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Growth of bulk group-iii nitride crystals

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Publication number
WO2013010118A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
group
crystal
nitride
ill
growth
Prior art date
Application number
PCT/US2012/046758
Other languages
French (fr)
Inventor
Siddha Pimputkar
James S. Speck
Original Assignee
The Regents Of The University Of California
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL-GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B17/00Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL-GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/40AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403AIII-nitrides
    • C30B29/406Gallium nitride

Abstract

A method of producing a Group-Ill nitride crystal by coating at least one surface of the seed with a thin wetting layer or film comprised of one or more Group- Ill and alkali metals.

Description

GROWTH OF BULK GROUP-HI NITRIDE CRYSTALS

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit under 35 U.S.C. Section 119(e) of copending and commonly-assigned applications:

U.S. Provisional Application Serial No. 61/507,182, filed on July 13, 2011, by Siddha Pimputkar and James S. Speck, entitled "GROWTH OF BULK GROUP-III NITRIDE CRYSTALS AFTER COATING THEM WITH A GROUP-III METAL AND AN ALKALI METAL," attorneys' docket number 30794.420-US-P1 (2012- 021-1);

which application is incorporated by reference herein.

This application is related to the following co-pending and commonly- assigned U.S. patent applications:

U.S. Utility Patent Application Serial No. 13/128,092, filed on May 6, 2011, 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-WO (2009-288-2), which application is a national stage application that claims the benefit of or priority to P.C.T. International Patent Application Serial No. PCT/US09/063233, filed on November 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 Serial No. 61/112,550, filed on November 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);

U.S. Utility Patent Application Serial No. 13/048,179, filed on March 15, 2011, by Siddha Pimputkar, James S. Speck, and Shuji Nakamura, and entitled "GROUP-III NITRIDE CRYSTAL AMMONOTHERMALLY GROWN USING AN INITIALLY OFF-ORIENTED NONPOLAR OR SEMIPOLAR GROWTH SURFACE OF A GROUP-III NITRIDE SEED CRYSTAL," attorney's docket number 30794.376- US-U1 (2010-585-1), which application claims the benefit under 35 U.S.C. Section 119(e) of U.S. Provisional Patent Application Serial No. 61/314,095, filed on March 15, 2010, by Siddha Pimputkar, James S. Speck, and Shuji Nakamura, and entitled "GROUP-III NITRIDE CRYSTAL GROWN USING AN INITIALLY OFF- ORIENTED NONPOLAR AND/OR SEMIPOLAR GROUP-III NITRIDE AS A SEED CRYSTAL USING THE AMMONOTHERMAL METHOD AND METHOD OF PRODUCING THE SAME," attorney's docket number 30794.376-US-P1 (2010- 585-1); and

P.C.T. International Patent Application Serial No. PCT/US12/xxxxxx, filed on July 13, 2012, by Siddha Pimputkar, Shuji Nakamura and James S. Speck, entitled "USE OF GROUP-III NITRIDE CRYSTALS GROWN USING A FLUX METHOD AS SEEDS FOR AMMONOTHERMAL GROWTH OF A GROUP-III NITRIDE CRYSTAL," attorneys' docket number 30794.419-WO-U1 (2012-020-2), which application claims the benefit under 35 U.S.C. Section 119(e) of U.S. Provisional Application Serial No. 61/507,170, filed on July 13, 2011, by Siddha Pimputkar and Shuji Nakamura, entitled "USE OF GROUP-III NITRIDE CRYSTALS GROWN USFNG A FLUX METHOD AS SEEDS FOR AMMONOTHERMAL GROWTH OF A GROUP-III NITRIDE CRYSTAL," attorneys' docket number 30794.419-US-P1 (2012-020-1), and U.S. Provisional Application Serial No. 61/507,187, filed on July 13, 2011, by Siddha Pimputkar and James S. Speck, entitled "METHOD OF

GROWFNG A BULK GROUP-III NITRIDE CRYSTAL USING A FLUX BASED METHOD THROUGH PREPARING THE FLUX PRIOR TO BRINGFNG IT FN CONTACT WITH THE GROWING CRYSTAL," attorneys' docket number

30794.421-US-P1 (2012-022);

P.C.T. International Patent Application Serial No. PCT/US12/xxxxxx, filed on July 13, 2012, by Siddha Pimputkar, Shuji Nakamura and James S. Speck, entitled "METHOD FOR IMPROVING THE TRANSPARENCY AND QUALITY OF

GROUP-III NITRIDE CRYSTALS AMMONOTHERMALLY GROWN IN A HIGH PURITY GROWTH ENVIRONMENT," attorneys' docket number 30794.422-WO- Ul (2012-023-2), which application claims the benefit under 35 U.S.C. Section 119(e) of U.S. Provisional Application Serial No. 61/507,212, filed on July 13, 2011, by Siddha Pimputkar and Shuji Nakamura, entitled "HIGHER PURITY GROWTH ENVIRONMENT FOR THE AMMONOTHERMAL GROWTH OF GROUP-III NITRIDES," attorneys' docket number 30794.422-US-P1 (2012-023-1); U.S.

Provisional Application Serial No. 61/551,835, filed on October 26, 2011, by Siddha Pimputkar, Shuji Nakamura, and James S. Speck, entitled "USE OF BORON TO IMPROVE THE TRANSPARENCY OF AMMONOTHERMALLY GROWN

GROUP-III NITRIDE CRYSTALS," attorneys' docket number 30794.438-US-P1 (2012-248-1); and U.S. Provisional Application Serial No. 61/552,276, filed on October 27, 2011, by Siddha Pimputkar, Shuji Nakamura, and James S. Speck, entitled "USE OF SEMIPOLAR SEED CRYSTAL GROWTH SURFACE TO IMPROVE THE QUALITY OF AN AMMONOTHERMALLY GROWN GROUP- III NITRIDE CRYSTAL," attorneys' docket number 30794.439-US-Pl (2012-249-1); all of which applications are incorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention.

This invention relates to a method of growing a bulk Group-Ill nitride crystal using a flux method, wherein the Group-Ill nitride seed crystals are coated with a Group-Ill metal and an alkali metal. 2. Description of the Related Art.

(Note: This application references a number of different publications as indicated throughout the specification by one or more reference numbers within brackets, e.g., [x]. A list of these different publications ordered according to these reference numbers can be found below in the section entitled "References." Each of these publications is incorporated by reference herein.)

Bulk Group-Ill nitride crystals, such as bulk Gallium Nitride (GaN) crystals, are essential for the generation of low defect Group-Ill nitride substrates, which, in turn, are used for the fabrication of electronic and optoelectronic devices. Bulk Group-Ill nitride crystals can be grown using various methods, such as an ammonothermal method, a high pressure nitrogen solution growth method, or other flux methods, such as a sodium flux method, wherein a major component of the flux is elemental sodium (Na).

Of all the methods currently used to produce bulk Group-Ill nitride crystals, the sodium flux method appears the most promising due to its demonstrated growth rates and resulting properties of the crystals. Specifically, the sodium flux method, which grows bulk GaN crystals from a flux that contains at least a Group-Ill element (such as Ga), an alkali metal (such as Na), and some dissolved nitrogen, has demonstrated high growth rates, e.g., approximately 30 micrometers per hour for sodium flux growth as compared to approximately 5 micrometers per hour for ammonothermal growth.

What is needed in the art, then, is a method that provides further

improvements to the sodium flux method for the growth of bulk Group-Ill nitride crystals. The present invention satisfies this need.

SUMMARY OF THE INVENTION

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 specification, the present invention discloses a method of growing bulk Group-Ill nitride crystals using flux methods. The flux may contain Group-Ill and alkali metals, such as Ga and Na, and other additives to modify the solubility of nitrogen into the flux, which is needed for the growth of Group-Ill nitride crystals. In order to further enhance growth rates, and additionally modify the properties of a growing Group-Ill nitride crystal, it is beneficial to reduce the distance needed for nitrogen to migrate from its source (the atmosphere) to the crystal's surface. This invention proposes coating at least one surface of a Group-Ill nitride crystal with a thin wetting layer or film of flux-containing material comprised of the Group-Ill and alkali metals, before and during the sodium flux growth, thereby reducing the overall diffusion length of nitrogen and increasing the growth rate of the crystal.

BRIEF DESCRIPTION OF THE DRAWINGS

Referring now to the drawings in which like reference numbers represent corresponding parts throughout:

FIG. 1 is a schematic of an apparatus used in the sodium flux method according to one embodiment of the present invention.

FIG. 2 is a flowchart that illustrates an exemplary process for performing sodium flux growth according to one embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the following description of the preferred embodiment, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration 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.

Overview

This invention provide an improved rate of flux growth of Group-Ill nitride crystals by thinning the layer of material around the growing Group-Ill nitride crystal, thereby reducing the distance a newly dissolved nitrogen atom, radical or molecule needs to travel until it integrates into the growing crystal. Specifically, the present invention provides an environment with sufficient Group-Ill metals and alkali metals, such that a thin Group-III-containing and alkali-containing layer adheres to the surface of the Group-Ill nitride crystal, to form a continuous wetting layer, even if any further supplied Group-Ill metals and alkali metals then form droplets that no longer provide full, continuous surface coverage. The material used to coat the crystal typically has some nitrogen present, and the crystal and/or the flux is at least partially exposed to a nitrogen-containing environment.

Sodium Flux Growth of Group-Ill Nitride Crystals

In its most fundamental form, the sodium flux method grows Group-Ill nitride crystals in a flux comprising a fluid or melt containing at least one Group-Ill metal, such as Al, Ga and/or In, and at least one alkali metal, such as Na. The fluid is contained within a chamber or vessel, and is subject to conditions that allow for the addition or removal of nitrogen to or from the fluid. For example, the fluid may be placed within a nitrogen-containing atmosphere and heated to a desirable temperature (typically greater than 700°C), wherein the fluid is brought into contact with one or more surfaces of a seed upon which the Group-Ill nitride crystal is formed.

The challenges this growth method faces are primarily related to the solubility of nitrogen into the flux and, once the nitrogen has been dissolved into the flux, the diffusion time required for the nitrogen to come into the vicinity of the growing Group-Ill nitride crystal. Multiple methods have been proposed, such as stirring or agitating the fluid, to increase the amount of dissolved nitrogen in close proximity of the crystal and, although these methods may be effective, they are not necessarily scalable and economic. This invention proposes an alternative method of preparing a crystal for the sodium flux growth by coating it with a continuous thin wetting layer comprised of one or more Group-Ill metals and one or more alkali metals. FIG. 1 is a schematic of an apparatus used in the sodium flux method in its most general form. In one embodiment of the present invention, the sodium flux method makes use of a vessel or chamber 100 (which may be open or closed) having a crucible 102 that contains a fluid 104 that is a crystal growth solution comprised of at least one Group-Ill metal, such as Al, Ga and/or In, and at least one alkali metal, such as Na. The fluid 104 may contain any number of additional elements, compounds, or molecules to modify growth characteristics and crystal properties, such as B, Li, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sr, C, Bi, Sb, Sn, Be, Si, Ge, Zn, P and/or N.

Additionally, the chamber 100 contains a growth atmosphere 106 in which the fluid 104 is placed that can be a nitrogen-containing atmosphere 106, including, but not limited to, molecules such as diatomic N2, ammonia NH3, hydrazine N2H6, and atomic nitrogen N, or an atmosphere 106 with only trace amounts of nitrogen present, for example, an atmosphere 106 comprised mainly of hydrogen, argon, etc. The atmosphere 106 may be at vacuum, or may have a pressure greater than

approximately 1 atmosphere (atm) and up to approximately 1000 atm.

The crucible 102 may include one or more heaters 108 so that fluid 104 may be heated and then held at one or more set temperatures, and one or more temperature gradients may be established within the chamber 100. In one embodiment, the fluid 104 is held at a temperature greater than approximately 200°C and below

approximately 1200°C during growth.

The chemical potential of the fluid 104 may be raised or lowered with respect to vacuum through the use of a power source operating at arbitrary frequencies (f >= 0Hz) and voltages. The fluid 104 and atmosphere 106 in which it has been placed may be subject to electromagnetic fields, both static and/or dynamic.

Once the chamber 100 containing the fluid 104 has been adequately prepared, a seed 110 can then be brought into contact with the fluid 104, wherein the seed 110 and/or the fluid 104 is at least partially exposed to the nitrogen-containing atmosphere 106. Once the seed 110 has been brought into contact with the fluid 104, the seed 110 and/or fluid 104 may be subject to mechanical movements 112, such as stirring or agitating, to enhance the growth of the Group-Ill nitride crystal.

In a preferred embodiment, the seed 110 itself is a Group-Ill nitride crystal, such as GaN, and may be a single crystal or a polycrystal. However, this should not be seen as limiting for this invention. This invention specifically includes growing a Group-Ill nitride crystal on an arbitrary material, wherein the seed 110 may be an amorphous solid, a polymer containing material, a metal, a metal alloy, a

semiconductor, a ceramic, a non-crystalline solid, a poly-crystalline material, an electronic device, an optoelectronic device, etc.

When the seed 110 is a Group-Ill nitride crystal, it may have one or more facets exposed, including facets that are polar, nonpolar and semipolar planes. For example, the Group-Ill nitride seed crystal 110 may have a large polar c-plane {0001 } facet or a {0001 } approaching facet exposed; or the Group-Ill nitride seed crystal 110 may have a large nonpolar m-plane {10-10} facet or a {10-10} approaching facet exposed; or the Group-Ill nitride seed crystal 110 may have a large semipolar {10-11 } facet or a {10-11 } approaching facet exposed; or the Group-Ill nitride seed crystal 110 may have a large nonpolar a-plane {11-20} facet or a {11-20} approaching facet exposed.

In one embodiment of the present invention, the seed 110 is prepared prior to growth by coating the seed 110 with a thin wetting layer 114 comprised of one or more Group-Ill metals and one or more alkali metals. Moreover, the thin wetting layer 114 is maintained on the Group-Ill nitride crystal during growth. The thin wetting layer 114 minimizes the distance the nitrogen must travel to integrate to the crystal, namely, through the thin wetting layer 114 rather than the flux 104.

The coating of the seed 110 or the resulting Group-Ill crystal is based on evaporation from a liquid and/or solid source, containing the Group-Ill and alkali metals, onto the seed 110 and/or the resulting crystal, which results in the formation of the thin wetting layer 114 onto the surfaces of the seed 110 or the resulting crystal. Consequently, the seed 110 and/or the resulting crystal are continuously or intermittently brought into contact with the flux 104 by dripping or flowing the flux 104 over the surfaces of the seed 110 or resulting crystal, or by submersing or submerging the seed 110 or resulting crystal into the flux 104 itself. Preferably, this occurs with at least one facet of the seed 110 or resulting crystal and/or the flux 104 exposed to the atmosphere 106 or at least close to the interface between the flux 104 and the atmosphere 106.

Nitrogen is then deposited onto the wetting layer 114, or conditions are provided such that nitrogen goes onto the wetting layer 114, wherein the nitrogen from the wetting layer 114, incorporates into the seed 110 and/or resulting crystal. For example, the wetting layer 114 may be bombarded with nitrogen (e.g., nitrogen gas at high pressure), and once there is enough nitrogen, nitrogen incorporates into the seed 100 and/or resulting crystal. For example, the Ga is a source for growth of Group III element on the seed 110 and/or crystal, the Na is a catalyst for the growth and, as the nitrogen goes into the alloy, it chemically reacts with the Ga.

The resulting Group-Ill nitride crystal that is grown on the seed 1 10 is characterized as AlxByGazIn(i_x_y_z)N, where 0 <= x <= 1, 0 <= y <= 1, 0 <= z <= l, and x + y + z <= 1. For example, the Group-Ill nitride crystal may be, but is not limited to, A1N, GaN, InN, AlGaN, AlInN, InGaN, etc. The Group-Ill nitride crystal may also have layers with different compositions, and the Group-Ill nitride crystal may have layers with different structural, electronic, optical, and/or magnetic properties.

Process Flowchart

FIG. 2 is a flowchart that illustrates an exemplary process for performing the method of sodium flux growth according to one embodiment of the present invention.

Block 200 represents placing a flux comprised of a fluid or melt 104 into a crucible 102 of a vessel or chamber 100, wherein the fluid 104 is a crystal growth solution comprised of at least one Group-Ill metal, such as Al, Ga and/or In, and at least one alkali metal, such as Na. Block 202 represents coating the seed 110 prior to growth with a thin wetting layer 114 comprised of the flux.

Block 204 represents placing the coated seed 119 into the chamber 100.

Block 206 represents filling the chamber 100 with a growth atmosphere 106 to a desired pressure level, wherein the growth atmosphere 106 can be a nitrogen- containing atmosphere 106 or an atmosphere 106 with only trace amounts of nitrogen present.

Block 208 represents heating the crucible 102 and/or chamber 100 to one or more set temperatures, and establishing one or more temperature gradients within the chamber 100.

Block 210 represents, once the chamber 100 containing the fluid 104 has been adequately prepared and the seed 110 coated with the thin wetting layer 114, growing the Group-Ill nitride crystal by bringing the seed 110 into contact with the fluid 104 or by bringing the fluid 104 into contact with the seed 110, wherein the seed 110 and/or the fluid 104 is at least partially exposed to the nitrogen-containing atmosphere 106. This Block may include subjecting the seed 110 and/or fluid 104 to mechanical movements 112, such as stirring or agitating or spray coating, to maintain the thin wetting layer 114 on the seed 110 and the growing Group-Ill crystal, in order to reduce the distance the nitrogen in the atmosphere 106 needs to travel to integrate into the seed 110, i.e., the nitrogen need only pass through the thin wetting layer 114 rather than through the flux 104 contained within the crucible 102.

Block 212 represents the resulting product created by the process, namely, a Group-Ill nitride crystal grown by the method described above. A Group-Ill nitride substrate may be created from the Group-Ill nitride crystal, and a device may be created using the Group-Ill nitride substrate.

Seed Crystal Coating Layer

As noted above, the coating applied to the seed crystal in the present invention, prior to and/or during the growth of the Group-Ill nitride crystals using the sodium flux method, improves the growth rate by reducing the distance a newly dissolved nitrogen atom, radical or molecule needs to travel until it integrates into the growing crystal. This is accomplished by maintaining a thin wetting layer of material around the growing Group-Ill nitride crystal prior to and/or during the sodium flux growth.

It has been seen in other growth techniques, such as MBE (Molecular Beam Epitaxy), that in an environment with sufficient Ga, a few monolayers of Ga adhere to the surface and form a continuous wetting layer. Using the MBE technique, any further supplied Ga then form droplets, which no longer provide full, continuous surface coverage. The present invention also uses the concept of a wetting layer, but in conjunction with the sodium flux method, wherein the wetting layer has a thickness of one or more monolayers of the Group-Ill metals and the alkali metals, that coats the Group-Ill nitride seed crystal prior to and during the sodium flux growth.

The method used to provide and maintain the wetting layer is not limited. In one embodiment, the wetting layer is not thicker than approximately 5-10 monolayers of the Group-Ill nitride crystal, although in another embodiment, the wetting layer is not thicker than approximately 1-5 mm of the Group-Ill nitride crystal. Moreover, while it is beneficial to only have a few monolayers of Group-Ill and alkali metal material around the crystal, it is further disclosed that a few micrometers of Group-Ill and alkali metal material around the crystal may be beneficial for overall growth characteristics.

The method used for coating the crystal may be comprised from the following non-exclusive list:

1. Physically dipping the crystal into solution and then removing it, while subjecting the crystal to a nitrogen-containing environment for extended periods of time.

2. Coating the crystal by placing it in proximity of one or more crucibles containing one or more Group-Ill elements and alkali metals that are melted, wherein a stream of one or more Group-Ill elements and/or alkali metals are directed towards the crystal.

3. Moving the melt containing one or more Group-Ill elements and alkali metals, so that it is brought into contact with the crystal. This could be done by dripping the melt onto the crystal from above and letting it coat the crystal while gravity pulls the melt over the surfaces of the crystal.

The method of the present invention may provide Group-Ill nitride substrates, which, in turn, can be used for the generation or fabrication of electronic and optoelectronic devices.

Possible Modifications and Improvements

Further modifications and improvements to this invention can be envisioned as the following:

1. The viscosity of the fluid may be modified by changing its

temperature, pressure, and/or adding other elements, compounds, or materials, before and/or during growth.

2. The vapor pressure of the various elements of interest can be modified by changing their temperature, pressure, and/or adding other elements, compounds, or materials, before and/or during growth.

3. The melt that coats the crystal may have any number of additional elements, molecules, and compounds present, which may further modify the:

a. growth rate of the crystal;

b. electronic properties of the crystal;

c. optical properties of the crystal;

d. magnetic properties of the crystal;

e. structural properties of the crystal;

f. surface roughness during growth;

g- predominate or predominant planes present during growth; h. size, density and distribution of growth fronts, growth planes. microfacets, macrofacets; i. impurity uptake into the crystal.

4. The orientations of exposed surfaces of the Group-Ill nitride crystal can be any combination of polar, non-polar and/or semi-polar orientations.

5. The use of specially prepared crystal with a specific surface structure and/or orientations to enforce a particular growth mode and/or direction during growth.

6. The control of layer thickness on the crystal may be achieved through modifications in the viscosity of the melt, the deposition rate of arriving material, the speed at which the crystal is moved, the speed at which the crystal is rotated, etc.

7. The orientation of the crystal may be positioned such that its main (i.e., largest) surface is fully exposed (e.g., parallel), at an angle to, or perpendicular to, the melt or a stream of elements that, at least in part, make up the melt.

8. The environment in which the crystal is placed, after having at least a monolayer coating of Group-Ill nitride material and alkali metal applied, may include at least one nitrogen-containing material, but may also specifically not contain nitrogen. Materials that may be useful for the successful growth include atomic nitrogen (N), diatomic nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrogen plasma, nitrogen radicals, and nitrogen plasma.

9. The composition of the flux may be modified and changed at any time during growth.

Advantages and Improvements

The present invention may provide a method to create cheap, high quality Group-Ill nitride substrates.

Nomenclature

The terms "Group-Ill nitride" or "Ill-nitride" or "nitride" as used herein refer to any composition or material related to (B, Al, Ga, In)N semiconductors having the formula BwAlxGayInzN where 0 < w < l, 0 < x < l, 0 < y < l, 0 < z < l, and w + x + y + z = 1. These terms as used herein are intended to be broadly construed to include respective nitrides of the single species, B, Al, Ga, and In, as well as binary, ternary and quaternary compositions of such Group III metal species. Accordingly, these terms include, but are not limited to, the compounds of AIN, GaN, InN, AlGaN, AlInN, InGaN, and AlGalnN. When two or more of the (B, Al, Ga, In)N component species are present, all possible compositions, including

stoichiometric proportions as well as off-stoichiometric proportions (with respect to the relative mole fractions present of each of the (B, Al, Ga, In)N component species that are present in the composition), can be employed within the broad scope of this invention. Further, compositions and materials within the scope of the invention may further include quantities of dopants and/or other impurity materials and/or other inclusional materials.

This invention also covers the selection of particular crystal orientations, directions, terminations and polarities of Group-Ill nitrides. When identifying crystal orientations, directions, terminations and polarities using Miller indices, the use of braces, { }, denotes a set of symmetry-equivalent planes, which are represented by the use of parentheses, ( ). The use of brackets, [ ], denotes a direction, while the use of brackets, < >, denotes a set of symmetry-equivalent directions.

Many Group-Ill nitride devices are grown along a polar orientation, namely a c-plane {0001 } of the crystal, although this results in an undesirable quantum- confined Stark effect (QCSE), due to the existence of strong piezoelectric and spontaneous polarizations. One approach to decreasing polarization effects in Group- Ill nitride devices is to grow the devices along nonpolar or semipolar orientations of the crystal.

The term "nonpolar" includes the {11-20} planes, known collectively as a- planes, and the {10-10} planes, known collectively as m-planes. Such planes contain equal numbers of Group-Ill and Nitrogen atoms per plane and are charge-neutral. Subsequent nonpolar layers are equivalent to one another, so the bulk crystal will not be polarized along the growth direction. The term "semipolar" can be used to refer to any plane that cannot be classified as c-plane, a-plane, or m-plane. In crystallographic terms, a semipolar plane would be any plane that has at least two nonzero h, i, or k Miller indices and a nonzero 1 Miller index. Subsequent semipolar layers are equivalent to one another, so the crystal will have reduced polarization along the growth direction.

References

The following references are incorporated by reference herein.

[1] Takakura, N. et al., Semiconductor Light Emitting Element Employing Group-III Metal Nitride Crystal and Process for Producing Group-III Metal Nitride Crystal. Japanese Patent Publication No. JP2005175276A2, published on June 30, 2005.

[2] Sasaki, T., Mori, Y., Yoshimura, M., Kawamura, F. and Hirota, R., Method of Manufacturing Group-III Nitride Crystal. US Patent No. 7,288,151, issued October 30, 2007.

[3] Sasaki, T. et al., Method for Manufacturing Nitride Single Crystal of Group-III Element, Apparatus Used for the Same, and Nitride Single Crystal of Group-III Element Obtained by the Method. Japanese Patent Publication No.

JP2006089376A2, published on April 6, 2006 .

[4] Sasaki, T., Mori, Y., Yoshimura, M., Kawamura, S. and Hirota, T.,

Production Method for Group-III Nitride Crystal. Japanese Patent Publication No. JP2005194147A2, published on July 21, 2005.

[5] Takakura, N. et al., Semiconductor Light Emitting Element Employing Group-III Metal Nitride Crystal and Process for Producing Group-III Metal Nitride Crystal. Japanese Patent Publication No. JP2005175275 A2, published on June 30, 2005.

[6] Sasaki T. et al., Method For Manufacturing Nitride Single Crystal Of Group III Element, Apparatus Used For The Same, And Nitride Single Crystal Of Group III Element Obtained By The Method, Japanese Patent Publication No.

JP2004307333A2, published on November 4, 2004.

Conclusion

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.

Claims

WHAT IS CLAIMED IS:
1. A method of growing a Group-Ill nitride crystal using a flux comprised of one or more Group-Ill metals and one or more alkali metals, comprising:
coating at least one surface of a seed with a thin wetting layer comprised of one or more Group-Ill metals and one or more alkali metals; and
growing the Group-Ill nitride crystal on the seed in a growth atmosphere, by bringing the flux into contact with the seed or by bringing the seed into contact with the flux, wherein the seed or flux is at least partially exposed to the growth atmosphere.
2. The method of claim 1, wherein the seed is a Group-Ill nitride crystal.
3. The method of claim 1, wherein the Group-Ill metal is one or more of
Al, Ga or In, and the alkali metal is Na.
4. The method of claim 1, wherein the coating step is performed intermittently or continuously.
5. The method of claim 1, wherein the coating step is performed by dripping or flowing the flux over one or more surfaces of the seed.
6. The method of claim 1, wherein the coating step is performed by submersing or submerging the seed within the flux and placing one facet of the seed within some specified distance of an interface between the flux and the atmosphere.
7. The method of claim 1, further comprising subjecting the seed, the Group-Ill nitride crystal, or the flux to mechanical movements, such as stirring or agitating, to shorten a distance required for the nitrogen to integrate with the seed or the Grou -III nitride crystal.
8. The method of claim 1, wherein the growing step further comprises maintaining the thin wetting layer on the Group-Ill nitride crystal during the growth of the Group-Ill nitride crystal.
9. The method of claim 1, wherein the Group-Ill nitride crystal has one or more polar, non-polar or semi-polar facets exposed.
10. A Group-Ill nitride crystal grown using the method of claim 1.
11. An apparatus for growing a Group-Ill nitride crystal using a flux comprised of one or more Group-Ill metals and one or more alkali metals, comprising:
means for coating at least one surface of a seed with a thin wetting layer comprised of one or more Group-Ill metals and one or more alkali metals; and
a chamber for growing the Group-Ill nitride crystal on the seed in a growth atmosphere, by bringing the flux into contact with the seed or by bringing the seed into contact with the flux, wherein the seed or flux is at least partially exposed to the growth atmosphere.
12. The apparatus of claim 11, wherein the seed is a Group-Ill nitride crystal.
13. The apparatus of claim 11, wherein the Group-Ill metal is one or more of Al, Ga or In, and the alkali metal is Na.
14. The apparatus of claim 11, wherein the means for coating is performed intermittently or continuously.
15. The apparatus of claim 11, wherein the means for coating is performed by dripping or flowing the flux over one or more surfaces of the seed.
16. The apparatus of claim 11, wherein the means for coating is performed by submersing or submerging the seed within the flux and placing one facet of the seed within some specified distance of an interface between the flux and the atmosphere.
17. The apparatus of claim 11, further comprising means for subjecting the seed, the Group-Ill nitride crystal, or the flux to mechanical movements, such as stirring or agitating, to shorten a distance required for the nitrogen to integrate with the seed or the Group-Ill nitride crystal.
18. The apparatus of claim 11 , wherein the chamber further comprises means for maintaining the thin wetting layer on the Group-Ill nitride crystal during the growth of the Group-Ill nitride crystal.
19. The apparatus of claim 11, wherein the Group-Ill nitride crystal has one or more polar, non-polar or semi-polar facets exposed.
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