In-situ acceptor activation in group III-v nitride compound semiconductors

• US 5,926,726 A
• Filed: 09/12/1997
• Issued: 07/20/1999
• Est. Priority Date: 09/12/1997
• Status: Expired due to Term

• Current Assignee: JDS Uniphase Corporation (Lumentum Holdings Inc.), Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: SDL Inc (RWS Holdings Plc), Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Connell, G.A. Neville, Bour, David P., Scifres, Donald R.
• Primary Examiner(s): Bowers, Charles
• Assistant Examiner(s): CHRISTIANSON, KEITH ALAN
• Application Number:
  US08/928,250
• Time in Patent Office: 676 Days
• Field of Search: 438/478, 438/507, 438/508, 438/509, 257/190, 372/45, 117/952
• US Class Current: 438/507
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 29/403 AIII-nitrides
• CPC Class Codes: C30B 29/406 Gallium nitride
• CPC Class Codes: H01L 21/02458 Nitrides
• CPC Class Codes: H01L 21/0254 Nitrides
• CPC Class Codes: H01L 21/02579 P-type
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 33/007 comprising nitride compounds
• CPC Class Codes: H01L 33/325 characterised by the doping materials

Abstract

A method of manufacturing a p-type III-V nitride compound semiconductor utilizing vapor phase epitaxy is carried out in a MOCVD reactor by growing a III-V nitride compound semiconductor in the reactor employing a reaction gas containing a p-type impurity and then annealing in-situ the nitride compound semiconductor to bring about acceptor activation, the annealing carried out at a temperature below the growth temperature of the III-V nitride compound semiconductor during reactor cooldown. A nitrogen (N) reactant or precursor is provided in the reactor during the annealing step which can produce a reactive form of N capable of suppressing surface decomposition and does not produce atomic hydrogen. Also, acceptor activation is achieved through the employment of a cap layer comprising a n-type Group III-V nitride material, e.g., n-GaN, grown on the p-doped Group III-V nitride layer preventing the occurrence of hydrogenation of the underlying p-doped layer during cooldown. This non-post-growth activation eliminates the need for a subsequent thermal anneal step since any acceptor passivation is prevented in the first instance.

Claims

1. A method of manufacturing a p-type III-V nitride compound semiconductor utilizing vapor phase epitaxy comprising the steps of:

growing a III-V nitride compound semiconductor in a reactor employing a reaction gas containing a p-type impurity;

annealing said nitride compound semiconductor at a temperature below the growth temperature of the III-V nitride compound semiconductor to activate acceptors of the p-type impurity;

the improvement comprising the carrying out the step of annealing in-situ in the reactor during reactor cooldown immediately after semiconductor growth in a reactor ambient comprising a nitrogen precursor of dimethylhydrazine, phenylhydrazine or tertiarybutylamine.

2. The method according to claim 1 wherein said reaction contains at least one of a gallium source of trimethyl gallium, and an aluminum source selected from the group consisting of trimethyl aluminum and triethyl aluminum, an indium source selected from the group consisting of trimethyl indium and triethyl indium, together with a nitrogen precursor.

3. The method according to claim 1 wherein the p-type impurity is at least one selected the group consisting of Zn, Cd, Be, Mg, Ca, and Ba.

4. A method of manufacturing and activating in-situ a p-type III-V nitride compound semiconductor utilizing vapor phase epitaxy in a reactor comprising the steps of:

growing in the reactor a Group III-V nitride layer with a p-type dopant utilizing at least one Group III reactant with a nitrogen reactant at a growth temperature;

discontinuing the growth of the p-type Group III-V nitride layer by switch out of the p-type dopant and all of the reactants;

introducing a nitrogen precursor in the reactor that pyrolyzes into atomic nitrogen and molecular hydrogen for preventing decomposition of the as-grown p-type Group III-V nitride layer; and

reducing reactor temperature below the growth temperature to a temperature where dehydrogenation of the as-grown p-type Group III-V nitride layer is achieved while controlling the rate of reactor cooling in a temperature range conducive to p-type acceptor activation for a period of time sufficient for activation of the p-type acceptors of the p-type dopant in the as-grown p-type Group III-V nitride layer.

5. The method of manufacturing and activating in-situ of claim 4 further comprising the steps of:

discontinuing the flow of the nitrogen reactant in the reactor at a given temperature and permitting the occurrence of activation of the p-type acceptors.

6. The method of manufacturing and activating in-situ of claim 5 wherein said discontinuance of flow of the nitrogen reactant is below 900°

C.

7. The method of manufacturing and activating in-situ of claim 4 wherein said reactor temperature is monotonically reduced.

8. The method of manufacturing and activating in-situ of claim 4 wherein said reactor temperature is reduced in steps.

9. The method of manufacturing and activating in-situ of claim 4 wherein said reactor temperature is reduced to a first level for a period of time to permit the occurrence of activation and then further reduced to a second level where the flow of the nitride precursor is terminated.

10. The method of manufacturing and activating in-situ of claim 4 wherein said nitrogen precursor comprises dimethylhydrazine, phenylhydrazine or tertiarybutylamine.

11. The method of manufacturing and activating in-situ of claim 4 wherein the nitrogen reactant comprises ammonia and comprises the further steps of:

reducing the temperature in the reactor from the growth temperature to a temperature where decomposition of the as-grown p-type Group III-V nitride layer will not substantially occur in the presence of ammonia;

switching out of the reactor the ammonia and continuing with the steps of introducing the nitrogen precursor and controlling the rate of reactor cooling to permit acceptor activation.

12. The method of manufacturing and activating in-situ of claim 11 wherein, during cooldown, the reactor temperature is held at a given temperature for a predetermined period of time to permit completion of acceptor activation.

13. The method of manufacturing and activating in-situ of claim 11 wherein, during cooldown, the temperature of the reactor is monotonically reduced during a period of time to permit completion of acceptor activation.

14. The method of manufacturing and activating in-situ of claim 11 wherein said reactor temperature is monotonically reduced.

15. The method of manufacturing and activating in-situ of claim 11 wherein said reactor temperature is reduced in steps.

16. A method of manufacturing and activating in-situ a p-type III-V nitride compound semiconductor utilizing vapor phase epitaxy in a reactor comprising the steps of:

growing in the reactor a III-V nitride compound semiconductor in a reactor employing a reaction gas containing a p-type impurity utilizing at least one Group III reactant with a nitrogen reactant at a growth temperature;

switching out of the reactor the Group III reactant or reactants while continuing the flow of the nitrogen reactant to prevent surface decomposition of the as-grown III-V nitride compound semiconductor;

reducing the temperature in the reactor from the growth temperature to a temperature where decomposition of the as-grown III-V nitride compound semiconductor will not substantially occur;

switching out of the reactor the nitrogen reactant at a temperature where significant decomposition of the as-grown III-V nitride compound semiconductor will not occur and switching in a combined ambient gas permitting acceptor activation, said combined ambient gas comprising N₂ and H₂ ;

controlling the rate of cooldown in the presence of said combined ambient gas within a temperature range in which acceptor activation occurs until activation is completed; and

thereafter, cooling the reactor to room temperature.

17. The method of manufacturing and activating in-situ of claim 16 wherein said nitrogen reactant is NH₃.

18. The method of manufacturing and activating in-situ of claim 16 wherein the temperature of the reactor is monotonically decreased during acceptor activation.

19. The method of manufacturing and activating in-situ of claim 18 wherein said monotonical decrease in temperature is continuous.

20. The method of manufacturing and activating in-situ of claim 18 wherein said monotonical decrease in temperature is accomplished in a stepped manner.

21. The method of manufacturing and activating in-situ of claim 16 wherein the growth of said III-V nitride compound semiconductor takes place at a temperature below 1,000°

C. but above about 850°

C. and said activation takes place at a temperature at about 850°

C. or less.

22. The method of manufacturing and activating in-situ of claim 21 wherein the semiconductor growth takes place at around the temperature of 900°

C.

23. The method of manufacturing and activating in-situ of claim 16 wherein, during the step of reactor temperature reduction where decomposition of the as-grown III-V nitride compound semiconductor will substantially occur, a flow of NH₃ is maintained in the reactor until the temperature of the reactor is reduced to a temperature in the range of about 600°

C. to about 800°

C., after which the NH₃ flow is switched out of the reactor.

24. The method of manufacturing and activating in-situ of claim 16 wherein the acceptor activation temperature range is in a range of about 600°

C. to about 900°

C.

25. The method of manufacturing and activating in-situ of claim 16 wherein the step of switchout of the nitrogen reactant occurs in a temperature range of about 600°

C. to about 900°

C.

26. A method of manufacturing a p-type III-V nitride compound semiconductor utilizing vapor phase epitaxy comprising the steps of:

growing a III-V nitride compound semiconductor layer on a substrate in a reactor employing a reaction gas containing a p-type impurity; and

growing a III-V nitride compound semiconductor cap layer on the p-type III-V nitride compound semiconductor layer in a reactor employing a reaction gas containing a n-type impurity to prevent hydrogen passivation of the p-type III-V nitride compound semiconductor layer during subsequent growth or cooldown.

27. The method of claim 26 wherein said the p-type III-V nitride compound semiconductor layer comprises p-GaN and said the n-type III-V nitride compound semiconductor cap layer comprises n-GaN.

28. The method of claim 27 wherein the p-type impurity is at least one selected the group consisting of Zn, Cd, Be, Mg, Ca, and Ba.

29. The method of claim 26 further comprising the step of removing the n-type III-V nitride compound semiconductor cap layer and forming a metal ohmic contact with the p-type III-V nitride compound semiconductor layer.