III-V aresenide-nitride semiconductor materials and devices

• US 5,689,123 A
• Filed: 10/01/1996
• Issued: 11/18/1997
• Est. Priority Date: 04/07/1994
• Status: Expired due to Fees

• Current Assignee: JDS Uniphase Corporation (Lumentum Holdings Inc.)
• Original Assignee: SDL Inc (RWS Holdings Plc)
• Inventors: Welch, David F., Major, Jo S., Scifres, Donald R.
• Primary Examiner(s): JACKSON JR, JEROME
• Application Number:
  US08/724,321
• Time in Patent Office: 413 Days
• Field of Search: 259/184, 259/201, 259/190, 259/18, 259/22
• US Class Current: 257/190
• CPC Class Codes: C23C 16/303 Nitrides
• 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: H01L 33/32 containing nitrogen
• CPC Class Codes: H01S 5/32 comprising PN junctions, e.g. hetero- or double- heterostructures H01S5/34, H01S5/36 take precedence
• CPC Class Codes: H01S 5/323 in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
• CPC Class Codes: H01S 5/32341 blue laser based on GaN or GaP
• CPC Class Codes: H01S 5/3235 emitting light at a wavelength longer than 1000 nm, e.g. InP-based 1300 nm and 1500 nm lasers
• CPC Class Codes: H01S 5/32366 (In)GaAs with small amount of N
• CPC Class Codes: H01S 5/32375 In(As)N with small amount of P, or In(As)P with small amount of N

Abstract

III-V arsenide-nitride semiconductor crystals, methods for producing such crystals and devices employing such crystals. Group III elements are combined with group V elements, including at least nitrogen and arsenic, in concentrations chosen to lattice match commercially available crystalline substrates. Epitaxial growth of these III-V crystals results in direct bandgap materials, which can be used in applications such as light emitting diodes and lasers. Varying the concentrations of the elements in the III-V crystals varies the bandgaps, such that materials emitting light spanning the visible spectra, as well as mid-IR and near-UV emitters, can be created. Conversely, such material can be used to create devices that acquire light and convert the light to electricity, for applications such as full color photodetectors and solar energy collectors. The growth of the III-V crystals can be accomplished by growing thin layers of elements or compounds in sequences that result in the overall lattice match and bandgap desired.

Claims

1. A III-V compound semiconductor material having at least nitrogen and arsenic disposed at Group V lattice sites wherein concentration of nitrogen to arsenic in said material is either less than about 5% or greater than about 90% comprising misicible regions for said material when utilizing MOCVD, said nitrogen and arsenic being proportioned at said Group V lattice sites of said material within said concentration so that said material is substantially lattice matched to a semiconductor substrate upon which said material is deposited while providing a direct bandgap level lower than the case where either the nitrogen or the arsenic is absent from the material.

2. The semiconductor material of claim 1 wherein nitrogen atoms are present at at least 2% of the group V lattice sites.

3. The semiconductor material of claim 1 wherein the As-to-N ratio in said direct bandgap material is selected to produce said lattice match.

4. The semiconductor material of claim 1 wherein said direct bandgap material is lattice matched to said substrate due to strain.

5. The semiconductor material of claim 1 wherein said substrate is selected from the group consisting of GaP, Si, GaAs, Ge, SiC, ZnSe, ZnO and diamond.

6. A III-V semiconductor single crystal composite material comprising:

a series of layers having nitrogen and at least one other Group V atomic species disposed at Group V lattice sites in said series of layers,

said series of layers containing nitrogen in one set of said layers and said least one other Group V atomic species in another set of said layers,

said layers being sufficiently thin in the monolayer regime to avoid formation of defects,

said layer sets arranged with their overall nitrogen to the other Group V atomic species ratio to substantially provide lattice match of said composite material layers to a crystalline substrate while providing an overall direct bandgap level for the combined series of layers lower than the case where either the nitrogen or said least one other Group V atomic species is absent from the layers.

7. The composite material of claim 6 wherein at least one layer of said composite material has a direct bandgap.

8. The composite material of claim 6 wherein said thin layers are composed of In_w Al_x Ga_1-x-w N and In_w Al_x Ga_1-x-w As.

9. The composite material of claim 6 wherein at least one of said layers in said series of layers is a monolayer.

10. The composite material of claim 6 wherein said substrate is selected from the group consisting of GaP, Si, GaAs, Ge, InN, SiC, ZnSe, ZnO and diamond.

11. The composite material of claim 6 wherein the material has a composition selected such that a lattice constant of said material is less than 1% different from a lattice constant of said crystalline substrate selected from the group consisting of GaP, Si, GaAs, Ge, InN, ZnSe, ZnO and diamond so that said material and said substrate are lattice matched.

12. The composite material of claim 6 having a composition selected such that a lattice constant of the material is greater than 1% different than a lattice constant of said crystalline substrate selected from the group consisting of GaP, Si, GaAs, Ge, InN, SiC, ZnSe, ZnO and diamond so that said material and said substrate are lattice matched under strain.

13. A compound III-V semiconductor material having an overall composition with at least one element from the group consisting of B, Al, Ga and In disposed at Group III lattice sites, and a concentration of both nitrogen atoms and arsenic atoms at Group V lattice sites, the number of nitrogen and arsenic atoms present at the Group V lattice sites within an immiscible region for arsenide-nitride material, said material comprises a series of layers of III-V semiconductor compounds, one set of said layers in said series having a substantial concentration of nitrogen atoms over arsenic atoms, another set of said layers in said series having a significant concentration of arsenic atom over nitrogen atoms, each of said layers being sufficiently thin to avoid the formation of defects due to mismatched lattices.

43. The compound III-V semiconductor material of claim 13 wherein nitrogen is the majority component in the Group V sites with up to about 20% arsenic at said Group V sites.

44. The compound III-V semiconductor material of claim 13 wherein nitrogen at said Group V sites is between about 5% and about 90%.

45. The compound III-V semiconductor material of claim 13 wherein said nitrogen concentration layers and said arsenic concentration layers are interspersed monolayers.

46. The compound III-V semiconductor material of claim 45 wherein there is about five monolayers of GaAs for every monolayer of GaN.

47. The compound III-V semiconductor material of claim 46 wherein said sets of layers result in an overall Group V lattice site concentration of nitrogen of approximately 17% and of arsenic of approximately 83%.

48. The compound III-V semiconductor material of claim 13 wherein said series of layers is grown by low-pressure metal organic vapor deposition.

49. The compound III-V semiconductor material of claim 48 wherein a nitrogen source used in said deposition is hydra fine, phenol-hyrazine or metal organic source.

50. The compound III-V semiconductor material of claim 48 wherein nitrogen source used in said deposition is ammonia in combination with a catalyst to enhance the cracking efficiency of ammonia.

51. The compound III-V semiconductor material of claim 50 wherein said catalyst is arsine or phosphine.

14. A compound semiconductor material having a zinc blende crystal lattice and an overall composition with at least one dement from the group consisting of B, Al, Ga and In disposed at group III lattice sites, and also including a concentration of N atoms of at least 2% disposed at group V lattice sites and a concentration of As atoms of at least 2% disposed at group V lattice sites,

said compound semiconductor material comprising a direct bandgap material composed of In_w Al_x Ga_1-x-w As_1-y-z P_z N_y, where 0≦

w≦

1, 0≦

x≦

1, 0.02≦

y≦

0.98, 0≦

z≦

0.96 and 0.02≦

1-y-z≦

0.98, w, x, y, and z being chosen such that a lattice constant of the material is substantially matched with a lattice constant of a semiconductor substrate selected from the group consisting of GaP, Si, GaAs, Ge, InN, SiC, ZnSe, ZnO and diamond.

15. The semiconductor material of claim 14 wherein w=0, z=0 and 0.14≦

y≦

0.20.

16. The semiconductor material of claim 14 wherein w=0, z>

0 and 0.02≦

y≦

0.10.

17. The semiconductor material of claim 14 wherein w>

0, z=0 and 0.14≦

y≦

0.27.

18. The semiconductor material of claim 14 wherein y≦

0.90.

19. The semiconductor material of claim 14 wherein w>

0 and y≦

0.05.

20. A semiconductor compound comprising a zinc-blende crystal material composed of a sequence of thin semiconductor compound layers in the monolayer regime disposed on top of one another, each thin layer in said sequence having at least one element from the group consisting of Al, B, Ga and In atoms disposed at Group III lattice sites and at least one element from the group consisting of As, P and N atoms disposed at Group V lattice sites, one set of said monolayer regime layers in said sequence having a substantial proportion of N atoms disposed at said Group V lattice sites and another set of said monolayer regime layers in said sequence having a substantial portion of As atoms disposed at said Group V lattice sites, said sets of layers sequentially chosen to provide a lattice constant that is less than 1% different from a lattice constant of a crystalline substrate upon which said monolayer regime layers are deposited while providing an overall direct bandgap level for the combined series of monolayer regime layers lower than the case where either the N or the As is absent from the material.

21. The semiconductor compound of claim 20 wherein after deposition of said sequence of thin layers, said crystal lattice material has been heated such that an appreciable number of atoms in each thin layer have diffused into adjoining layers.

22. A III-V semiconductor material having at least one element from the group consisting of Al, Ga and In disposed at Group III lattice sites, and having at least nitrogen and arsenic disposed at Group V lattice sites,

other elements which can be disposed at said Group V lattice sites being selectable from the group consisting of P and Sb,

the concentration of nitrogen at said Group V lattice sites either about 5% or less or about 90% or more comprising a miscible region for said material when utilizing MOCVD, said nitrogen and arsenic being proportioned at said Group V lattice sites of said material within said nitrogen concentration so that said material is substantially lattice matched to a semiconductor substrate upon which said material is deposited, said nitrogen being chosen to achieve a specified energy gap reduction relative to the energy gap of comparable III-V semiconductor material where nitrogen is at 100% of said group V lattice sites.

23. The semiconductor material of claim 22 wherein the material is a mixed crystal composed of Al_x Ga_y In_1-x-y Sb_m As_n P_p N_1-m-n-p, where x and y range from 0 to 1, m and p range from 0 to 0.48, n ranges from 0.02 to 0.50 and 1-m-n-p≧

0.50.

24. The semiconductor material of claim 22 wherein said material is a direct bandgap material.

25. The semiconductor material of claim 22 wherein said material has a cubic structure.

26. The semiconductor material of claim 22 wherein said material has a wurtzite structure.

27. The semiconductor material of claim 22 wherein said material is composed of a plurality of thin layers, each thinner than a critical thickness to avoid defect formation.

28. The semiconductor material of claim 27 wherein each of said thin layers contains both nitrogen and at least one other element from the group consisting of P, As and Sb disposed at the group V lattice sites of said layers.

29. The semiconductor material of claim 28 wherein said plurality of thin layers forms a semiconductor heterostructure.

30. The semiconductor material of claim 28 wherein at least one of said thin layers is strained.

31. The semiconductor material of claim 30 wherein at least one strained layer has at least Ga and N at respective group III and group V lattice sites.

32. The semiconductor material of claim 30 wherein the remainder of said thin layers are substantially lattice matched to a single crystal substrate.

33. The semiconductor material of claim 27 wherein said thin layers contain substantially all nitrogen at group V lattice sites in a first set of layers and substantially all of said at least one other element at said group V lattice sites in a second set of layers intermixed with said first set of layers.

34. The semiconductor material of claim 33 wherein the overall composite of said intermixed first and second sets of thin layers is lattice matched to a single crystal substrate to within about 3%.

35. The semiconductor material of claim 22 further comprising a single crystal substrate upon which said material is formed.

36. The semiconductor material of claim 35 wherein said material is substantially lattice matched to said single crystal substrate.

37. The semiconductor material of claim 35 wherein said substrate is an indirect bandgap material.

38. A III-V semiconductor material having at least one element from the group consisting of Al, Ga and In disposed at group III lattice sites, and having at least nitrogen and arsenic disposed at group V lattice sites, other elements which can be disposed at the group V lattice sites being selectable from the group consisting of P and Sb, the concentration of nitrogen being at least 50% of the group V lattice sites and the concentration of arsenic and each other element at said group V lattice sites being chosen to achieve a specified energy gap reduction relative to comparable material with nitrogen at 100% of said group V lattice sites, a single crystal substrate upon which said material is formed being selected from the group consisting of InN, ZnO, SiC and Al₂ O₃.

39. A high temperature electronic device comprising:

a semiconductor crystal substrate,

a structure disposed on said substrate of at least one III-V semiconductor material layer including N atoms and As atoms at Group V lattice sites with said N atoms at said Group V lattice sites within the range of either about 5% or less than or about 90% or more than said As atoms,

said N atoms and As atoms being proportioned at said Group V sites of said material layer so as to be substantially..lattice matched to said substrate while providing a direct bandgap level lower than the case where either the nitrogen or the arsenic is absent from the structure,

said structure having p-type and n-type dopants therein defining at least one p-n junction, and

means for applying electrical voltage and current to selected regions of said structure associated with said at least one p-n junction.

40. The device of claim 39 wherein at least one III-V semiconductor material layer of said structure is a direct bandgap material layer.

41. The device of claim 39 wherein said structure has a lattice constant that is less than 1% different from a lattice constant of said substrate.

42. The device of claim 39 wherein said structure is lattice matched to said substrate under strain.

52. A compound III-V semiconductor material having an overall composition with at least one element from the group consisting of B, Al, Ga and In disposed at Group III lattice sites, and also including a concentration of both nitrogen atoms and arsenic atoms at Group V lattice sites, the number of nitrogen atoms present at the Group V lattice sites is in an immiscible region for arsenide-nitride material, said material comprises a series of layers of III-V semiconductor compounds, one set of said layers in said series having a substantial concentration of nitrogen atoms over arsenic atoms, another set of said layers in said series having a substantial concentration of arsenic atoms over nitrogen atoms, each of said layers being sufficiently thin within the monolayer regime to avoid the formation of defects due to mismatched lattices.

53. The compound III-V semiconductor material of claim 52 wherein arsenic is the majority component in the Group V sites with above 5% nitrogen at said Group V sites.

54. A compound III-V semiconductor material comprising:

an overall composition with at least one element from the group consisting of B, Al, Ga and In disposed at Group III lattice sites, and a concentration of both N atoms and As atoms at Group V lattice sites,

the concentration of N atoms at said Group V lattice sites within a range of either about 5% or less than or about 90% or more than said As atoms,

said N atoms and As atoms being proportioned at the Group V sites so as to be substantially lattice matched to said substrate and to reduce the direct bandgap to a desired level within said N atom concentration range.

55. The compound III-V semiconductor material of claim 54 wherein said arsenide-nitride compound is GaAsN, InAsN, GaPN, InPN, InGaAsN, AlGaN, AlGaAsN or AlGaInAsN.

56. The compound III-V semiconductor material of claim 54 wherein said arsenide-nitride compound comprises GaAs_1-x N_x or InAs_1-x N_x where x≦

0.5 or x≦

0.9.

57. The compound III-V semiconductor material of claim 54 wherein said arsenide-nitride compound is lattice matched to a substrate comprising GaAs, ZnO or SiC.

58. The compound III-V semiconductor material of claim 54 wherein said arsenide-nitride compound is utilized in a heterostructure light emitting device.

59. The compound III-V semiconductor material of claim 58 wherein said heterostructure comprises AlGaN, AlGaAsN, AlGaInAsN or SiC.

60. The compound III-V semiconductor material of claim 58 wherein inclusion of As atoms, P atoms or Sb atoms at Group V lattice sites in a layer of said heterostructure light emitting device comprising an active region having a bandgap chosen within said N atom concentration range.