U.S. patent application number 14/149121 was filed with the patent office on 2014-05-01 for reactor designs for use in ammonothermal growth of group-iii nitride crystals.
This patent application is currently assigned to THE REGENTS OF THE UNIVERSITY OF CALIFORNIA. The applicant listed for this patent is The Regents of the University of California. Invention is credited to Derrick Shane Kamber, Shuji Nakamura, Siddha Pimputkar, James S. Speck.
Application Number | 20140116326 14/149121 |
Document ID | / |
Family ID | 42153216 |
Filed Date | 2014-05-01 |
United States Patent
Application |
20140116326 |
Kind Code |
A1 |
Pimputkar; Siddha ; et
al. |
May 1, 2014 |
REACTOR DESIGNS FOR USE IN AMMONOTHERMAL GROWTH OF GROUP-III
NITRIDE CRYSTALS
Abstract
Reactor designs for use in ammonothermal growth of group-III
nitride crystals. Internal heating is used to enhance and/or
engineer fluid motion, gas mixing, and the ability to create
solubility gradients within a vessel used for the ammonothermal
growth of group-III nitride crystals. Novel baffle designs are used
for control and improvement of continuous fluid motion within a
vessel used for the ammonothermal growth of group-III nitride
crystals.
Inventors: |
Pimputkar; Siddha; (Santa
Barbara, CA) ; Kamber; Derrick Shane; (Goleta,
CA) ; Speck; James S.; (Goleta, CA) ;
Nakamura; Shuji; (Santa Barbara, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Regents of the University of California |
Oaklan |
CA |
US |
|
|
Assignee: |
THE REGENTS OF THE UNIVERSITY OF
CALIFORNIA
Oakland
CA
|
Family ID: |
42153216 |
Appl. No.: |
14/149121 |
Filed: |
January 7, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13128083 |
May 6, 2011 |
8641823 |
|
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PCT/US2009/063239 |
Nov 4, 2009 |
|
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14149121 |
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61112560 |
Nov 7, 2008 |
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Current U.S.
Class: |
117/71 ; 117/224;
422/245.1 |
Current CPC
Class: |
C30B 7/10 20130101; H01L
21/67109 20130101; C30B 7/105 20130101; Y10T 428/24355 20150115;
B01D 9/0031 20130101; Y10T 117/1096 20150115; C30B 29/40 20130101;
C30B 29/403 20130101; B01D 9/0013 20130101 |
Class at
Publication: |
117/71 ; 117/224;
422/245.1 |
International
Class: |
C30B 7/10 20060101
C30B007/10 |
Claims
1. An apparatus for growing one or more crystals, comprising: (a) a
vessel including a first zone containing source materials and a
second zone containing seed crystals, wherein the reaction vessel
is filled with a solvent for dissolving the source materials in the
first zone and transporting the dissolved source materials to the
seed crystals in the second zone for growth of the crystals; and
(b) at least one baffle positioned within the vessel and having a
plurality of openings configured to control a flow of a fluid
comprised of the solvent and the dissolved source materials therein
between the first and second zones, wherein the openings in the
baffle control motion patterns for the fluid through the
baffle.
2. The apparatus of claim 1, wherein the source materials comprise
group-III containing source materials, the seed crystals comprise
group-III nitride seed crystals, the solvent comprises a
nitrogen-containing solvent, and the crystals comprise group-III
nitride crystals.
3. The apparatus of claim 1, wherein the baffle establishes a
circular motion of the fluid within the vessel.
4. The apparatus of claim 1, wherein the fluid enters the baffle
through one or more of the openings near an outer edge of the
baffle and the fluid exits the baffle through one or more of the
openings in a region that is closer to a center of the baffle.
5. The apparatus of claim 1, wherein the fluid enters the baffle
through one or more of the openings in a region that is closer to a
center of the baffle and the fluid exits the baffle through one or
more of the openings closer nearer to an outer edge of the
baffle.
6. The apparatus of claim 1, wherein the openings redirect the
fluid through the baffle.
7. The apparatus of claim 1, wherein the baffle suppresses
nucleation and growth on undesired locations or surfaces within the
vessel, and enhances growth on desired locations or surfaces within
the vessel.
8. The apparatus of claim 1, wherein the baffle changes a
temperature, pressure or other properties of the fluid while the
fluid flows through the baffle.
9. The apparatus of claim 1, wherein the baffle incorporates one or
more heaters or coolers for the fluid.
10. A method of growing one or more crystals, comprising: (a)
placing source materials into a first zone of a vessel; (b) placing
seed crystals into a second zone of a vessel; (c) filling the
vessel with a solvent for dissolving the source materials in the
first zone and transporting the dissolved source materials to the
seed crystals in the second zone for growth of the crystals; and
(d) using at least one baffle positioned within the vessel and
having a plurality of openings to control a flow of a fluid
comprised of the solvent and the dissolved source materials therein
between the first and second zones, wherein the openings in the
baffle control motion patterns for the fluid through the
baffle.
11. The method of claim 10, wherein the source materials comprise
group-III containing source materials, the seed crystals comprise
group-III nitride seed crystals, the solvent comprises a
nitrogen-containing solvent, and the crystals comprise group-III
nitride crystals.
12. The method of claim 10, wherein the baffle establishes a
circular motion of the fluid within the vessel.
13. The method of claim 10, wherein the fluid enters the baffle
through one or more of the openings near an outer edge of the
baffle and the fluid exits the baffle through one or more of the
openings in a region that is closer to a center of the baffle.
14. The method of claim 10, wherein the fluid enters the baffle
through one or more of the openings in a region that is closer to a
center of the baffle and the fluid exits the baffle through one or
more of the openings closer nearer to an outer edge of the
baffle.
15. The method of claim 10, wherein the openings redirect the fluid
through the baffle.
16. The method of claim 10, wherein the baffle suppresses
nucleation and growth on undesired locations or surfaces within the
vessel, and enhances growth on desired locations or surfaces within
the vessel.
17. The method of claim 10, wherein the baffle changes a
temperature, pressure or other properties of the fluid while the
fluid flows through the baffle.
18. The method of claim 10, wherein the baffle incorporates one or
more heaters or coolers for the fluid.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation that claims the benefit
under 35 U.S.C. Section 120 of:
[0002] U.S. Utility patent application Ser. No. 13/128,083, filed
on May 6, 2011, by Siddha Pimputkar, Derrick S. Kamber, James S.
Speck and Shuji Nakamura, entitled "REACTOR DESIGNS FOR USE IN
AMMONOTHERMAL GROWTH OF GROUP-III NITRIDE CRYSTALS," attorneys'
docket number 30794.296-US-WO (2009-283-2), which application
claims the benefit under 35 U.S.C. Section 365(c) of:
[0003] P.C.T. International Patent Application Serial No.
US2009/063239, filed on Nov. 4, 2009, by Siddha Pimputkar, Derrick
S. Kamber, James S. Speck and Shuji Nakamura, entitled "REACTOR
DESIGNS FOR USE IN AMMONOTHERMAL GROWTH OF GROUP-III NITRIDE
CRYSTALS," attorneys' docket number 30794.296-WO-U1 (2009-283-2),
which application claims the benefit under 35 U.S.C. Section 119(e)
of:
[0004] U.S. Provisional Patent Application Ser. No. 61/112,560,
filed on Nov. 7, 2008, by Siddha Pimputkar, Derrick S. Kamber,
James S. Speck and Shuji Nakamura, entitled "REACTOR DESIGNS FOR
USE IN AMMONOTHERMAL GROWTH OF GROUP-III NITRIDE CRYSTALS,"
attorneys' docket number 30794.296-US-P1 (2009-283/285-1),
[0005] all of which applications are incorporated by reference
herein.
[0006] This application is related to the following co-pending and
commonly-assigned U.S. patent applications:
[0007] U.S. Utility patent application Ser. No. 11/921,396, filed
on Nov. 30, 2007, by Kenji Fujito, Tadao Hashimoto and Shuji
Nakamura, entitled "METHOD FOR GROWING GROUP-III NITRIDE CRYSTALS
IN SUPERCRITICAL AMMONIA USING AN AUTOCLAVE," attorneys' docket
number 30794.129-US-WO (2005-339-2), which application claims the
benefit under 35 U.S.C. Section 365(c) of P.C.T. International
Patent Application Serial No. US2005/024239, filed on Jul. 8, 2005,
by Kenji Fujito, Tadao Hashimoto and Shuji Nakamura, entitled
"METHOD FOR GROWING GROUP III-NITRIDE CRYSTALS IN SUPERCRITICAL
AMMONIA USING AN AUTOCLAVE," attorneys' docket number
30794.129-WO-01 (2005-339-1);
[0008] U.S. Utility patent application Ser. No. 11/784,339, filed
on Apr. 6, 2007, by Tadao Hashimoto, Makoto Saito, and Shuji
Nakamura, entitled "METHOD FOR GROWING LARGE SURFACE AREA GALLIUM
NITRIDE CRYSTALS IN SUPERCRITICAL AMMONIA AND LARGE SURFACE AREA
GALLIUM NITRIDE CRYSTALS," attorneys' docket number 30794.179-US-U1
(2006-204), which application claims the benefit under 35 U.S.C.
Section 119(e) of U.S. Provisional Patent Application Ser. No.
60/790,310, filed on Apr. 7, 2006, by Tadao Hashimoto, Makoto
Saito, and Shuji Nakamura, entitled "A METHOD FOR GROWING LARGE
SURFACE AREA GALLIUM NITRIDE CRYSTALS IN SUPERCRITICAL AMMONIA AND
LARGE SURFACE AREA GALLIUM NITRIDE CRYSTALS," attorneys' docket
number 30794.179-US-P1 (2006-204);
[0009] U.S. Utility patent application Ser. No. 11/765,629, filed
on Jun. 20, 2007, by Tadao Hashimoto, Hitoshi Sato and Shuji
Nakamura, entitled "OPTO-ELECTRONIC AND ELECTRONIC DEVICES USING
N-FACE OR M-PLANE GaN SUBSTRATE PREPARED WITH AMMONOTHERMAL
GROWTH," attorneys' docket number 30794.184-US-U1 (2006-666), now
U.S. Pat. No. 7,755,172, which application claims the benefit under
35 U.S.C. Section 119(e) of U.S. Provisional Patent Application
Ser. No. 60/815,507, filed on Jun. 21, 2006, by Tadao Hashimoto,
Hitoshi Sato, and Shuji Nakamura, entitled "OPTO-ELECTRONIC AND
ELECTRONIC DEVICES USING N-FACE GaN SUBSTRATE PREPARED WITH
AMMONOTHERMAL GROWTH," attorneys' docket number 30794.184-US-P1
(2006-666);
[0010] U.S. Utility patent application Ser. No. 12/234,244, filed
on Sep. 19, 2008, by Tadao Hashimoto and Shuji Nakamura, entitled
"GALLIUM NITRIDE BULK CRYSTALS AND THEIR GROWTH METHOD," attorneys'
docket number 30794.244-US-U1 (2007-809), now U.S. Pat. No.
8,253,221, which application claims the benefit under 35 U.S.C.
Section 119(e) of U.S. Provisional Patent Application Ser. No.
60/973,662, filed on Sep. 19, 2007, by Tadao Hashimoto and Shuji
Nakamura, entitled "GALLIUM NITRIDE BULK CRYSTALS AND THEIR GROWTH
METHOD," attorneys' docket number 30794.244-US-P1 (2007-809-1);
[0011] U.S. Utility patent application Ser. No. 11/977,661, filed
on Oct. 25, 2007, by Tadao Hashimoto, entitled "METHOD FOR GROWING
GROUP III-NITRIDE CRYSTALS IN A MIXTURE OF SUPERCRITICAL AMMONIA
AND NITROGEN, AND GROUP III-NITRIDE CRYSTALS GROWN THEREBY,"
attorneys' docket number 30794.253-US-U1 (2007-774-2), now U.S.
Pat. No. 7,803,344, which application claims the benefit under 35
U.S.C. Section 119(e) of U.S. Provisional Patent Application Ser.
No. 60/854,567, filed on Oct. 25, 2006, by Tadao Hashimoto,
entitled "METHOD FOR GROWING GROUP-III NITRIDE CRYSTALS IN MIXTURE
OF SUPERCRITICAL AMMONIA AND NITROGEN AND GROUP-III NITRIDE
CRYSTALS," attorneys' docket number 30794.253-US-P1 (2007-774);
[0012] U.S. Utility patent application Ser. No. 12/612,477, filed
Nov. 4, 2009, by Siddha Pimputkar, Derrick S. Kamber, Makoto Saito,
Steven P. DenBaars, James S. Speck and Shuji Nakamura, entitled
"GROUP-III NITRIDE MONOCRYSTAL WITH IMPROVED CRYSTAL QUALITY GROWN
ON AN ETCHED-BACK SEED CRYSTAL AND METHOD OF PRODUCING THE SAME,"
attorneys' docket number 30794.288-US-U1 (2009-154-2), which
application claims the benefit under 35 U.S.C. Section 119(e) of
U.S. Provisional Patent Application Ser. No. 61/111,644, filed on
Nov. 5, 2008, by Siddha Pimputkar, Derrick S. Kamber, Makoto Saito,
Steven P. DenBaars, James S. Speck and Shuji Nakamura, entitled
"GROUP-III NITRIDE MONOCRYSTAL WITH IMPROVED CRYSTAL QUALITY GROWN
ON AN ETCHED-BACK SEED CRYSTAL AND METHOD OF PRODUCING THE SAME,"
attorneys' docket number 30794.288-US-P1 (2009-154-1);
[0013] P.C.T. International Patent Application Serial No.
PCT/US2009/063240, filed on Nov. 4, 2009, by Derrick S. Kamber,
Siddha Pimputkar, Makoto Saito, Steven P. DenBaars, James S. Speck
and Shuji Nakamura, entitled "GROUP-III NITRIDE MONOCRYSTAL WITH
IMPROVED PURITY AND METHOD OF PRODUCING THE SAME," attorneys'
docket number 30794.295-WO-U1 (2009-282-2), which application
claims the benefit under 35 U.S.C. Section 119(e) of U.S.
Provisional Patent Application Ser. No. 61/112,555, filed on Nov.
7, 2008, by Derrick S. Kamber, Siddha Pimputkar, Makoto Saito,
Steven P. DenBaars, James S. Speck and Shuji Nakamura, entitled
"GROUP-III NITRIDE MONOCRYSTAL WITH IMPROVED PURITY AND METHOD OF
PRODUCING THE SAME," attorneys' docket number 30794.295-US-P1
(2009-282-1);
[0014] P.C.T. International Patent Application Serial No.
PCT/US2009/063238, filed on Nov. 4, 2009, by Siddha Pimputkar,
Derrick S. Kamber, James S. Speck and Shuji Nakamura, entitled
"NOVEL VESSEL DESIGNS AND RELATIVE PLACEMENTS OF THE SOURCE
MATERIAL AND SEED CRYSTALS WITH RESPECT TO THE VESSEL FOR THE
AMMONOTHERMAL GROWTH OF GROUP-III NITRIDE CRYSTALS," attorneys'
docket number 30794.297-WO-U1 (2009-284-2), which application
claims the benefit under 35 U.S.C. Section 119(e) of U.S.
Provisional Patent Application Ser. No. 61/112,552, filed on Nov.
7, 2008, by Siddha Pimputkar, Derrick S. Kamber, James S. Speck and
Shuji Nakamura, entitled "NOVEL VESSEL DESIGNS AND RELATIVE
PLACEMENTS OF THE SOURCE MATERIAL AND SEED CRYSTALS WITH RESPECT TO
THE VESSEL FOR THE AMMONOTHERMAL GROWTH OF GROUP-III NITRIDE
CRYSTALS," attorneys' docket number 30794.297-US-P1
(2009-284-1);
[0015] P.C.T. International Patent Application Serial No.
PCT/US2009/063287, filed on Nov. 4, 2009, by Siddha Pimputkar,
Derrick S. Kamber, James S. Speck and Shuji Nakamura, entitled
"ADDITION OF HYDROGEN AND/OR NITROGEN CONTAINING COMPOUNDS TO THE
NITROGEN-CONTAINING SOLVENT USED DURING THE AMMONOTHERMAL GROWTH OF
GROUP-III NITRIDE CRYSTALS," attorneys' docket number
30794.298-WO-U1 (2009-286-2), which application claims the benefit
under 35 U.S.C. Section 119(e) of U.S. Provisional Patent
Application Ser. No. 61/112,558, filed on Nov. 7, 2008, by Siddha
Pimputkar, Derrick S. Kamber, James S. Speck and Shuji Nakamura,
entitled "ADDITION OF HYDROGEN AND/OR NITROGEN CONTAINING COMPOUNDS
TO THE NITROGEN-CONTAINING SOLVENT USED DURING THE AMMONOTHERMAL
GROWTH OF GROUP-III NITRIDE CRYSTALS TO OFFSET THE DECOMPOSITION OF
THE NITROGEN-CONTAINING SOLVENT AND/OR MASS LOSS DUE TO DIFFUSION
OF HYDROGEN OUT OF THE CLOSED VESSEL," attorneys' docket number
30794.298-US-P1 (2009-286-1);
[0016] P.C.T. International Patent Application Serial No.
PCT/US2009/063236, filed on Nov. 4, 2009, by Siddha Pimputkar,
Derrick S. Kamber, James S. Speck and Shuji Nakamura, entitled
"CONTROLLING RELATIVE GROWTH RATES OF DIFFERENT EXPOSED
CRYSTALLOGRAPHIC FACETS OF A GROUP-III NITRIDE CRYSTAL DURING THE
AMMONOTHERMAL GROWTH OF A GROUP-III NITRIDE CRYSTAL," attorneys'
docket number 30794.299-WO-U1 (2009-287-2), which application
claims the benefit under 35 U.S.C. Section 119(e) of U.S.
Provisional Patent Application Ser. No. 61/112,545, filed on Nov.
7, 2008, by Siddha Pimputkar, Derrick S. Kamber, James S. Speck and
Shuji Nakamura, entitled "CONTROLLING RELATIVE GROWTH RATES OF
DIFFERENT EXPOSED CRYSTALLOGRAPHIC FACETS OF A GROUP-III NITRIDE
CRYSTAL DURING THE AMMONOTHERMAL GROWTH OF A GROUP-III NITRIDE
CRYSTAL," attorneys' docket number 30794.299-US-P1(2009-287-1);
and
[0017] P.C.T. International Patent Application Serial No.
PCT/US2009/063233, filed on Nov. 4, 2009, by Siddha Pimputkar,
Derrick S. Kamber, James S. Speck and Shuji Nakamura, entitled
"USING BORON-CONTAINING COMPOUNDS, GASSES AND FLUIDS DURING
AMMONOTHERMAL GROWTH OF GROUP-III NITRIDE CRYSTALS," attorneys'
docket number 30794.300-WO-U1 (2009-288-2), which application
claims the benefit under 35 U.S.C. Section 119(e) of U.S.
Provisional Patent Application Ser. No. 61/112,550, filed on Nov.
7, 2008, by Siddha Pimputkar, Derrick S. Kamber, James S. Speck and
Shuji Nakamura, entitled "USING BORON-CONTAINING COMPOUNDS, GASSES
AND FLUIDS DURING AMMONOTHERMAL GROWTH OF GROUP-III NITRIDE
CRYSTALS," attorneys' docket number 30794.300-US-P1
(2009-288-1);
[0018] all of which applications are incorporated by reference
herein.
BACKGROUND OF THE INVENTION
[0019] 1. Field of the Invention
[0020] This invention relates to ammonothermal growth of group-III
nitrides.
[0021] 2. Description of the Related Art
[0022] Ammonothermal growth of group-III nitrides, for example,
GaN, involves placing, within a reactor vessel, group-III
containing source materials, group-III nitride seed crystals, and a
nitrogen-containing solvent, such as ammonia, sealing the vessel
and heating the vessel to conditions such that the vessel is at
elevated temperatures (between 23.degree. C. and 1000.degree. C.)
and high pressures (between 1 atm and, for example, 30,000 atm).
Under these temperatures and pressures, the nitrogen-containing
solvent may become a supercritical fluid which normally exhibits
enhanced solubility of the group-III containing source materials
into solution. The solubility of the group-III containing materials
into the nitrogen-containing solvent is dependent on the
temperature, pressure and density of the solvent, among other
things. By creating two different zones within the vessel, it is
possible to establish a solubility gradient where, in one zone, the
solubility will be higher than in a second zone. The group-III
containing source materials are then preferentially placed in the
higher solubility zone and the seed crystals in the lower
solubility zone. By establishing fluid motion of the solvent with
the dissolved source materials between these two zones, for
example, by making use of natural convection, it is possible to
transport the group-III containing source materials from the higher
solubility zone to the lower solubility zone where the group-III
containing source materials are deposited onto the seed
crystals.
[0023] The current state of the art uses a device or vessel that
contains the supercritical solvent and this vessel is heated to
raise the entire vessel contents to elevated temperatures and
pressures. The heating of the vessel is commonly performed by
heating the outer walls of the vessel and, by virtue of heat
transfer, heating the inner walls of the vessel, which, in turn,
heats the solvent, group-III containing source materials, group-III
nitride seed crystals and other material present within the
vessel.
[0024] For the ammonothermal growth of group-III nitride crystals,
it is important to establish solubility gradients. One method of
producing these gradients is to establish temperature gradients
since the solubility is a function of temperature, among other
variables. Therefore, it is crucial for the growth characteristics
of the group-III nitride crystals to establish well defined and
controllable temperature gradients across well defined and placed
spatial zones within the reactor.
[0025] In addition, many current reactor designs for the
ammonothermal growth of group-III nitride crystals involve placing
the group-III containing source materials and group-III nitride
seed crystals within a vessel, where the vessel has a small ratio
of inner diameter to length of vessel. By virtue of this design,
the vessel has a long cylindrical shape wherein the group-III
containing source materials or group-III nitride seed material are
preferentially placed in different zones of the vessel, and the
different zones are often separated by the use of baffle plates,
which function as restriction devices for the fluid flow of the
solvent, so it is possible to establish temperature gradients
between the two zones.
[0026] Thus, what is needed in the art are new reactor vessel
designs for use in ammonothermal growth of group-III nitride
crystals. Specifically, what is needed in the art are improved
techniques for heating reactor vessels used in ammonothermal growth
of group-III nitride crystals. In addition, what is needed in the
art are improved baffle designs for reactor vessels used in
ammonothermal growth of group-III nitride crystals. The present
invention satisfies these needs.
SUMMARY OF THE INVENTION
[0027] To overcome the limitations in the prior art described
above, and to overcome other limitations that will become apparent
upon reading and understanding the present invention, the present
invention discloses improved reactor vessel designs for use in
ammonothermal growth of group-III nitride crystals. The
improvements include internal heating, which is used to enhance
and/or engineer fluid motion, gas mixing, and the ability to create
solubility gradients within the vessel, and novel baffle designs,
which are used for control and improvement of continuous fluid
motion within the vessel.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Referring now to the drawings in which like reference
numbers represent corresponding parts throughout:
[0029] FIG. 1 is a schematic of a high-pressure vessel according to
an embodiment of the present invention.
[0030] FIG. 2 is a flowchart illustrating the method according to
an embodiment of the present invention.
[0031] FIGS. 3(a) and 3(b) illustrate one possible embodiment of a
baffle used in the high-pressure vessel of the present
invention.
[0032] FIG. 4 illustrates another possible embodiment of a baffle
used in the high-pressure vessel of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0033] In the following description of the preferred embodiment,
reference is made to a specific embodiment in which the invention
may be practiced. It is to be understood that other embodiments may
be utilized and structural changes may be made without departing
from the scope of the present invention.
Apparatus Description
[0034] FIG. 1 is a schematic of an ammonothermal growth system
comprising a high-pressure reaction vessel 10 according to one
embodiment of the present invention. The vessel, which is an
autoclave, may include a lid 12, gasket 14, inlet and outlet port
16, and external heaters/coolers 18a and 18b. A baffle plate 20
divides the interior of the vessel 10 into two zones 22a and 22b,
wherein the zones 22a and 22b are separately heated and/or cooled
by the external heaters/coolers 18a and 18b, respectively. An upper
zone 22a may contain one or more group-III nitride seed crystals 24
and a lower zone 22b may contain one or more group-III-containing
source materials 26, although these positions may be reversed in
other embodiments. Both the group-III nitride seed crystals 24 and
group-III-containing source materials 26 may be contained within
baskets or other containment devices, which are typically comprised
of a Ni--Cr alloy. The vessel 10 and lid 12, as well as other
components, may also be made of a Ni--Cr based alloy. Finally, the
interior of the vessel 10 is filled with a nitrogen-containing
solvent 28 to accomplish the ammonothermal growth.
Process Description
[0035] FIG. 2 is a flow chart illustrating a method for obtaining
or growing a group-III nitride-containing crystal using the
apparatus of FIG. 1 according to one embodiment of the present
invention.
[0036] Block 30 represents placing one or more group-III nitride
seed crystals 24, one or more group-III containing source materials
26, and a nitrogen-containing solvent 28 in the vessel 10, wherein
the seed crystals 24 are placed in a seed crystals zone (i.e.,
either 22a or 22b, namely the opposite of the zone 22b or 22a
containing the source materials 26, the source materials 26 are
placed in a source materials zone (i.e., either 22b or 22a, namely
the opposite of the zone 22a or 22b containing the seed crystals
24). The seed crystals 24 comprise a group-III containing crystal;
the source materials 26 comprise a group-III containing compound, a
group-III element in its pure elemental form, or a mixture thereof,
i.e., a group-III nitride monocrystal, a group-III nitride
polycrystal, a group-III nitride powder, group-III nitride
granules, or other group-III containing compound; and the
nitrogen-containing solvent 28 is supercritical ammonia or one or
more of its derivatives. An optional mineralizer may be placed in
the vessel 10 as well, wherein the mineralizer increases the
solubility of the source materials 26 in the supercritical
nitrogen-containing solvent 28 as compared to the supercritical
nitrogen-containing solvent 28 without the mineralizer.
[0037] Block 32 represents growing group-III nitride crystals on
one or more surfaces of the seed crystals 24, wherein the
conditions for growth include forming a temperature gradient
between the seed crystals 24 and the source materials 26 that
causes a higher solubility of the source materials 26 in the source
materials zone and a lower solubility, as compared to the higher
solubility, of the source materials 26 in the seed crystals zone.
Specifically, growing the group-III nitride crystals on one or more
surfaces of the seed crystal 24 occurs by changing the source
materials zone temperatures and the seed crystals zone temperatures
to create a temperature gradient between the source materials zone
and the seed crystals zone that produces a higher solubility of the
materials 26 in the solvent 28 in the source materials zone as
compared to the seed crystals zone. For example, the source
materials zone and seed crystals zone temperatures may range
between 0.degree. C. and 1000.degree. C., and the temperature
gradients may range between 0.degree. C. and 1000.degree. C.
[0038] Block 34 comprises the resulting product created by the
process, namely, a group-III nitride crystal grown by the method
described above. A group-III nitride substrate may be created from
the group-III nitride crystal, and a device may be created using
the group-III nitride substrate.
Fluid Motion within the Vessel
[0039] According to the present invention, fluid motion within the
vessel 10 may be accomplished via a unique configuration of
internal heaters and/or a unique baffle device design. These are
described in more detail below.
Using Internal Heating to Enhance and/or Engineer Fluid Motion, Gas
Mixing, and the Ability to Create Solubility Gradients within a
Vessel Used for the Ammonothermal Growth of Group-III Nitride
Crystals
[0040] The present invention intends the use of internal
heater(s)/cooler(s), in combination with, or instead of, external
heaters/coolers 18a, 18b, which elevate or lower the exterior walls
and, sequentially, the interior walls of the vessel 10 containing
the seed crystals 24, the source materials 26, and the solvent 28,
to different temperatures at different well defined spatial areas
of the vessel 10.
[0041] In one embodiment, the baffle 20 is the internal
heater/cooler. However, any number of internal heaters/coolers may
be placed within the vessel 10 in any number of spatial locations
within the vessel 10. The temperature of each internal
heater/cooler may be the same or different depending on the
particular effect that one wishes to achieve. The internal
heater/cooler may present itself in any shape, form, size or
material, yet it may be preferable to use high purity metals, or
high purity metal coated ceramics. The internal heaters/coolers may
or may not have a protective coating surrounding the elements
thereof to prevent corrosion or other detrimental effects from the
surrounding environment on their operation.
[0042] Although the internal heaters/coolers may be integrated into
or onto other components present within the vessel, such as, but
not limited to, the baffle 20, which are used to guide and/or
restrict fluid flow within the vessel 10, the internal
heaters/coolers may also be integrated into other components, such
as a basket or containing device sometimes used to hold the seed
crystals 24 r source materials 26.
[0043] The internal heaters/coolers may also be designed to
encompass the entire inner surface of the vessel 10, thereby
potentially eliminating the need for external heating or cooling of
the vessel 10 to elevate or lower the temperatures within the
vessel 10. This could potentially allow for the creation of higher
pressure vessels, as the material barring the pressure is at a
lower temperature, and enhance the mechanical characteristics of
the current state of the art vessel designs used for the
ammonothermal growth of group-III nitride crystals.
[0044] Some of the many possible purposes of the internal
heaters/coolers are to establish a temperature gradient across a
spatial zone surrounding the heaters/coolers and other spatial
zones within the vessel 10. By establishing this temperature
gradient, it is possible to establish solubility gradients, which,
in turn, may be used to enhance the growth of the group-III nitride
crystals. The ability to engineer different solubility zones within
the vessel 10, without the restriction and sole use of external
heaters/coolers and devices which manage the fluid flow within the
vessel 10, for example, baffle devices 20, is substantial and will
allow for more efficient and more effective designs which, in turn,
may allow for the increased growth rates and improved crystal
quality of the group-III nitride crystals.
[0045] Other immediate benefits of the internal heaters/coolers may
be the ability to establish a zone around each heater/cooler that
is at a higher or lower density than the surrounding fluid due to
the difference in temperature between the zone and the surrounding
medium. This density difference may provide fluid dynamical forces
within the vessel 10, thereby enhancing fluid motion and hence mass
transport of the solvent 28 with the dissolved source materials 26.
One example of this particular aspect of the invention, although
this should not be seen limiting in any way, would be a
heater/cooler that is relatively long, held vertically and results
in a temperature higher than the surrounding solvent 28. By heating
the solvent 28, the solvent 28 will become a lower density material
and will want to rise along the surface of the heater/cooler. The
rising of the local, hotter supercritical solvent 28 is a
demonstration of both a controlled convective flow within the
vessel 10 and enhanced fluid motion. Not only does this example
provide enhanced fluid motion, but the local hotter solvent 28
fluid may have a higher or lower solubility of the source materials
26 and therefore it may be advantageous to place either the source
materials 26 or seed crystals 24 close to this zone within the
vessel 10.
[0046] While the primary purpose of the internal heaters/coolers is
to provide a controllable temperature gradient of any size between
different spatial regions of the vessel 10, the internal
heaters/coolers may also simultaneously be used as structural units
within the vessel 10 to control and/or engineer fluid patterns
within the vessel 10 itself. For example, the baffle 20 with an
integrated heater/cooler can simultaneously heat or cool the
solvent 28 and restrict solvent 28 flow. Alternatively, the
internal heaters/coolers may be integrated into baskets or other
devices used to hold the seed crystals 24 and/or contain the source
materials 26, as well as provide a local temperature that is
different from the surrounding solvent 28 fluid. The internal
heaters/coolers may also be used, for example, as a liner material
for the vessel 10 in a lower solubility zone where the growth of
the group-III nitride crystals occurs. By changing the local
temperature near the vessel 10 wall, it may be possible to prevent
nucleation and sequential growth of the material on the vessel 10
wall surfaces as the solubility may be increased just in the
vicinity of the walls.
Novel Baffle Designs for Control and Improvement of Continuous
Fluid Motion within a Vessel Used for the Ammonothermal Growth of
Group-III Nitride Crystals
[0047] In order to improve on the mass transport within the vessel
10, the present invention also uses novel baffle devices 20 that
enhance the mixing of fluids, e.g., the solvent 28 with the
dissolved source materials 26, and additionally guide the fluid
motion to circulate the fluid to a much greater degree, and
furthermore, allow for greater penetration of the fluid into
various areas of the vessel 10. This is achieved by the baffle
devices 20 enhancing circular fluid motion patterns and
additionally redirecting the flow of the fluid within the baffle
device 20 itself.
[0048] FIGS. 3(a) and 3(b) illustrate one possible embodiment of
the baffle device 20 according to the present invention.
Specifically, FIG. 3(a) is a side view of an exemplary baffle
device 20 wherein the arrows 36 show the motion of the fluid
through the baffle device 20, and FIG. 3(b) is a top view of the
baffle device 20 showing the openings 38 and 40 for fluid
transfer.
[0049] The basic idea entails having the fluid enter the baffle
device 20, for example, on one side (e.g., the top surface), in the
openings 40 near the outer edge of the baffle device 20 and exit
through the openings 38 that are in a region that is closer to the
center of the baffle device 20. Similarly, on the opposite side of
the baffle device 20 (i.e., the bottom surface), the fluid may
enter through the openings 40 near the outer edge of the baffle
device 20 and exit through the openings 38 that are in a region
that is closer to the center of the baffle device 20.
[0050] Alternative embodiments may reverse this fluid flow, namely
the fluid may enter the baffle 20 through the region that is closer
to the center of the baffle 20, and exit the baffle 20 near the
outer edge of the baffle 20.
[0051] By virtue of this design for the baffle device 20, it may be
possible to establish a continual motion of fluid within the vessel
10. The seed crystals 24 and source materials 26 can then be placed
in the appropriate areas of the vessel 10 to provide optimal
conditions for growth on the seed crystals 24 and/or for
dissolution of the source materials 26 into the solvent 28.
[0052] Moreover, by incorporating internal heaters/coolers into the
baffle device 20 itself, or by adding other internal
heaters/coolers into the vessel 10, or by applying or extracting
heat from the outside the walls of the vessel 10 by use of other
heating or cooling mechanisms or devices, specifically in the
region of the baffle 20, it is further possible to intentionally
change the temperature, and hence, solubility, of the fluid exiting
the baffle device 20 as compared to the fluid entering the baffle
device 20.
[0053] This invention further includes the idea of designing the
baffle device 20 not only to improve on fluid motion within the
vessel 10, but also to guide particular fluids into one or more
specific zones within the vessel 10. One example of this idea,
which should not be considered limiting in any way, would be for
the baffle device 20 to guide nutrient rich solvent 28, for
example, solvent 28 coming from the source materials zone, towards
the center of the vessel 10. By doing so, it may be possible to
suppress nucleation and growth of group-III nitride material on
undesired locations and/or surfaces within the vessel 10, for
example, on the walls of the vessel 10, and further enhance growth
of group-III nitride material on desired locations within the
vessel 10, for example, on the group-III nitride seed crystals
24.
[0054] This invention is not limited to the above schematic
presentation of one possible baffle device 20 design, but includes
any possible design, which passively or actively redirects fluid
motion and/or guides fluid motion without major redirection. This
invention further includes the possibility and ability, depending
on design of the baffle device 20, to change the temperature,
pressure and/or other properties of the fluid while flowing through
the baffle device. For example, if one uses a baffle device 20
design in combination with a heating element, it may be possible to
heat the fluid simultaneously while flowing through the baffle
device 20 itself.
[0055] Another possible example of a baffle device which guides
fluid motion is schematically presented in FIG. 4, which shows the
vessel 10 having a funnel-shaped baffle device 42 that establishes
a continual circular motion of the fluid within the vessel 10,
wherein the arrows 44 indicate the fluid motion of the solvent 28
through the vessel 10. Note that this baffle device 42 may
incorporate heating and/or cooling mechanisms that supplement or
eliminate the need for other heating and/or cooling devices outside
of the vessel 10 and/or inside the vessel 10. Further, while the
fluid motion in FIG. 4 is fairly simple, other fluid motion could
be engineered as well by means of the design of the baffle device
42. Such design could create any number of difference zones within
the vessel 10 having different characteristics, including but not
limited to, solubility, fluid velocity, laminar or turbulent fluid
flow patterns, and relative direction of fluid motion within the
zones, temperature, pressure, and density of the various atoms,
molecules, compounds and/or complexes.
CONCLUSION
[0056] This concludes the description of the preferred embodiment
of the present invention. The foregoing description of one or more
embodiments of the invention has been presented for the purposes of
illustration and description. It is not intended to be exhaustive
or to limit the invention to the precise form disclosed. Many
modifications and variations are possible in light of the above
teaching. It is intended that the scope of the invention be limited
not by this detailed description, but rather by the claims appended
hereto.
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