group III metal in a first source zone of a reaction chamber;

locating at least one acceptor impurity metal in a second source zone of said reaction chamber;

locating a substrate within a growth zone of said reaction chamber;

heating said substrate to a first temperature;

heating said at least one Group III metal to a second temperature;

heating said at least one acceptor impurity metal to a third temperature;

introducing a halide reaction gas into said first source zone to form at least one halide metal compound;

transporting said at least one halide metal compound to said growth zone;

introducing a reaction gas into said growth zone, said reaction gas containing at least one Group V element;

introducing an inert gas into said second source zone;

flowing said inert gas through said second source zone in order to deliver said at least one acceptor impurity metal to said growth zone; and

growing said p-type III-V layer through a reaction of said reaction gas and said at least one halide metal compound, wherein said p-type III-V layer contains said at least one acceptor impurity metal.

2. The method of claim 1, further comprising the step of positioning said at least one acceptor impurity metal on a sapphire boat within said second source zone.

3. The method of claim 1, further comprising the step of positioning said at least one Group III metal on a sapphire boat within said first source zone.

4. The method of claim 1, further comprising the step of positioning said at least one Group III metal on a silicon carbide boat within said first source zone.

5. The method of claim 1, further comprising the step of pre-filling said reaction chamber with a flowing inert gas.

6. The method of claim 1, wherein said first temperature is within the temperature range of 800°

C. to 1200°

C.

7. The method of claim 1, wherein said first temperature is within the temperature range of 1000°

C. to 1100°

C.

8. The method of claim 1, wherein said second temperature is within the temperature range of 750°

C. to 1050°

C.

9. The method of claim 1, wherein said third temperature is within the temperature range of 450°

C. to 700°

C.

10. The method of claim 1, wherein said third temperature is within the temperature range of 550°

C. to 650°

C.

11. The method of claim 1, wherein said third temperature is approximately 615°

C.

12. The method of claim 1, wherein said halide reactive gas is HCl.

13. The method of claim 1, wherein said reaction gas is ammonia gas.

14. The method of claim 1, further comprising the steps of:

locating a second Group III metal in a third source zone of said reaction chamber;

heating said second Group III metal to a fourth temperature;

introducing said halide reaction gas into said third source zone to form a second halide metal compound; and

transporting said second halide metal compound to said growth zone simultaneously with said at least one halide metal compound, said III-V layer formed by said reaction gas reacting with both said at least one halide metal compound and said second metal halide metal, wherein said III-V layer contains said at least one acceptor impurity metal, wherein said III-V layer is a p-type III-V layer.

15. The method of claim 14, further comprising the step of positioning said second Group III metal on a sapphire boat within said third source zone.

16. The method of claim 14, further comprising the step of positioning said second Group III metal on a silicon carbide boat within said third source zone.

17. The method of claim 14, wherein said at least one Group III metal is Ga and said second Group III metal is Al.

18. The method of claim 1, further comprising the steps of:

positioning a second acceptor impurity metal on a sapphire boat;

locating said sapphire boat and said second acceptor impurity metal within a third source zone of said reaction chamber;

heating said second acceptor impurity metal to a fourth temperature;

introducing said inert gas into said third source zone; and

flowing said inert gas through said third source zone in order to deliver said second acceptor impurity metal to said growth zone simultaneously with said at least one acceptor impurity metal, wherein said grown III-V layer contains both said at least one acceptor impurity metal and said second acceptor impurity metal.

19. The method of claim 18, wherein said at least one acceptor impurity metal is Zn and said second acceptor impurity metal is Mg.

20. The method of claim 1, further comprising the step of growing a second III-V layer, wherein said second III-V layer is an n-type III-V layer, wherein said step of growing said second III-V layer is further comprised of the step of preventing transport of said at least one acceptor impurity metal to said growth zone.

21. The method of claim 20, wherein said second III-V layer is interposed between said substrate and said p-type III-V layer.

22. The method of claim 1, further comprising the step of annealing said grown III-V layer.

23. The method of claim 22, said annealing step further comprised of the step of heating said III-V layer to a temperature within the range of 700°

C. to 800°

C., said heating step performed within a nitrogen atmosphere.

24. The method of claim 23, wherein said annealing step is performed for approximately 10 minutes.

25. The method of claim 1, wherein a concentration of said at least one acceptor impurity metal within said grown III-V layer is in the range of 10¹⁸ to 10²¹ atoms cm⁻

3.

26. The method of claim 1, wherein a concentration of said at least one acceptor impurity metal within said grown III-V layer is in the range of 10¹⁹ to 10²⁰ atoms cm⁻

3.

27. The method of claim 1, further comprising the step of pre-conditioning said reaction chamber.

28. The method of claim 27, wherein said pre-conditioning step is further comprised of saturating said growth zone and said first and second source zones with said at least one acceptor impurity metal.

29. The method of claim 1, further comprising the step of etching said substrate, said at least one Group III metal, and said at least one acceptor impurity metal to remove surface contamination, said etching step performed prior said growing step.

30. The method of claim 29, wherein said etching step is performed prior to said transporting steps.

31. The method of claim 29, wherein said etching step is performed prior to said heating steps.

32. The method of claim 1, further comprising the step of selecting said substrate from the group of substrates consisting of sapphire, silicon carbide, or gallium nitride.

33. The method of claim 1, further comprising the step of selecting p-type silicon carbide as said substrate.

34. A method of growing a p-type GaN material utilizing HVPE techniques, the method comprising the steps of:

positioning a gallium source on a first sapphire boat;

locating said first sapphire boat and said gallium source within a first source zone of a reaction chamber;

positioning a magnesium metal on a second sapphire boat;

locating said second sapphire boat and said magnesium metal within a second source zone of said reaction chamber;

locating a substrate within a growth zone of said reaction chamber;

heating said substrate to a first temperature within the temperature range of 1000°

C. to 1100°

C.;

heating said gallium source to a second temperature within the temperature range of 750°

C. to 1050°

C.;

heating said magnesium metal to a third temperature within the temperature range of 550°

C. to 650°

C.;

introducing a halide reaction gas into said first source zone to form a gallium chloride compound;

transporting said gallium chloride compound to said growth zone;

introducing an ammonia gas into said growth zone;

introducing an inert gas into said second source zone;

flowing said inert gas through said second source zone in order to deliver said magnesium metal to said growth zone; and

growing said p-type GaN layer through a reaction of said ammonia gas and said gallium chloride compound, wherein said p-type GaN layer contains a concentration of said magnesium metal in the range of 10¹⁹ to 10²⁰ atoms cm<sup>−

3</sup>.

35. The method of claim 34, further comprising the steps of:

positioning a zinc metal on a third sapphire boat;

locating said third sapphire boat and said zinc metal within a third source zone of said reaction chamber;

heating said zinc metal to a fourth temperature;

introducing said inert gas into said third source zone; and

flowing said inert gas through said third source zone in order to deliver said zinc metal to said growth zone simultaneously with said magnesium metal, wherein said grown p-type GaN layer contains a combined concentration of said magnesium metal and said zinc metal in the range of 10¹⁹ to 10²⁰ atoms cm<sup>−

3</sup>.

36. A method of growing a p-type AlGaN material utilizing HVPE techniques, the method comprising the steps of:

positioning a gallium source on a first sapphire boat;

locating said first sapphire boat and said gallium source within a first source zone of a reaction chamber;

positioning a magnesium metal on a second sapphire boat;

locating said second sapphire boat and said magnesium metal within a second source zone of said reaction chamber;

positioning a aluminum source on a silicon carbide boat;

locating said silicon carbide boat and said aluminum source within a third source zone of said reaction chamber;

locating a substrate within a growth zone of said reaction chamber;

heating said substrate to a first temperature within the temperature range of 1000°

C. to 1100°

C.;

heating said gallium source to a second temperature within the temperature range of 750°

C. to 1050°

C.;

heating said magnesium metal to a third temperature within the temperature range of 550°

C. to 650°

C.;

heating said aluminum source to a fourth temperature within the temperature range of 700°

C. to 850°

C.;

introducing a halide reaction gas into said first source zone to form a gallium chloride compound;

introducing said halide reaction gas into said third source zone to form an aluminum trichloride compound;

simultaneously transporting said gallium chloride compound and said aluminum trichloride compound to said growth zone;

introducing an ammonia gas into said growth zone;

introducing an inert gas into said second source zone;

flowing said inert gas through said second source zone in order to deliver said magnesium metal to said growth zone; and

growing said p-type AlGaN layer through a reaction of said ammonia gas and said gallium chloride compound, wherein said p-type AlGaN layer contains a concentration of said magnesium metal in the range of 10¹⁹ to 10²⁰ atoms cm<sup>−

3</sup>.

37. The method of claim 36, further comprising the steps of:

positioning a zinc metal on a third sapphire boat;

locating said third sapphire boat and said zinc metal within a third source zone of said reaction chamber;

heating said zinc metal to a fifth temperature;

introducing said inert gas into said third source zone; and

flowing said inert gas through said third source zone in order to deliver said zinc metal to said growth zone simultaneously with said magnesium metal, wherein said grown p-type AlGaN layer contains a combined concentration of said magnesium metal and said zinc metal in the range of 10¹⁹ to 10²⁰ atoms cm<sup>−

3</sup>.