U.S. patent number 3,829,556 [Application Number 05/237,896] was granted by the patent office on 1974-08-13 for growth of gallium nitride crystals.
This patent grant is currently assigned to Bell Telephone Laboratories, Incorporated. Invention is credited to Ralph Andre Logan, Carl Dryer Thurmond.
United States Patent |
3,829,556 |
Logan , et al. |
August 13, 1974 |
GROWTH OF GALLIUM NITRIDE CRYSTALS
Abstract
The size and photoluminescent efficiency of crystals of gallium
nitride, grown in a solution of molten gallium and bismuth, are
improved by maintaining the partial pressure of ammonia vapor in a
hydrogen gas atmosphere flowing above the solution at a value which
is, at most, about an order of magnitude greater than the
"equilibrium pressure" of formation vs. decomposition of gallium
nitride. The photoluminescent efficiency of a blue band, whose
energy is centered around 4,350 angstroms, emitted by such gallium
nitride crystals is also improved by introducing zinc vapor into
the carrier gas.
Inventors: |
Logan; Ralph Andre (Morristown,
NJ), Thurmond; Carl Dryer (Morristown, NJ) |
Assignee: |
Bell Telephone Laboratories,
Incorporated (Murray Hill, NJ)
|
Family
ID: |
22895695 |
Appl.
No.: |
05/237,896 |
Filed: |
March 24, 1972 |
Current U.S.
Class: |
423/409;
252/62.3GA; 117/67; 117/952 |
Current CPC
Class: |
C09K
11/7492 (20130101); C30B 19/02 (20130101); C30B
29/406 (20130101) |
Current International
Class: |
C30B
19/00 (20060101); C30B 19/02 (20060101); C09K
11/74 (20060101); C01h 021/06 () |
Field of
Search: |
;423/409 ;75/134T
;252/62.3GA |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3414441 |
December 1968 |
Gershenzon et al. |
|
Other References
Johnson et al.: "Journal of Physical Chemistry," Vol. 36, (1932),
p. 2,652. .
Maruska et al.: "Applied Physics Letters," Vol. 15, No. 10, Nov.
15, 1969, pp. 327-329..
|
Primary Examiner: Vertiz; Oscar R.
Assistant Examiner: Miller; Hoke S.
Attorney, Agent or Firm: Caplan; D. I.
Claims
What is claimed is:
1. A method of growing a crystal of gallium nitride which comprises
the steps of:
a. placing a substrate of sapphire in a solution comprising molten
gallium which contains bismuth as an inhibitor of the growth of
gallium nitride, at a temperature in the range of between about
850.degree.C and about 1,050.degree.C; and
b. flowing a gas mixture comprising ammonia vapor in hydrogen gas
across the exposed surface of the solution, said ammonia vapor
being maintained at a predetermined partial pressure which is no
more than about an order of magnitude greater than the equilibrium
partial pressure of ammonia vapor with respect to the formation vs.
decomposition of gallium nitride in said solution, whereby a single
crystal layer of gallium nitride is grown on the substrate in the
solution.
2. The method recited in claim 1 in which the composition of the
solution is in the range between about 10 atomic percent to about
90 atomic percent bismuth in gallium, and the partial pressure of
ammonia vapor does not exceed 0.03.
3. The method recited in claim 1 in which a temperature gradient is
established across the exposed surface of the solution, said
temperature gradient being in the range of about 17.degree. to
about 33.degree. C. per inch.
4. The method recited in claim 1 in which the said partial pressure
of the ammonia vapor is no more than about five times the said
equilibrium partial pressure.
5. The method recited in claim 4 in which the partial pressure of
ammonia vapor is about twice the equilibrium pressure.
6. The method recited in claim 1 in which the substrate has a
predeposit thereon of epitaxial gallium nitride.
7. The method recited in claim 1 which further includes introducing
zinc vapor into the gas mixture.
8. The method recited in claim 7 in which the partial pressure of
zinc vapor is of the order of 0.1 atmosphere.
9. A method of growing a crystal of gallium nitride which
comprises:
a. placing a substrate of sapphire in a solution comprising molten
gallium and an inhibitor of the growth of gallium nitride, at a
temperature in the range of between about 850.degree.C and about
1,050.degree.C, said inhibitor being essentially a member of the
group consisting of bismuth, antimony, tin, thallium and
indium;
b. flowing a gas mixture containing ammonia vapor in hydrogen
across the exposed surface of the solution, said ammonia vapor
being at a predetermined partial pressure no more than five times
the equilibrium pressure for the formation vs. decomposition of
gallium nitride, whereby a single crystal layer of gallium nitride
is grown on the substrate in the solution.
10. The method of claim 9 in which a temperature gradient is
maintained in the range of about 17.degree. to about 33.degree.C
per inch across the exposed surface of the solution during the step
of flowing the gas mixture.
Description
FIELD OF THE INVENTION
This invention relates to methods for growing luminescent crystals
and, more particularly, to a technique for the growth of
photoluminescent gallium nitride crystals.
BACKGROUND OF THE INVENTION
The development of technologies using optical displays and optical
sources, such as the computer and communication technologies, has
necessitated a search for light-emitting devices which can emit
light at certain desired visible wavelengths or combinations
thereof (colors). It has long been known that semiconductive
gallium nitride can emit visible blue light when irradiated with
the invisible ultraviolet. Thus, blue photoluminescent
semiconductor devices, that is, devices emitting blue light under
excitation by an optical source, can be made using semiconductive
gallium nitride crystals as the photoluminescent material
("phosphor").
It has also been known in the prior art that gallium nitride
crystals can be formed from molten gallium by passing ammonia at
atmospheric pressure over the molten gallium at a temperature of
the order of 1,000.degree. C. See: W. C. Johnson et al., Journal of
Physical Chemistry, Vol. 36, p. 2651 (1932). However, crystals of
gallium nitride formed by such methods are limited to a particle
size of about a micron. See: H. G. Grimmeiss, Journal Applied
Physics, Vol. 41, p. 4054 (1960). Crystals of such a small size are
not very useful for devices.
On the other hand, in the growth of gallium phosphide crystals from
gallium solutions, an improvement in crystal size has been reported
by adding bismuth to the molten gallium growth solution, in order
to inhibit the formation of spurious gallium phosphide crystal
nuclei and thereby to allow more raw material to be available for
the growth of fewer but larger gallium phosphide crystals. See: F.
A. Trumbore et al., Applied Physics Letters, Vol. 9, p. 4 (1966).
It has been thought in the art, however, that any growth of gallium
nitride crystals from a solution, similar to that just mentioned
for gallium phosphide, cannot possibly yield reasonably large
crystals, since the amount of gallium nitride which can be
dissolved in the solution was believed to be too small. It would
therefore be desirable to have available a solution growth method
for growing gallium nitride crystals of considerably larger size
than previously obtained.
SUMMARY OF THE INVENTION
We have discovered a method by which gallium nitride crystals can
be grown in solution to a crystal size of the order of 1 centimeter
square by several mils thick or more, on a substrate such as
sapphire. In order to achieve this relatively large size growth, we
have utilized a modified solution growth technique in which a
gallium nitride crystal is grown on the substrate immersed in a
heated growth solution of molten gallium and bismuth, in the
presence of ammonia vapor above the solution in a furnace. We have
found that it is important that the rate of reaction of ammonia
with gallium be slowed by maintaining the partial pressure of the
ammonia vapor above the solution at a value which is much lower
than used in the prior art. The main consequence of this slower
reaction rate is the elimination of the undesired spreading of
solution which occurs at higher ammonia vapor pressures, whereby
the liquid gallium flows up and over the walls of the container
("boat") into the furnace.
In setting forth the range of the partial pressure of ammonia vapor
in hydrogen gas to be used in accordance with this invention, it is
convenient to define this range in terms of the "equilibrium
pressure" at which the competing processes, of formation of gallium
nitride from gallium vs. decomposition of gallium nitride by
hydrogen, are characterized by equal rates. In these terms, we have
found that the partial pressure of ammonia vapor should be
maintained in the range from slightly greater than this equilibrium
pressure to less than about five, and at most ten times this
equilibrium pressure, and preferably about twice this equilibrium
pressure.
In a specific embodiment of the invention, ammonia vapor in a
carrier gas, hydrogen, is passed over the surface of a growth
solution of gallium and bismuth at an elevated temperature.
Advantageously, zinc vapor is also introduced into the carrier gas,
in order to incorporate zinc as an impurity into the gallium
nitride crystals and thereby to improve the photoluminescent
efficiency. Immersed in the growth solution are substrates, such as
sapphire, for the epitaxial crystal growth of gallium nitride. A
temperature gradient is maintained across the surface of the growth
solution, such that the upstream end of the growth solution with
respect to the flowing carrier gas is at a somewhat higher
temperature than the downstream end. Thereby, while nitrogen from
the ammonia vapor will continuously dissolve into the growth
solution, mainly at the higher temperature (upstream) region of the
solution, a growth of gallium nitride crystals on the substrates
will tend to occur in the lower temperature (downstream) region.
This crystal growth thus occurs in a controllable fashion in which
the partial pressure of ammonia vapor in the carrier gas is
continuously maintained at a suitable value as set forth
previously.
Crystals of gallium nitride grown in accordance with our invention
have exhibited as much as 25 percent (photoluminescent efficiency)
conversion at room temperature of ultraviolet light from a nitrogen
gas laser (3,500 angstroms) into visible blue light (ranging from
about 3,800 to 6,200 angstroms). Such crystals are also expected to
be useful as the lasing material in solid state laser sources of
blue light.
BRIEF DESCRIPTION OF THE DRAWING
This invention can be better understood from the following detailed
description when read in conjunction with the drawing in which the
FIGURE shows gallium nitride crystals being grown in a furnace,
partly in perspective, in accordance with a specific embodiment of
the invention.
DETAILED DESCRIPTION
As shown in the FIGURE, a furnace 10 is maintained at a temperature
profile indicated immediately beneath it, by conventional heating
means (not shown). It should be understood that the precise
temperatures indicated in the FIGURE are not crucial, but can vary
over wide ranges so long as the overall general shape of the
profile is maintained. The furnace 10 has an inlet 11 and an outlet
12 for the flow of ambient gas. At the inlet, this gas is composed
of ammonia vapor in the carrier gas, hydrogen, at a total pressure
of 1 atmosphere. Toward the downstream end of the furnace 10 is
located a carbon heat sink 13 partially surrounding a growth boat
14; whereas toward the upstream of this furnace 10 is located a
zinc dopant boat 15. In this way, doping impurities of zinc are
vaporized from the dopant boat 15 and then flow with the ambient
gas over the growth boat 14.
By way of illustration only, typical dimensions for the various
elements and their mutual spacing are as follows. The growth boat
14 is about three inches long in the x direction, one-half inch
wide in the z direction, and one-half inch deep in the y direction.
The heat sink 13 is about four inches long in the x direction and
is about three-quarter inch wide in the z direction, and has a
recess about one inch long in the x direction and one-half inch
wide in the z direction, in order to accommodate a portion of the
growth boat 14 in close contact therewith. About 12 inches to the
left-hand side of the growth boat 14 and at a distance of about two
inches from the inlet side of the furnace 10, the dopant boat 15 is
located. This dopant boat 15 is about three inches long in the x
direction, one-half inch wide in the z direction, and one-half inch
deep in the y direction. The furnace 10 is in the form of a
cylinder having a cross-section diameter of about seven-eighths
inch. This furnace 10, as well as the growth boat 14 and the dopant
boat 15, can be made of pyrolitic carbon or quartz, for
example.
In order to grow gallium nitride crystals, a growth solution alloy
of gallium and bismuth is introduced into the growth boat 14 to
fill the boat typically about nine-tenths full. Then, sapphire
substrates oriented typically (0001) are placed on the top surface
of the solution in the growth boat 14. Next, these substrates 21
are covered with more solution of gallium and bismuth so that the
growth solution in the growth boat 14 fills this boat, thereby
leaving these substrates 21 suspended in the growth solution. Each
of these substrates 21 has a cross section of approximately 1
cm.sup.2 in the xz plane and advantageously has been coated with a
predeposit of a gallium nitride epitaxial layer on the surface
where gallium nitride is to be grown. For example, well-known vapor
phase reactions of the prior art can be used for this predeposit,
typically three microns thick. However, it should be understood
that this pre-deposit is not necessary, but such a predeposit is
useful in nucleating growth so that a gallium nitride crystal is
grown over the entire predeposited region of the substrate rather
than a major fraction thereof.
The temperature profile indicated in the temperature profile in the
drawing is then established in which the average temperature of the
growth alloy is in the range of about 850.degree. C. to
1,050.degree. C., typically about 1,000.degree. C. The left-hand
end of the growth boat 14 is maintained at a temperature gradient
corresponding to a temperature difference of about 75.degree. C.
over a distance of about 3 inches in the x direction (allowing for
the 1 inch recess in the carbon heat sink 13). This temperature
difference is not critical and can vary by about 50.degree. C., and
thus the corresponding temperature gradient can be in the range of
about 17.degree. C. to 33.degree. C. per inch. The dopant boat 15
is maintained at a temperature in the range of about 500.degree. C.
to about 825.degree. C. and contains molten zinc 15.5. Thereby,
zinc vapor at partial pressures of between approximately 0.001 and
0.1 atmosphere is introduced into the carrier gas of hydrogen
containing ammonia vapor, flowing from the inlet 11. The rate of
gas flow from inlet 11 to outlet 12 is maintained at a rate of
typically 140 cm.sup.3 per minute. With the temperature profile
maintained as indicated in the FIGURE, gallium nitride then grows a
single crystal layer on the sapphire substrates 21 to a thickness
of a few mils in a time period of about 16 hours.
The solution in the growth boat 14 contains gallium and bismuth
typically in a 50/50 ratio by atomic percent. For this 50/50
mixture, advantageously the partial pressure of ammonia at the
inlet 11 is adjusted to be in the range of about 3 .times.
10.sup.-.sup.3 and 1 .times. 10.sup.-.sup.2 atmospheres, typically
6 .times. 10.sup.-.sup.3 atmospheres. However, a different ratio of
bismuth to gallium also can be used in this invention. In
particular, this ratio can be as high as about 90 atomic percent
bismuth in combination with using a somewhat higher partial
pressure of ammonia (0.03 atmosphere) in the hydrogen gas flowing
into the inlet pipe 11. Likewise, as little as 30 atomic percent
bismuth in gallium solution may be used in combination with a
partial pressure of ammonia of about 4 .times. 10.sup.-.sup.3
atmosphere in the flowing hydrogen gas.
It should be recognized that higher concentrations of bismuth in
the gallium solution in the boat 14 correspond to a greater ammonia
partial pressure in the carrier gas flowing from the inlet pipe 11
to the outlet pipe 12, in order to maintain the same conditions
relative to equilibrium conditions (rate of decomposition in
hydrogen equal to the rate of formation from gallium of gallium
nitride), according to the well-known stoichiometric relations:
2 NH.sub.3 + 2 Ga .fwdarw. 2 GaN + 3H.sub.2.
Gallium nitride semiconductor crystals grown by the above-described
method are characterized by n-type conductivity. Utilizing these
crystals grown by the above-described method, conversion of at
least 25 percent of the output radiation of a nitrogen gas laser
(about 3,500 A) into visible blue light has been achieved.
While this invention has been described in detail in terms of a
specific embodiment, various modifications may be made without
departing from the scope of this invention. For example, inhibitors
other than bismuth can be used in the molten gallium growth
solution, such as antimony, lead, tin, thallium, and indium. In
addition, instead of the use of sapphire substrate, other
substrates can be used, such as silicon carbide or other substrates
with lattice structures compatible with the growth of gallium
nitride. Moreover, it should be recognized by the skilled worker
that as there becomes available in the art a method for making
p-type gallium nitride crystals, then such crystals could be used
as the substrate for making p-n junctions by the above-described
method in accordance with the invention. Such p-n junctions would
be especially useful for making electroluminescent devices, that
is, light-emitting diodes excited by electrical current.
Alternatively, various surface barriers, such as Schottky barriers
formed by such metals as gold or aluminum, on the n-type gallium
nitride crystals grown by the method of this invention, can be
utilized instead of p-n junctions for the fabrication of
electroluminescent devices.
* * * * *