# US 12,000,063 B2 · Large area group III nitride crystals and substrates, methods of making, and methods of use

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- Number: US 12,000,063 B2
- Document ID: US12000063B2
- Status: Granted
- Kind: B2
- Application number: 17/173,170
- Filed: 2021-02-10
- Published: 2021-08-12
- Granted: 2024-06-04
- Earliest claimed: 2020-02-11
- Assignees: SLT Technologies, Inc.
- Applicants: SLT Technologies, Inc
- Inventors: Drew W. Cardwell; Mark P. D'Evelyn
- Web page: https://patentgrep.com/patent/US12000063B2

## CPC

- C30B 25/18: characterised by the substrate
- C01B 21/0632: {with gallium, indium or thallium}
- C30B 25/04: Pattern deposit, e.g. by using masks
- C30B 29/406: {Gallium nitride}
- C30B: SINGLE-CRYSTAL GROWTH (by using ultra-high pressure, e.g. for the formation of diamonds, B01J3/06); UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL (zone-refining of metals or alloys C22B); PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (casting of metals, casting of other substances by the same processes or devices B22D; working of plastics B29; modifying the physical structure of metals or alloys C21D, C22F); SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (for producing semiconductor devices or parts thereof H10); APPARATUS THEREFOR
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

Embodiments of the present disclosure include techniques related to techniques for processing materials for manufacture of group-III metal nitride and gallium based substrates. More specifically, embodiments of the disclosure include techniques for growing large area substrates using a combination of processing techniques. Merely by way of example, the disclosure can be applied to growing crystals of GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and others for manufacture of bulk or patterned substrates. Such bulk or patterned substrates can be used for a variety of applications including optoelectronic and electronic devices, lasers, light emitting diodes, solar cells, photo electrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, and transistors, and others.

## Claims

### Claim 1

A free-standing group III metal nitride substrate comprising at least two crystals, each of the at least two crystals comprising:
a group III metal selected from gallium, aluminum, and indium, or combinations thereof, and nitrogen, wherein:
each of the at least two crystals having a wurtzite crystal structure comprises a first surface having a maximum dimension greater than 10 millimeters in a first direction and a maximum dimension greater than 4 millimeters in a second direction orthogonal to the first direction, an average concentration of threading dislocations between 102 cm−2 and 1×106 cm−2, an average concentration of stacking faults below 103 cm−1, a symmetric x-ray rocking curve full width at half maximum less than 200 arcsec,
the magnitudes of a crystallographic miscut of the first surfaces of each of the at least two crystals are equal, to within 0.5 degree,
the directions of crystallographic miscuts of the first surfaces of each of the at least two crystals are equal, to within 10 degrees,
each of the at least two crystals is bonded to a matrix member comprising polycrystalline GaN that is textured in a c-direction, and
a polar misorientation angle γ between a first surface of a first crystal of the at least two crystals and a first surface of a second crystal of the at least two crystals is greater than about 0.005 degrees and less than about 0.2 degrees and misorientation angles α and β are greater than about 0.01 degrees and less than about 1 degree.

### Claim 2 (depends on 1)

The free-standing group III metal nitride substrate of claim 1, wherein the free-standing group III metal nitride substrate has a maximum dimension in the first direction greater than 40 millimeters.

### Claim 3 (depends on 2)

The free-standing group III metal nitride substrate of claim 2, wherein the magnitude of the crystallographic miscut of the first surfaces of each of the at least two crystals is equal, to within 0.2 degree and the directions of the crystallographic miscuts of the first surfaces of each of the at least two crystals is equal, to within 2 degrees.

### Claim 4 (depends on 2)

The free-standing group III metal nitride substrate of claim 2, wherein each of the first surfaces has a crystallographic orientation that is within 5 degrees of an orientation selected from {20−2±1}, {30−3±1}, and {10−10} and a miscut in the a-direction that is less than 0.5 degree.

### Claim 5 (depends on 4)

The free-standing group III metal nitride substrate of claim 4, wherein each of the first surfaces has a crystallographic orientation that is within 1 degree of an orientation selected from {20−2±1}, {30−3±1}, and {10−10} and a miscut in the a-direction that is less than 0.1 degree.

### Claim 6 (depends on 2)

The free-standing group III metal nitride substrate of claim 2, wherein the maximum dimension in the first direction is between 45 and 110 millimeters.

### Claim 7 (depends on 2)

The free-standing group III metal nitride substrate of claim 2, wherein the free-standing group III metal nitride substrate further comprises:
a thickness is between about 150 micrometers and about 2 millimeters,
a total thickness variation is less than about 25 micrometers, and
a macroscopic bow is less than about 50 micrometers.

### Claim 8 (depends on 1)

The free-standing group III metal nitride crystal of claim 1, wherein a gap is formed between adjacent edges of each of the at least two crystals, the gap being at least partially filled by the matrix member.

### Claim 9 (depends on 1)

The free-standing group III metal nitride crystal of claim 1, wherein the first surface of each of the crystals of the at least two crystals has a crystallographic orientation within 5 degrees of a semipolar orientation selected from {6 0−6 ±1}, {5 0−5 ±1}, {4 0−4 ±1}, {3 0−3±1}, {5 0−5 ±2}, {7 0−7 ±3}, {2 0−2±1}, {3 0−3±2}, {4 0−4 ±3}, {5 0−5 ±4}, {1 0−1±1}, {1 0−1±2}, {1 0−1±3}, {2 1−3±1}, and {3 0−3±4}.

### Claim 10 (depends on 1)

The free-standing group III metal nitride crystal of claim 1, wherein the first surface has impurity concentrations of:
oxygen (O) between 1×1016 cm−3 and 1×1019 cm−3,
hydrogen (H) between 1×1016 cm−3 and 2×1019 cm−3, and
at least one of fluorine (F) and chlorine (Cl) between 1 ×1015 cm−3 and 1×1019 cm−3.

### Claim 11 (depends on 1)

The free-standing group III metal nitride crystal of claim 1, further comprising an interfacial layer at an interface between at least one crystal of the at least two crystals and the matrix member.

### Claim 12 (depends on 11)

The free-standing group III metal nitride crystal of claim 11, wherein the interfacial layer comprises at least one of graphite, boron nitride, molybdenum disulfide, and tungsten disulfide.

### Claim 13 (depends on 1)

The free-standing group III metal nitride crystal of claim 1, wherein the first surfaces of each of the crystals of the at least two crystals are substantially parallel to a first plane.

### Claim 14 (depends on 1)

The free-standing group III metal nitride crystal of claim 1, wherein the matrix member has a diameter that is greater than 40 mm.

### Claim 15 (depends on 1)

The free-standing group III metal nitride crystal of claim 1, wherein the matrix member further comprises a porous member.

### Claim 16 (depends on 15)

The free-standing group III metal nitride crystal of claim 15, wherein the porous member comprises at least one of graphite, carbon fiber, silica fiber, aluminosilicate fiber, borosilicate fiber, a silicon carbide coating, a pyrolytic boron nitride coating, or a pyrolytic graphite coating.

### Claim 17

A free-standing group III metal nitride substrate comprising at least two crystals, each of the at least two crystals comprising:
a group III metal selected from gallium, aluminum, and indium, or combinations thereof, and nitrogen, wherein:
each of the at least two crystals having a wurtzite crystal structure comprises a first surface, an average concentration of threading dislocations between 102 cm−2 and 1×106 cm−2, an average concentration of stacking faults below 103 cm−1, a symmetric x-ray rocking curve full width at half maximum less than 200 arcsec,
each of the first surfaces has a crystallographic orientation that is within 5 degrees of an orientation selected from {20−2±1}, {30−3±1}, and {10−10} and a miscut in the a-direction that is less than 0.5 degree;
the magnitudes of a crystallographic miscut of the first surfaces of each of the at least two crystals are equal, to within 0.2 degree,
the directions of crystallographic miscuts of the first surfaces of each of the at least two crystals are equal, to within 2 degrees,
each of the at least two crystals is bonded to a matrix member comprising polycrystalline GaN, and
a polar misorientation angle γ between a first surface of a first crystal of the at least two crystals and a first surface of a second crystal of the at least two crystals is greater than about 0.005 degrees and less than about 0.2 degrees and misorientation angles α and β are greater than about 0.01 degrees and less than about 1 degree.

### Claim 18 (depends on 17)

The free-standing group III metal nitride substrate of claim 17, wherein each of the first surfaces has a crystallographic orientation that is within 1 degree of an orientation selected from {20−2±1}, {30−3±1}, and {10−10} and a miscut in the a-direction that is less than 0.1 degree.