Method for growing III-V compound semiconductor structures with an integral non-continuous quantum dot layer utilizing HVPE techniques

• US 6,599,133 B2
• Filed: 05/18/2001
• Issued: 07/29/2003
• 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., Melnik, Yuri V., Dmitriev, Vladimir A., Nikolaev, Audrey E.
• Primary Examiner(s): Pham, Long
• Assistant Examiner(s): Louie, Wai-Sing
• Application Number:
  US09/860,624
• Publication Number:
  US 20020025661A1
• Time in Patent Office: 802 Days
• Field of Search: 438/505, 438/46, 438/47, 257/79-103
• US Class Current: 438/22
• 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−z}N, InGaN_1−a−bP_aAs_b, or Al_xB_yIn_zGa_{1−x−y−z}N_1−a−bP_aAs_b.

Claims

1. A method of fabricating a compound semiconductor device without the inclusion of a low temperature buffer layer, the method utilizing HVPE techniques and comprising the steps of:

locating a Ga metal in a first source zone of a reaction chamber;

locating an Al metal in a second source zone of said reaction chamber;

locating an In metal in a third source zone of said reaction chamber;

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

locating in at least one supplemental source zone of said reaction chamber at least one supplemental Group III material or at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material, wherein said at least one supplemental Group III material is selected from the group of materials consisting of Al and B, and wherein said at least one supplemental Group V material is selected from the group of materials consisting of P and As;

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

heating said substrate to a first temperature, wherein said first temperature is greater than 900°

C.;

heating said Ga metal to a second temperature;

heating said Al metal to a third temperature;

heating said In metal to a fourth temperature;

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

heating said at least one supplemental Group III material or said at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material to at least a sixth temperature;

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

introducing said halide reaction gas into said second source zone to form an Al halide compound;

transporting said Ga halide compound and said Al halide compound to said growth zone via a flowing inert gas;

introducing a reaction gas into said growth zone, said reaction gas containing N;

growing a first AlGaN layer on said substrate, said first AlGaN layer formed by said reaction gas reacting with said Ga halide compound and said Al halide compound, wherein said first AlGaN layer is an n-type AlGaN layer;

discontinuing said step of transporting said Al halide compound to said growth zone;

growing a first GaN layer on said first AlGaN layer, said first GaN layer formed by said reaction gas reacting with said Ga halide compound, wherein said first GaN layer is an n-type GaN layer;

transporting said in metal to said growth zone via said flowing inert gas;

transporting said at least one supplemental Group III material or said at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material to said growth zone via said flowing inert gas;

growing a non-continuous quantum dot layer on said first GaN layer, said non-continuous quantum dot layer comprised of a plurality of quantum dot regions, said plurality of quantum dot regions comprised of Ga, N, In, and said at least one supplemental Group III material or said at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material;

discontinuing said step of transporting said at least one supplemental Group III material or said at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material to said growth zone;

discontinuing said step of transporting said In metal to said growth zone;

transporting said at least one acceptor impurity metal to said growth zone via said flowing inert gas;

growing a second GaN layer, wherein said non-continuous quantum dot layer is interposed between said first GaN layer and said second GaN layer, said second GaN layer formed by said reaction gas reacting with said Ga halide compound, wherein said second GaN layer contains said at least one acceptor impurity metal, and wherein said second GaN layer is a p-type GaN layer;

resuming said step of transporting said Al halide compound to said growth zone; and

growing a second AlGaN layer on said second GaN layer, said second AlGaN layer formed by said reaction gas reacting with said Ga halide compound and said Al halide compound, wherein said second AlGaN layer contains said at least one acceptor impurity metal, and wherein said second AlGaN layer is a p-type AlGaN layer.

2. The method of claim 1, wherein said step of locating said at least one supplemental Group III material or said at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material in at least one supplemental source zone of said reaction chamber is comprised of locating Al metal within said second source zone, said second source zone equivalent to said at least one supplemental source zone.

3. The method of claim 1, further comprising the step of introducing said halide reaction gas into said at least one supplemental source zone prior to said step of transporting said at least one supplemental Group III material or said at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material to said growth zone.

4. The method of claim 1, wherein said step of growing said non-continuous quantum dot layer is further comprised of growing a plurality of Al_xB_yIn_zGa₁₋

x−

y−

zN quantum dot regions, wherein 0.01≦

x+y≦

0.2.

5. The method of claim 4, wherein 0.01≦

x+y≦

0.03 and x+y+z≦

0.2.

6. The method of claim 4, wherein 0.01≦

x+y≦

0.03 and x+y+z≦

0.15.

7. The method of claim 1, wherein said step of growing said non-continuous quantum dot layer is further comprised of growing a plurality of InGaN₁₋

x−

yP_xAs_y quantum dot regions, wherein 0.01≦

x+y≦

0.2.

8. The method of claim 7, wherein 0.01≦

x+y≦

0.03.

9. The method of claim 1, wherein said step of growing said non-continuous quantum dot layer is further comprised of growing a plurality of Al_xB_yIn_zGa₁₋

x−

y−

zN<sub>1−

a−

b</sub>P_aAs_b quantum dot regions, wherein 0.01≦

x+y≦

0.2 and 0.01≦

a+b≦

0.2.

10. The method of claim 9, wherein 0.01≦

x+y≦

0.03, x+y+z≦

0.2, and 0.01≦

a+b≦

0.03.

11. The method of claim 9, wherein 0.01≦

x+y≦

0.03, x+y+z≦

0.15, and 0.01≦

a+b≦

0.03.

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

depositing a first contact on said second AlGaN layer; and

depositing a second contact on said substrate.

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

discontinuing said step of transporting said Al halide compound to said growth zone; and

growing a third GaN layer on said second AlGaN layer, said third GaN layer formed by said reaction gas reacting with said Ga halide compound, wherein said third GaN layer contains said at least one acceptor impurity metal, and wherein said third GaN layer is a p-type GaN layer.

14. The method of claim 13, further comprising the steps of:

depositing a first contact on said third GaN layer; and

depositing a second contact on said substrate.

15. The method of claim 1, further comprising the step of selecting Mg as said at least one acceptor impurity metal.

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

17. The method of claim 16, further comprising the steps of:

positioning said Ga metal on a second sapphire boat within said first source zone;

positioning said Al metal on a third sapphire boat within said second source zone; and

positioning said In metal on a fourth sapphire boat within said third source zone.

18. The method of claim 16, further comprising the steps of:

positioning said Ga metal on a second sapphire boat within said first source zone;

positioning said Al metal on a silicon carbide boat within said second source zone; and

positioning said In metal on a third sapphire boat within said third source zone.

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

locating a second acceptor impurity metal in a fifth source zone of said reaction chamber;

heating said second acceptor impurity metal to a seventh temperature; and

transporting said second acceptor impurity metal to said growth zone simultaneously with said at least one acceptor impurity metal.

20. The method of claim 19, further comprising the step of positioning said second acceptor impurity metal on a sapphire boat within said fifth source zone.

21. The method of claim 19, further comprising the step of selecting Zn as said second acceptor impurity metal.

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

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

C. to 1100°

C.

24. The method of claim 1, wherein said second and third temperatures are within the temperature range of 750°

C. to 1050°

C.

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

C. to 700°

C.

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

C. to 650°

C.

27. The method of claim 1, wherein said fifth temperature is approximately 615°

C.

28. The method of claim 1, further comprising the step of annealing said second GaN layer and said second AlGaN layer.

29. The method of claim 28, said annealing step further comprised of the step of heating said second GaN layer and said second AlGaN layer to a temperature within the range of 700°

C. to 800°

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

30. The method of claim 29, wherein said annealing step is performed for approximately 10 minutes.

31. The method of claim 1, further comprising the step of selecting a transport rate associated with said step of transporting said at least one acceptor impurity metal to said growth zone, wherein said selected transport rate achieves a concentration of said at least one acceptor impurity metal within said second GaN layer and said second AlGaN layer of between 10¹⁸ to 10²¹ atoms cm⁻

3.

32. The method of claim 1, further comprising the step of selecting a transport rate associated with said step of transporting said at least one acceptor impurity metal to said growth zone, wherein said selected transport rate achieves a concentration of said at least one acceptor impurity metal within said second GaN layer and said second AlGaN layer of between 10¹⁹ to 10²⁰ atoms cm⁻

3.

33. The method of claim 13, further comprising the step of selecting a transport rate associated with said step of transporting said at least one acceptor impurity metal to said growth zone, wherein said selected transport rate achieves a concentration of said at least one acceptor impurity metal within said third GaN layer of between 10¹⁸ to 10²¹ atoms cm⁻

3.

34. The method of claim 13, further comprising the step of selecting a transport rate associated with said step of transporting said at least one acceptor impurity metal to said growth zone, wherein said selected transport rate achieves a concentration of said at least one acceptor impurity metal within said third GaN layer of between 10¹⁹ to 10²⁰ atoms cm⁻

3.

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

36. The method of claim 35, wherein said pre-conditioning step is further comprised of saturating said growth zone and said first, second, third, and fourth source zones and said at least one supplemental source zone with said at least one acceptor impurity metal.

37. The method of claim 1, further comprising the step of co-doping said second GaN layer and said second AlGaN layer with O.

38. The method of claim 13, further comprising the step of co-doping said third GaN layer with O.

39. The method of claim 1, further comprising the step of doping said first GaN layer with at least one donor impurity selected from the group of materials consisting of O, Si, Ge, and Sn.

40. The method of claim 1, further comprising the step of etching said substrate, said Ga metal, said Al metal, said In metal, said at least one acceptor impurity metal, and said at least one supplemental Group III material or said at least one supplemental Group V material or both said at least one supplemental Group III material and said at least one supplemental Group V material to remove surface contamination, said etching step performed prior said first growing step.

41. The method of claim 1, further comprising the step of doping said first AlGaN layer with at least one donor impurity selected from the group of materials consisting of O, Si, Ge, and Sn.