Preparation process of compound semiconductor

• US 4,767,494 A
• Filed: 09/19/1986
• Issued: 08/30/1988
• Est. Priority Date: 07/04/1986
• Status: Expired due to Term

• Current Assignee: Nippon Telegraph and Telephone Corporation
• Original Assignee: Nippon Telegraph and Telephone Corporation
• Inventors: Makimoto, Toshiki, Kobayashi, Naoki, Horikoshi, Yoshiji
• Primary Examiner(s): Doll, John
• Assistant Examiner(s): BRENEMAN, ROBERT B
• Application Number:
  US06/909,287
• Time in Patent Office: 711 Days
• Field of Search: 156/606, 156/610, 156/612, 156/613, 156/DIG. 70, 156/DIG. 89, 156/DIG. 113, 148/DIG. 72, 148/DIG. 160, 427/51, 427/86, 437/110
• US Class Current: 117/93
• 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 29/48 AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
• CPC Class Codes: C30B 29/68 Crystals with laminate structure, e.g. "superlattices"
• CPC Class Codes: H01L 21/02395 Arsenides
• CPC Class Codes: H01L 21/02463 Arsenides
• CPC Class Codes: H01L 21/02505 consisting of more than two layers
• CPC Class Codes: H01L 21/02546 Arsenides
• CPC Class Codes: H01L 21/02551 Group 12/16 materials
• CPC Class Codes: H01L 21/02576 N-type
• CPC Class Codes: H01L 21/02579 P-type
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD

Abstract

A compound semiconductor thin film is formed by growing a plurality of molecular layers one over another. According to the present invention, while a carrier gas and a small quantity of hydride containing an element in Group V or VI are normally flowed, an organometallic compound which is diluted with hydrogen and which contains an element in Group III or II and a hydride which is diluted with hydrogen and which contains an element in Group V or VI are alternately introduced over a substrate so that an atomic layer of an element in Group III or II and an atomic layer of an element in Group V or VI are alternately grown over the substrate. According to this method, grown layers having a high degree of purity can be obtained. A portion such as a Ga-Ga two-layer structure formed in the growth of a surface of an element in Group III or II can easily be eliminated by the introduction of a hydrogen halide so that the surface defects and deep levels are significantly decreased and perfect crystals can be obtained. According to the present invention, a high-concentration doping of a III-V compound semiconductor becomes possible. The method of the present invention is advantageous in the fabrication of high-speed FETs and multi-quantum-well lasers using compound semiconductors.

Claims

1. A process for preparing compound semiconductor thin films in which an organometallic compound cotaining an element of Group III or II and a hydride containing an element of Group V or VI are transported over a heated substrate and are subjected to thermal decomposition, whereby a III-V or 11-VI compound semiconductor is grown over said heated substrate, the process comprising:

repeating a cycle consisting of the following steps, whereby a III-V or II-VI compound semiconductor is grown over said heated substrate by forming alternating layers of an element of Group III or II and an element of Group V or VI, respectively;

(a) introducing over said heated substrate a carrier gas comprising a hydride containing an element of Group V or VI and present in a first concentration, said carrier gas further comprising at least one organometallic compound containing an element of Group III or II and present in a concentration, to thermally decompose the organometallic compound and form a layer of at least one element of Group III or II, wherein said first concentration of said hydride is a molar fraction ranging from a value which corresponds to the equilibrium molar fraction of said element of Group V or VI on said III-V or II-VI compound semiconductor at the temperature of said heated substrate up to a value at which said element of Group V or VI is not substantially incorporated into said layer of at least one element of Group III or II;

(b) interrupting the introduction of said organometallic compound;

(c) introducing over said heated substrate a carrier gas comprising a hydride containing an element of Group V or VI and present in a second concentration, which second concentration is higher in hydride than said first concentration, to thermally decompose the hydride and form a layer of an element of Group V or VI on top of said layer of an element of Group III or II; and

(d) interrupting the introduction of said hydride at said second concentration.

2. The process as claimed in claim 1, wherein the temperature of said heated substrate is between 430°

C. and 520°

C.

3. The process as claimed in claim 1, wherein said carrier gas is hydrogen.

4. The process as claimed in claim 1, wherein said first concentration of said hydride in step (a) is a molar fraction ranging from a value which corresponds to the equilibrium molar fraction of said element of Group V or VI on said III-V or II-VI compound semiconductor at the temperature of said heated substrate up to 4×

10^-5.

5. The process as claimed in claim 1, wherein said second concentration of said hydride in step (c) is a molar fraction of greater than 1×

10^-3.

6. The process as claimed in claim 1, wherein the concentration of said at least organometallic compound in step (a) is a molar fraction of greater than 1×

10^-4.

7. The process as claimed in claim 1, wherein two kinds of organometallic compounds containing different Group III or II elements are introduced in step (a).

8. The process as claimed in claim 1, wherein said at least one organometallic compound contains ethyl radicals.

9. A process for preparing compound semiconductor thin films in which an organometallic compound containing an element of Group III or II and a hydride containing an element of Group V or VI are introduced over a heated substrate and are subjected to thermal decomposition, whereby a III-V or II-VI compound semiconductor is grown over said heated substrate, the process comprising:

repeating a cycle consisting of the following steps, whereby a III-V or II-VI compound semiconductor is grown over said heated substrate by forming alternating layers of an element of Group III or II and an element of Group V or VI, respectively;

(a) introducing over said heated substrate a first carrier gas comprising a hydride containing an element of Group V or VI and present in a first concentration, said first carrier gas further comprising at least one organometalIic compound containing an element of Group III or II and present in a concentration, to thermally decompose the organometallic compound and form a layer of at least one element of Group III or II, wherein said first concentration of said hydride is a molar fraction ranging from a value which corresponds to the equilibrium molar fraction of said element of Group V or VI on said III-V or II-VI compound semiconductor at the temperature of said heated substrate up to a value at which said element of Group V or VI is not substantially incorporated into said layer of at least one element of Group III or II;

(b) interrupting the introduction of said organometallic compound; and

(c) introducing over said heated substrate a second carrier gas comprising a hydride containing an element of Group V or VI and present in a second concentration, which second concentration is higher in hydride than said first concentration, to thermally decompose the hydride and form a layer of an element of Group V or VI on top of said layer of at least one element of Group III or II; and

(d) interrupting the introduction of said hydride at said second concentration; and

(e) introducing over said heated substrate a third carrier gas comprising a hydrogen halide and present in halide which is diluted by a third carrier gas to a concentration of said hydrogen halide.

10. The process as claimed in claim 9, wherein said, second, and third carrier gases in steps (c) and (e) consist of hydrogen.

11. The process as claimed in claim 9, wherein said first concentration of said hydride in step (a) is a molar fraction ranging from a value which corresponds to the equilibrium molar fraction of said element of Group V or VI on said III-V or II-VI compound semiconductor at the temperature of said heated substrate up to 4×

10^-5.

12. The process as claimed in claim 9, wherein said second concentration of said hydride in step (c) is a molar fraction of greater than 1×

10^-3.

13. The process as claimed in claim 9, wherein the concentration of said at least one organometallic compound in step (a) is a molar fraction greater than 1×

10^-4.

14. The process as claimed in claim 9, wherein the concentration of said hydrogen halide in step (e) is a molar fraction of greater than 1×

10^-4.

15. The process as claimed in claim 9, wherein said hydrogen halide is hydrogen chloride.

16. The process as claimed in claim 9, wherein said heated substrate is mantained at a temperature higher than 400°

C. but lower than 600°

C.

17. The process as claimed in claim 9, wherein two kinds of organometallic compounds containing different Group III or II elements are introduced in step (a).

18. The process as claimed in claim 9, wherein said at least one organometallic compound contains ethyl radicals.

19. A process for preparing compound semiconductor thin films, comprising:

repeating a cycle consisting of the following steps, whereby a compound semiconductor which is an arsenide of a Group III or II element is grown over said heated substrate by forming alternating layers of at least one element of Group III or II and arsenic, respectively;

(a) introducing over said heated substrate a carrier gas comprising hydrogen and arsine (AsH₃) present in a first concentration, said carrier gas further comprising at least one organometallic compound containig an element of Group III or II and present in a concentration, to thermally decompose the organometallic compound and form a layer of at least one of Group III or II, wherein said first concentration of arsine is a molar fraction ranging from a value which corresponds to the equilibrium molar fraction of arsenic on said III-V or II-VI compound semiconductor at the temperature of said heated substrate up to a value at which said arsenic is not substantially incorporated into said layer of at least one element of Group III or II;

(b) interrupting the introduction of said organometallic compound;

(c) introducing said heated substrate a carrier gas comprising hydrogen and arsine (AsH₃) and present in a second concentration, which second concentration is higher in arsine (AsH₃) than said first concentration, to thermally decompose the arsine (AsH₃) and form a layer of arsenic on top of said layer of at least one element of Group III or II;

and introducing in any of steps (a) through (c), of said cycle silane (SiH₄), thereby doping said III-V or II-VI compound semiconductor.

20. A process for preparing compound semiconductor thin films, comprising:

repeating a cycle consisting of the following steps, whereby a III-V compound semiconductor is grown over said heated substrate by forming alternating layers of an element of Group III and an element of Group V, respectively;

(a) introducing over said heated substrate a carrier gas comprising hydrogen and a hydride containing an element of Group V and present in a first concentration, said carrier gas further comprising at least one organometallic compound containing an element of Group III and present in a concentration, to thermally decompose the organometallic compound and form a layer of at least one element of Group III, wherein said first concentration of said hydride is a molar fraction ranging from a value which corresponds to the equilibrium molar fraction of said element of Group V on said III-V compound semiconductor at the temperature of said heated substrate up to a value at which said element of Group V is not substantially incorporated into said layer of at least one element of Group III;

(b) interrupting the introduction of said organometallic compound;

(c) introducing on said heated substrate a carrier gas comprising hydrogen and a hydride containing an element of Group V and present in a second concentration, which second concentration is higher in hydride than said first concentration, to thermally decompose the hydride and form a layer of an element of Group V on top of said layer of at least one element of Group III;

(d) interrupting the introduction of said hydride at said second concentration;

(e) introducing over said heated substrate a hydrogen halide which is diluted by said hydrogen carrier gas;

(f) interrupting the introduction of said hydrogen halide; and

(g) introducing over said heated substrate said carrier gas comprising hydrogen together with a compound containing an element in Group IV, VI or II, thereby doping said III-V compound semiconductor.

21. The process as claimed in claim 20, wherein said compound containing an element in Group IV, VI or II in step (g) is simultaneously introduced together with said at least one organometallic compound containing an element in Group III (a).

22. The process as claimed in claim 20, wherein said compound containing an element in Group IV, VI, or II in step (g) is introduced immediately after step (b).

23. The process as claimed in claim 20, wherein said compound containing an element in Group IV, VI or II in step (g) is introduced immediately after the interruption of the introduction of said hydride at said second concentration.

24. The process as claimed in claim 20, wherein said compound containing an element in Group IV, VI or II in step (g) is introduced during all of steps (a) through (f) of said cycle.

25. The process as claimed in claim 20, wherein said compound containing an element in Group IV, VI or II in step (g) and is silane (SiH₄).

26. The process as claimed in claim 25, wherein said silane has a molar fraction between 10^-7 and 10^-3.