High efficiency light emitting diodes from bipolar gallium nitride

• US 5,210,051 A
• Filed: 06/05/1991
• Issued: 05/11/1993
• Est. Priority Date: 03/27/1990
• Status: Expired due to Term

• Current Assignee: CREE Incorporated (Wolfspeed, Inc.)
• Original Assignee: Cree Research, Inc.
• Inventors: Carter, Calvin H. Jr.
• Primary Examiner(s): FOURSON III, GEORGE R
• Application Number:
  US07/710,827
• Time in Patent Office: 706 Days
• Field of Search: 437/107, 437/126, 437/127, 437/905, 437/173, 437/174, 148/DIG. 65, 148/DIG. 46, 148/DIG. 113, 148/DIG. 148, 148/DIG. 169
• US Class Current: 438/22
• CPC Class Codes: H01L 21/02378 Silicon carbide
• 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 21/02631 Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
• CPC Class Codes: H01L 24/32 of an individual layer connector
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/12032 Schottky diode
• CPC Class Codes: H01L 2924/12041 LED
• CPC Class Codes: H01L 33/0008 having p-n or hi-lo junctions
• CPC Class Codes: H01L 33/007 comprising nitride compounds
• CPC Class Codes: H01L 33/62 Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
• CPC Class Codes: Y10S 148/046 Electron beam treatment of devices
• CPC Class Codes: Y10S 148/113 Nitrides of boron or aluminum or gallium
• CPC Class Codes: Y10S 148/148 Silicon carbide
• CPC Class Codes: Y10S 438/925 Fluid growth doping control, e.g. delta doping

Abstract

The invention is a method of growing intrinsic, substantially undoped single crystal gallium nitride with a donor concentration of 7×10¹⁷ cm^-3 or less. The method comprises introducing a source of nitrogen into a reaction chamber containing a growth surface while introducing a source of gallium into the same reaction chamber and while directing nitrogen atoms and gallium atoms to a growth surface upon which gallium nitride will grow. The method further comprises concurrently maintaining the growth surface at a temperature high enough to provide sufficient surface mobility to the gallium and nitrogen atoms that strike the growth surface to reach and move into proper lattice sites, thereby establishing good crystallinity, to establish an effective sticking coefficient, and to thereby grow an epitaxial layer of gallium nitride on the growth surface, but low enough for the partial pressure of nitrogen species in the reaction chamber to approach the equilibrium vapor pressure of those nitrogen species over gallium nitride under the other ambient conditions of the chamber to thereby minimize the loss of nitrogen from the gallium nitride and the nitrogen vacancies in the resulting epitaxial layer.

Claims

1. A method of forming an epitaxial layer of p-type gallium nitride suitable for producing p-n junctions and junction diodes, the method comprising:

directing a molecular beam of nitrogen from an electron cyclotron resonance plasma containing nitrogen atoms onto the growth surface of a single crystal of silicon carbide that provides an acceptable lattice match for gallium nitride;

while

directing a molecular beam of gallium in the substantial absence of any other compounds onto the same silicon carbide growth surface;

while

maintaining the surface at a temperature of less than about 650°

C. but that is otherwise high enough to provide sufficient surface mobility for gallium atoms and nitrogen atoms to form a single crystal epitaxial layer of gallium nitride on the silicon carbide;

while

directing an acceptor species onto the surface until a desired epitaxial layer is formed; and

irradiating the epitaxial layer with an electron beam at an energy that is sufficient to activate the acceptor ions in the epitaxial layer, but that is less than the energy that would cause atomic displacement in the epitaxial layer thereby producing the epitaxial layer of p-type gallium nitride.

2. A method according to claim 1 wherein the step of introducing nitrogen atoms from a nitrogen-containing electron cyclotron resonance plasma comprises introducing nitrogen atoms that have been accelerated in the plasma at less than 100 electron volts.

3. A method according to claim 1 wherein the step of introducing nitrogen comprises introducing ammonia from an ammonia-containing electron cyclotron resonance plasma.

4. A method according to claim 1 wherein the step of directing nitrogen onto the growth surface comprises introducing ammonia from an ammonia-containing electron cyclotron resonance plasma.

5. A method according to claim 1 wherein the step of maintaining the surface at a temperature comprises maintaining the temperature at between about 600°

and 650°

C.

6. A method according to claim 1 wherein the step of directing an acceptor species onto the surface comprises directing a molecular beam of acceptor atoms in the substantial absence of other compounds.

7. A method according to claim 6 wherein the step of directing an acceptor species comprises directing magnesium atoms.

8. A method according to claim 1 wherein the step of directing an acceptor species onto the growth surface at a rate sufficient to produce a p-type epitaxial layer of gallium nitride upon the grown surface of silicon carbide comprises directing the acceptor species onto the surface at a rate sufficient for a the acceptor concentration to exceed the donor concentration of the n-type epitaxial layer formed during the preceding steps.

9. A method according to claim 1 wherein the step of directing nitrogen onto the growth surface of a single crystal of silicon carbide comprises directing the nitrogen onto the (0001) face of 6H silicon carbide.

10. A method according to claim 1 wherein the step of directing nitrogen onto the growth surface of a single crystal of silicon carbide comprises directing the nitrogen onto the (100) face of 3C silicon carbide.

11. A method according to claim 1 wherein the step of directing nitrogen onto the growth surface of a single crystal of silicon carbide comprises directing the nitrogen onto the (111) face of 3C silicon carbide.

12. A method according to claim 1 wherein the step of irradiating the surface follows the step of directing the acceptor species onto the surface.

13. A method according to claim 1 wherein the step of irradiating the surface is concurrent with the step of directing the acceptor species onto the surface.

14. A method according to claim 1 and further comprising the steps of:

directing a molecular beam of highly reactive, high flux, low uniform energy nitrogen atoms from an electron cyclotron resonance plasma containing nitrogen atoms onto the p-type epitaxial layer following the step of irradiating the surface;

while

directing a molecular beam of gallium atoms in the substantial absence of any other compounds onto the p-type epitaxial layer;

while

maintaining the p-type epitaxial layer at a temperature of less than about 650°

C. but that is otherwise high enough to provide sufficient surface mobility for the gallium atoms and the nitrogen atoms to form a single crystal epitaxial layer of n-type gallium nitride on the p-type epitaxial layer and a p-n junction between the layers.

15. A method according to claim 1 and further comprising the steps of:

directing a molecular beam of highly reactive, high flux, low uniform energy nitrogen atoms from an electron cyclotron resonance plasma containing nitrogen atoms onto the growth surface of a single crystal of silicon carbide that provides an acceptable lattice match for gallium nitride;

while

directing a molecular beam of gallium atoms in the substantial absence of any other compounds onto the same silicon carbide growth surface;

while

maintaining the surface at a temperature of less than about 650°

C. but that is otherwise high enough to provide sufficient surface mobility for the gallium atoms and the nitrogen atoms to form a single crystal epitaxial layer of gallium nitride on the silicon carbide;

all prior to the steps of forming the p-type epitaxial layer.