SOI substrate and process for preparing the same, and semiconductor device and process for preparing the same

• US 6,528,387 B1
• Filed: 12/20/1999
• Issued: 03/04/2003
• Est. Priority Date: 06/19/1997
• Status: Expired due to Fees

• Current Assignee: Asahi Kasei Kabushiki Kaisha
• Original Assignee: Asahi Kasei Kabushiki Kaisha
• Inventors: Morishita, Takashi, Moriyasu, Yoshitaka, Matsui, Masahiro, Ishida, Makoto
• Primary Examiner(s): Nguyen, Tuan H.
• Application Number:
  US09/446,306
• Time in Patent Office: 1,170 Days
• Field of Search: 438/404, 438/479, 438/480, 438/400, 438/14, 438/17
• US Class Current: 438/404
• CPC Class Codes: H01L 21/2007 Bonding of semiconductor wafers to insulating substrates or to semiconducting substrates using an intermediate insulating layer H01L21/2011 takes precedence; bonding of semiconductor wafers to semiconductor wafers for junction formation H01L21/187
• CPC Class Codes: H01L 21/76248 using lateral overgrowth techniques, i.e. ELO techniques
• CPC Class Codes: H01L 21/76264 SOI together with lateral isolation, e.g. using local oxidation of silicon, or dielectric or polycristalline material refilled trench or air gap isolation regions, e.g. completely isolated semiconductor islands
• CPC Class Codes: H01L 21/76275 Vertical isolation by bonding techniques
• CPC Class Codes: H01L 21/76281 Lateral isolation by selective oxidation of silicon
• CPC Class Codes: H01L 21/84 the substrate being other than a semiconductor body, e.g. being an insulating body

Abstract

When producing an SOS substrate by growing a silicon layer on a sapphire substrate, or when producing an SOI substrate by depositing an oxide layer or a fluoride layer, as an intermediate layer, on a silicon substrate, and growing a silicon layer on the deposited layer, (A) after growth of the silicon layer, heat treatment is performed in an oxidizing atmosphere to oxidize a part of a surface side of the silicon layer, and the resulting silicon oxide layer is removed by etching with hydrofluoric acid. (B) With this silicon layer as a seed layer, a silicon layer is regrown homoepitaxially thereon.

Claims

1. An SOI substrate comprising an insulating base, and a crystalline silicon layer epitaxially grown on the insulating base, wherein the insulating base is a single crystal oxide substrate, a multi-layered substrate comprising a silicon substrate and a crystalline oxide layer, or a crystalline fluoride layer deposited on the silicon substrate, and

wherein the defect density of the crystalline silicon layer determined by a defect density measuring method using an iodine-containing etching solution is not more than 4×

10⁸/cm² in an entire depth direction, and the surface roughness of the crystalline silicon layer is not more than 4 nm but not less than 0.05 nm.

2. The SOI substrate of claim 1, wherein the defect density of the crystal silicon layer determined by a defect density measuring method using an iodine-containing etching solution is not more than 1×

10⁷/cm² in an entire depth direction.

3. The SOI substrate of claim 1 or 2, wherein the full width at half maximum of the X-ray diffraction rocking curve of a (004)-peak in the crystalline silicon layer, grown parallel to the surface of the substrate, is not more than 1,000 arcsec but not less than 100 arcsec.

4. The SOI substrate of claim 1, wherein the lattice constant of a silicon (100) -plane in the crystalline silicon layer perpendicular to the surface of the substrate is not less than 5.41 Å

s but not more than 5.44 Å

s.

5. The SOI substrate of claim 1, wherein the lattice constant of a silicon (001)-plane in the crystalline silicon layer parallel to the surface of the substrate is not more than 5.44 Å

s but not less than 5.41 Å

s.

6. The SOI substrate of claim 1, wherein the ratio of the lattice constant of a silicon (001)-plane in the crystalline silicon layer parallel to the surface of the substrate to the lattice constant of a silicon (100)-plane in the crystalline silicon layer perpendicular to the surface of the substrate is not more than 1.005 but not less than 0.995.

7. The SOI substrate of claim 1, wherein the ratio of the intensity of a (220)-reflection to the intensity of a (004)-reflection in the crystalline silicon layer parallel to the surface of the substrate, both reflections determined in X-ray diffraction measurement, is not more than 0.1.

8. The SOI substrate of claim 1, wherein the insulating base is the single crystalline oxide substrate, and the single crystalline oxide substrate is a sapphire substrate.

9. The SOI substrate of claim 1, wherein the insulating base is on the multi-layered substrate, and the crystalline oxide layer deposited on the silicon substrate as a substrate of the laminated substrate comprises a member selected from the group consisting of α

-Al₂O₃, γ

-Al₂O₃, θ

-Al₂O₃, MgO.Al₂O₃, CeO₂, SrTiO₃, (Zr<sub>1−

x</sub>,Y_x)O_y, Pb(Zr,Ti)O₃, LiTaO₃, or LiNbO₃ and the fluoride layer comprises CaF₂.

10. The SOI substrate of claim 1 wherein the thickness of the silicon layer is 0.03 μ

m to 0.7 μ

m.

71. A semiconductor device having an SOI substrate used as a substrate, wherein the SOI substrate comprises an insulating base, and a crystalline silicon layer epitaxially grown on the insulating base, wherein the insulating base is a single crystalline oxide substrate, a multi-layered substrate comprising a silicon substrate and a crystalline oxide layer, or a crystalline fluoride layer deposited on the silicon substrate, and

wherein the defect density of the crystalline silicon layer determined by a defect density measuring method using an iodine-containing etching solution is not more than 4×

10⁸/cm² in an entire depth direction, and the surface roughness of the crystalline silicon layer is not more than 4 nm but not less than 0.05 nm

wherein the semiconductor device is at least one of a field effect transistor and a bipolar transistor, and wherein the device characteristics improved by using the SOI substrate of any one of claims 1, 2, 4, 5, 6, 7, 8, and 9 as the SOI substrate of the semiconductor device are at least one of mutual inductance, cut-off frequency, flicker noise, and electrostatic discharge.

11. A method for producing an SOI substrate having a silicon layer with a low defect density formed on an insulating base, comprising the steps of:

(a) forming a first silicon layer on the insulating base;

(b) heat treating the first silicon layer in an oxidizing atmosphere containing a gas mixture of oxygen and hydrogen or containing steam to oxidize a part of the first silicon layer;

(c) removing a silicon oxide film formed in the preceding step (b) by etching;

and

(d) epitaxially growing a second silicon layer on the remaining first silicon layer.

12. The method of claim 11, further comprising repeating the steps (b) to (d) two or more times with the silicon layer formed in the step (d) being regarded as the first silicon layer formed in the step (a) in each repeat of steps (b) to (d).

13. The method of claim 11, wherein the temperature of heat treatment in the oxidizing atmosphere is not lower than 600°

C. but not higher than 1,300°

C.

14. The method of claim 11, wherein the temperature of heat treatment in the oxidizing atmosphere is not lower than 800°

C. but not higher than 1,200°

C.

15. The method of claim 11 wherein the temperature for epitaxial growth of the second silicon layer on the remaining first silicon layer is not lower than 550°

C. but not higher than 1,050°

C.

16. The method of claim 11, wherein the temperature for epitaxial growth of the second silicon layer on the remaining first silicon layer is not lower than 650°

C. but not higher than 950°

C.

17. The method of claim 11, wherein the remaining first silicon layer is heat treated in a hydrogen atmosphere or in a vacuum before the step of epitaxially growing the second silicon layer on the remaining first silicon layer.

18. The method of claim 11, wherein no silicon oxide is formed on the surface of the remaining first silicon layer or in the second silicon layer in the step of epitaxially growing the second silicon layer on the remaining first silicon layer.

19. The method of claim 11, wherein the pressure used in epitaxially growing the second silicon layer on the remaining first silicon layer is 10⁻

7 Torr or less.

20. The method of claim 11, wherein a method for epitaxially growing the second silicon layer on the remaining first silicon layer is UHV-CVD or MBE.

21. The method of claim 11, wherein when epitaxially growing the second silicon layer on the remaining first silicon layer, a growth temperature is set higher at an initial stage of growth than in the subsequent stages.

22. The method of claim 21, wherein a method for epitaxially growing the second silicon layer is APCVD or LPCVD.

23. The method of claim 11, further including the step of heat treating the SOI substrate in a nitrogen atmosphere after the step of epitaxially growing the second silicon layer.

24. The method of claim 23, further including the step of heat treating the SOI substrate in an oxidizing atmosphere after the step of heat treating the SOI substrate in the nitrogen atmosphere.

25. The method of claim 11, further including the step of heat treating the SOI substrate in a hydrogen atmosphere after the step of epitaxially growing the second silicon layer.

26. The method of claim 25, wherein the temperature of the heat treatment in a hydrogen atmosphere is not lower than 800°

C. but not higher than 1,200°

C.

27. The method of any one of claims 13-22, 23, 24, 25, and 26, further including the step of implanting silicon ions immediately after the step of forming the first silicon layer, to make a deep portion of the silicon layer amorphous, and annealing said amorphous silicon to recrystallize at least a portion thereof.

28. The method of claim 27, further comprising repeating the steps (b) to (d) two or more times with the silicon layer formed in the step (d) being regarded as the first silicon layer formed in the step (a) in each repeat of steps (b) to (d).

29. The method of claim 27, wherein the insulating base is a single crystalline oxide substrate.

30. The method of claim 27, wherein the insulating base is a multi-layered substrate comprising a silicon substrate and at least one additional layer deposited on the silicon substrate selected from the group consisting of a crystalline oxide layer and a crystalline fluoride layer deposited on the silicon substrate.

31. The method of claim 11, further including the step of implanting silicon ions immediately after the step of forming the first silicon layer, to make a deep portion of the silicon layer amorphous, and annealing said amorphous silicon to recrystallize at least a portion thereof.

32. The method of claim 31, wherein the annealing is performed first in a nitrogen atmosphere, and then performed in an oxidizing atmosphere.

33. The method of claim 32, further including the step of removing a silicon oxide film by etching after the annealing in the oxidizing atmosphere.

34. The method of claim 11, further comprising the step of polishing the silicon layer after the step of epitaxially growing the second silicon layer.

35. The method of any one of claims 13-22, 23, 24, 25-33, and 34, wherein the step of forming the first silicon layer on the insulating base comprises epitaxially growing the first silicon layer on the insulating base.

36. The method of claim 35, further comprising repeating the steps (b) to (d) two or more times with the silicon layer formed in the step (d) being regarded as the first silicon layer formed in the step (a) in each repeat of steps (b) to (d).

37. The method of claim 35, wherein the insulating base is a single crystalline oxide substrate.

38. The method of claim 35, wherein the insulating base is a multi-layered substrate comprising a silicon substrate and at least one additional layer deposited on the silicon substrate selected from the group consisting of a crystalline oxide layer and a crystalline fluoride layer deposited on the silicon substrate.

39. The method of any one of claims 13-22, 23, 24, 25-33, and 34, wherein the insulating base is a single crystalline oxide substrate.

40. The method of claim 39, further comprising repeating the steps (b) to (d) two or more times with the silicon layer formed in the step (d) being regarded as the first silicon layer formed in the step (a) in each repeat of steps (b) to (d).

41. The method of claim 39, wherein the insulating base is a multi-layered substrate comprising a silicon substrate and at least one additional layer deposited on the silicon substrate selected from the group consisting of a crystalline oxide layer and a crystalline fluoride layer deposited on the silicon substrate.

42. The method of claim 11, wherein the step of forming the first silicon layer on the insulating base comprises epitaxially growing the first silicon layer on the insulating base.

43. The method of claim 11, wherein the insulating base is a single crystalline oxide substrate.

44. The method of claim 43, wherein the insulating base is a sapphire substrate.

45. The method of any one of claims 13-22, 23, 24, 25-33, and 34-44, wherein the insulating base is a multi-layered substrate comprising a silicon substrate and at least one additional layer deposited on the silicon substrate selected from the group consisting of a crystalline oxide layer and a crystalline fluoride layer deposited on the silicon substrate.

46. The method of claim 45, further comprising repeating the steps (b) to (d) two or more times with the silicon layer formed in the step (d) being regarded as the first silicon layer formed in the step (a) in each repeat of steps (b) to (d).

47. The method of claim 11, wherein the insulating base is a multi-layered substrate comprising a silicon substrate and at least one additional layer deposited on the silicon substrate selected from the group consisting of a crystalline oxide layer and a crystalline fluoride layer deposited on the silicon substrate.

48. The method of claim 47, wherein the crystalline oxide layer comprises any of α

-Al₂O₃, γ

-Al₂O₃, θ

-Al₂O₃, MgO•

Al₂O₃, CeO₂, SrTiO₃, (Zr<sub>1−

x</sub>,Y_x)O_y, Pb(Zr,Ti)O₃, LiTaO₃, or LiNbO₃, and any crystalline fluoride layer comprises CaF₂.

49. The method of any one of claims 13-22, 23, 24, 25-33, 34-47, further comprising repeating the steps (b) to (d) two or more times with the silicon layer formed in the step (d) being regarded as the first silicon layer formed in the step (a) in each repeat of steps (b) to (d).

62. An SOI substrate produced by the method of any one of claims 11-22, 23, 24, 25-33, 34-48, 50, 51, 53, 54, 55, and 56.

63. A semiconductor device having an SOI substrate produced by the method of any one of claims 11-22, 23, 24, 25-33, 34-48, 50, 51, 53, 54, 55, and 56.

64. The semiconductor device of claim 63, which is at least one of a field effect transistor and a bipolar transistor, and wherein the device performance improved by using the SOI substrate is at least one of transconductance, cut-off frequency, flicker noise, and electrostatic discharge.

50. A method for producing an SOI substrate having a silicon layer with a low defect density formed on an insulating base, comprising the steps of:

(a) forming a first silicon layer on the insulating base;

(b) implanting silicon ions into the first silicon layer, to make a deep portion of the first silicon layer amorphous, performing annealing for recrystallization, and then heat treating the first silicon layer in a hydrogen atmosphere; and

(c) epitaxially growing a second silicon layer on the first silicon layer heat treated in a hydrogen atmosphere.

51. The method of claim 50, wherein the steps (a) to (c) are performed in situ.

52. The method of claim 50 or 51, wherein the temperature of the heat treatment in hydrogen is not lower than 800°

C. but not higher than 1,200°

C.

53. The method of claim 50, further including the step of implanting silicon ions immediately after the step of heat treating the first silicon layer in a hydrogen atmosphere, to make a deep portion of the silicon layer amorphous, and performing annealing for recrystallization.

54. The method of claim 53, wherein the annealing is performed first in a nitrogen atmosphere, and then performed in an oxidizing atmosphere.

55. The method of claim 54, further including the step of removing a silicon oxide film by etching after the annealing in the oxidizing atmosphere.

56. The method of claim 50, further comprising the step of applying chemical and/or mechanical polishing to the silicon layer after the step of epitaxially growing the second silicon layer.

57. The method of any one of claims 50, 51, 53, 54, 55, and 56, wherein the step of forming the first silicon layer on the insulating base is the step of epitaxially growing the first silicon layer on the insulating base.

58. The method of any one of claims 50, 51, 53, 54, 55, and 56, wherein the insulating base is a single crystalline oxide substrate.

59. The method of claim 58, wherein the single crystalline oxide substrate is a sapphire substrate.

60. The method of any one of claims 50, 51, 53, 54, 55, and 56, wherein the insulating base is a multi-layered substrate comprising a silicon substrate as a substrate and a crystalline oxide layer or fluoride layer deposited on the silicon substrate.

61. The method of claim 60, wherein the crystalline oxide layer comprises any of α

-Al₂O₃, γ

-Al₂O₃, θ

-Al₂O₃, MgO•

Al₂O₃, CeO₂, SrTiO₃, (Zr<sub>1−

x</sub>,Y_x)O_y, Pb(Zr,Ti)O₃, LiTaO₃, or LiNbO₃, and the crystalline fluoride layer comprises CaF₂.

65. A semiconductor device having an SOI substrate used as a substrate,

wherein the SOI substrate comprising an insulating base, and a crystalline silicon layer epitaxially grown on the insulating base, wherein the insulating base is a single crystalline oxide substrate, a multi-layered substrate comprising a silicon substrate and a crystalline oxide layer, or a crystalline fluoride layer deposited on the silicon substrate, and

wherein the defect density of the crystalline silicon layer determined by a defect density measuring method using an iodine-containing etching solution is not more than 4×

10⁸/cm² in an entire depth direction, and the surface roughness of the crystalline silicon layer is not more than 4 nm but not less than 0.05 nm.

66. The semiconductor device of claim 65, which is MOSFET.

67. The semiconductor device of claim 65, which is a bipolar transistor.

68. The semiconductor device of claim 65, which is a diode.

69. The semiconductor device of claim 65, which is a semiconductor integrated circuit.

70. The semiconductor device of claim 65, which is a semiconductor integrated circuit composed of MOSFET.

72. A method for producing a semiconductor device on an SOI substrate comprising an insulating base, and a silicon layer formed on the insulating base, comprising the steps of:

(a) forming a first silicon layer on the insulating base;

(b) heat treating the first silicon layer in an oxidizing atmosphere comprising a mixture of oxygen and hydrogen or steam to oxidize a part of the first silicon layer;

(c) removing a silicon oxide film formed in the preceding step (b) by etching;

(d) epitaxially growing a second silicon layer on the remaining first silicon layer; and

(e) heat treating a silicon layer, formed in the preceding step (d), in an oxidizing atmosphere to oxidize a part of the surface of the silicon layer, and then removing a silicon oxide film, which has been formed, by etching to adjust the silicon layer to a desired thickness.

73. The method of claim 72, further implanting the step of injecting silicon ions after the step of forming the first silicon layer, to make a deep portion of the silicon layer amorphous, and annealing said amorphous silicon to recrystallize at least a portion thereof.

74. The method of claim 72, further comprising the step of heat treating a silicon layer in a hydrogen atmosphere after the step (d) of epitaxially growing the second silicon layer.

75. The method of claim 72, further comprising performing chemical and/or mechanical polishing of a silicon layer before or after the step (e).

76. A method for producing a semiconductor device on an SOI substrate comprising an insulating base, and a silicon layer formed on the insulating base, comprising the steps of:

(a) forming a first silicon layer on the insulating base;

(b) implanting silicon ions immediately after the step of forming the first silicon layer, to make a deep portion of the first silicon layer amorphous, annealing to recrystallize at least a portion thereof, and then heat treating the first silicon layer in a hydrogen atmosphere;

(c) epitaxially growing a second silicon layer on the first silicon layer heat treated in a hydrogen atmosphere; and

(d) heat treating a silicon layer, formed in the step (c), in an oxidizing atmosphere to oxidize a part of the silicon layer, and then removing the silicon oxide film, which has been formed, by etching to adjust the silicon layer to a desired thickness.

77. The method of claim 76, further comprising performing chemical and/or mechanical polishing to the resulting silicon layer before or after the step (d).