# US 2010/0163931 A1 · Group iii-v nitride layer and method for producing the same

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- Number: US 2010/0163931 A1
- Document ID: US20100163931A1
- Status: Published application
- Kind: A1
- Application number: 12/293,643
- Filed: 2007-03-19
- Published: 2010-07-01
- Earliest claimed: 2006-03-20
- Assignees: Kanagawa Academy of Science and Technology; The University of Tokyo; Mitsubishi Chemical Corporation
- Inventors: Hiroshi Fujioka; Atsushi Kobayashi; Hideyoshi Horie; Hidetaka Amanai; Satoru Magao
- Web page: https://patentgrep.com/patent/US20100163931A1

## CPC

- C23C 14/0026: {Activation or excitation of reactive gases outside the coating chamber}
- C23C 14/0617: {AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi}
- C23C 14/28: by wave energy or particle radiation (C23C14/32 - C23C14/48 take precedence)
- C30B 23/02: Epitaxial-layer growth
- C30B 23/025: {characterised by the substrate}
- C30B 29/403: {AIII-nitrides}
- H10P 14/22: using physical deposition, e.g. vacuum deposition or sputtering
- H10P 14/2914: {Oxides}
- H10P 14/2925: {Surface structures}
- H10P 14/2926: {Crystal orientations}
- H10P 14/3216: {Nitrides}
- H10P 14/3416: {Nitrides}
- H10P 14/36: {characterised by treatments done before the formation of the materials}
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- 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
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

There is disclosed a hexagonal Group III-V nitride layer exhibiting high quality crystallinity capable of improving the properties of a semiconductor device such as a light emitting element. This nitride layer is a Group III-V nitride layer belonging to hexagonal crystal formed by growth on a substrate having a different lattice constant, which has a growth-plane orientation of {1-100} and in which a full width at half maximum b1 of angle dependence of X-ray diffraction intensity in a {1-210} plane perpendicular to the growth-plane upon X-ray incident angle from a direction parallel to the growth-plane satisfies the condition of 0.01°≦b1≦0.5°, or the full width at half maximum b2 of angle dependence of X-ray diffraction intensity in a {0001} plane upon X-ray incident angle from a direction parallel to the growth-plane satisfies the condition of 0.01°≦b2≦0.5°.

## Claims

### Claim at position 1

1-45. (canceled)

### Claim 46

A Group III-V nitride layer belonging to hexagonal crystal formed by growing on a substrate having a different lattice constant, with the proviso that a substrate containing either Li or C as a principal constituent element is excluded,
wherein the Group III-V nitride layer satisfies at least one of the following conditions (i) to (iv):
(i) a growth-plane is a plane perpendicular to {0001} (hereinafter, referred to as a “nonpolar plane”) and a full width at half maximum b1 of angle dependence of X-ray diffraction intensity in a plane perpendicular to the growth-plane and parallel to c-axis [0001], upon X ray incident angle from a direction parallel to the growth-plane, satisfies the condition of 0.01°≦b1≦0.5°;
(ii) a growth-plane is a nonpolar plane and a full width at half maximum b2 of angle dependence of a X-ray diffraction intensity in {0001} plane, upon X-ray incident angle from a direction parallel to the growth-plane, satisfies the condition of 0.01°≦b2≦0.5°;
(iii) a growth-plane is a nonpolar plane, and when a diffraction plane is {1-100} plane or {11-20} plane which forms an angle of 60° or more and less than 90° with the growth-plane, a full width at half maximum b3 of angle dependence of X-ray diffraction intensity in the diffraction plane, upon X-ray incident angle from a direction parallel to a plane perpendicular to the diffraction plane and parallel to c-axis [0001], satisfies the condition of 0.01°≦b3≦0.5°; and
(iv) a growth-plane is a nonpolar plane and when, assuming that the growth-plane orientation is represented by {ijk0}, a diffraction plane is {ijk2} plane tilted from the growth-plane only to [0001] and [000-1] directions, a full width at half maximum b4 of angle dependence of X-ray diffraction intensity in the diffraction plane, upon X-ray incident angle from a direction parallel to a plane formed by tilting {0001} plane by an angle equal to a tilt angle from the growth-plane to the diffraction plane in the same direction, satisfies the condition of 0.01°≦b4≦0.5°.

### Claim 47

A Group III-V nitride layer belonging to hexagonal crystal formed by growing on a substrate having a different lattice constant, with the proviso that a substrate containing either Li or C as a principal constituent element is excluded,
wherein the growth-plane is a nonpolar plane and a full width at half maximum a1 of angle dependence of X-ray diffraction intensity in the growth-plane, upon X-ray incident angle from a direction parallel to a plane perpendicular to the growth-plane and parallel to c-axis [0001], satisfies the condition of 0.01°≦a1≦0.25°.

### Claim 48 (depends on 46)

The Group III-V nitride layer as claimed in claim 46, wherein a thickness T (nm) satisfies the condition of 5 nm≦T≦10000 nm.

### Claim 49 (depends on 47)

The Group III-V nitride layer as claimed in claim 47, wherein a thickness T (nm) satisfies the condition of 5 nm≦T≦10000 nm.

### Claim 50 (depends on 46)

The Group III-V nitride layer as claimed in claim 46, wherein the growth-plane is a nonpolar plane, and a full width at half maximum a2 of angle dependence of X diffraction intensity of the growth-plane, upon X-ray incident angle from a direction perpendicular to c-axis [0001], satisfies the condition of 0.05°≦a2≦0.5°.

### Claim 51 (depends on 47)

The Group III-V nitride layer as claimed in claim 47, wherein the growth-plane is a nonpolar plane, and a full width at half maximum a2 of angle dependence of X diffraction intensity of the growth-plane, upon X-ray incident angle from a direction perpendicular to c-axis [0001], satisfies the condition of 0.05°≦a2≦0.5°.

### Claim 52 (depends on 46)

The Group III-V nitride layer as claimed in claim 46, wherein the substrate has a crystal structure belonging to hexagonal crystal, and a nominal plane orientation of the substrate is identical to a growth-plane orientation a Group III-V nitride layer to be grown.

### Claim 53 (depends on 47)

The Group III-V nitride layer as claimed in claim 47, wherein the substrate has a crystal structure belonging to hexagonal crystal, and a nominal plane orientation of the substrate is identical to a growth-plane orientation a Group III-V nitride layer to be grown.

### Claim 54 (depends on 46)

The Group III-V nitride layer as claimed in claim 46, wherein the substrate is ZnO.

### Claim 55 (depends on 47)

The Group III-V nitride layer as claimed in claim 47, wherein the substrate is ZnO.

### Claim 56 (depends on 50)

The Group III-V nitride layer as claimed in claim 50, wherein the substrate is ZnO.

### Claim 57 (depends on 51)

The Group III-V nitride layer as claimed in claim 51, wherein the substrate is ZnO.

### Claim 58 (depends on 46)

The Group III-V nitride layer as claimed in claim 46, comprising at least
a first layer formed at a growth temperature of less than 500° C., directly on the substrate, and
a second layer formed on the first layer at a growth temperature of 400° C. or higher and higher than the growth temperature of the first layer.

### Claim 59 (depends on 47)

The Group III-V nitride layer as claimed in claim 47, comprising at least
a first layer formed at a growth temperature of less than 500° C., directly on the substrate, and
a second layer formed on the first layer at a growth temperature of 400° C. or higher and higher than the growth temperature of the first layer.

### Claim 60 (depends on 54)

The Group III-V nitride layer as claimed in claim 54, comprising at least
a first layer formed at a growth temperature of less than 500° C., directly on the substrate, and
a second layer formed on the first layer at a growth temperature of 400° C. or higher and higher than the growth temperature of the first layer.

### Claim 61 (depends on 55)

The Group III-V nitride layer as claimed in claim 55, comprising at least
a first layer formed at a growth temperature of less than 500° C., directly on the substrate, and
a second layer formed on the first layer at a growth temperature of 400° C. or higher and higher than the growth temperature of the first layer.

### Claim 62 (depends on 58)

The Group III-V nitride layer as claimed in claim 58, wherein the first layer has a thickness of less than 500 nm.

### Claim 63 (depends on 59)

The Group III-V nitride layer as claimed in claim 59, wherein the first layer has a thickness of less than 500 nm.

### Claim 64 (depends on 60)

The Group III-V nitride layer as claimed in claim 60, wherein the first layer has a thickness of less than 500 nm.

### Claim 65 (depends on 61)

The Group III-V nitride layer as claimed in claim 61, wherein the first layer has a thickness of less than 500 nm.

### Claim 66 (depends on 46)

A laminated structure comprising the Group III-V nitride layer as claimed in claim 46 and an additional layer formed over the layer.

### Claim 67 (depends on 47)

A laminated structure comprising the Group III-V nitride layer as claimed in claim 47 and an additional layer formed over the layer.

### Claim 68 (depends on 54)

A laminated structure comprising the Group III-V nitride layer as claimed in claim 54 and an additional layer formed over the layer.

### Claim 69 (depends on 55)

A laminated structure comprising the Group III-V nitride layer as claimed in claim 55 and an additional layer formed over the layer.

### Claim 70

A process for growing a Group III-V nitride layer belonging to hexagonal crystal on a substrate having a different lattice constant, with the proviso that a substrate containing Li as a principal constituent element is excluded,
the process comprising steps of:
(a) providing a substrate having, as a principal surface, a hexagonal nonpolar plane or a plane having a lattice structure identical to that of the hexagonal nonpolar plane,
(b) growing the Group III-V nitride layer on the principal surface of the substrate at least in two steps, comprising
(b-1) a first sub-growing step of growing a first layer on the principal surface of the substrate at a growth temperature of lower than 500° C. while maintaining a single crystal structure on the growth-plane, and
(b-2) a second sub-growing step of growing a second layer on the first layer at a growth temperature of 400° C. or higher and higher than the growth temperature in the first sub-growing step.

### Claim 71 (depends on 70)

The process as claimed in claim 70, wherein a growth rate of the first layer in the first sub-growing step was selected from the range of more than 10 nm/hr and less than 300 nm/hr, and a growth rate of the second layer in the second sub-growing step is selected from the range of 30 nm/hr to 5000 nm/hr.

### Claim 72 (depends on 70)

The process as claimed in claim 70, wherein in the first sub-growing step, the Group III element is intermittently supplied to the growth-plane and the Group V element is supplied in a form containing radicals.

### Claim 73 (depends on 72)

The process as claimed in claim 72, wherein in the first sub-growing step, the Group III element is intermittently supplied to the growth-plane and the Group V element is supplied in a form containing molecular nitrogen radicals.

### Claim 74 (depends on 72)

The process as claimed in claim 72, wherein in the first sub-growing step, stop period of the intermittent supply of the Group III element is selected from the range of 1 m sec to 10 sec.

### Claim 75 (depends on 73)

The process as claimed in claim 73, wherein in the first sub-growing step, stop period of the intermittent supply of the Group III element is selected from the range of 1 m sec to 10 sec.

### Claim 76 (depends on 72)

The process as claimed in claim 72, wherein in the second sub-growing step, the Group III element is intermittently supplied to the growth-plane and the Group V element is supplied in a form containing radicals.

### Claim 77 (depends on 76)

The process as claimed in claim 76, wherein in the second sub-growing step, the Group III element is intermittently supplied to the growth-plane and the Group V element is supplied in a form containing molecular nitrogen radicals.

### Claim 78 (depends on 70)

The process as claimed in claim 70, wherein in the first sub-growing step, the first layer is grown by pulse laser deposition.

### Claim 79 (depends on 72)

The process as claimed in claim 72, wherein in the first sub-growing step, the first layer is grown by pulse laser deposition.

### Claim 80 (depends on 73)

The process as claimed in claim 73, wherein in the first sub-growing step, the first layer is grown by pulse laser deposition.

### Claim 81 (depends on 70)

The process as claimed in claim 70, wherein in the first sub-growing step, the first layer is grown such that its thickness is less than 500 nm.

### Claim 82 (depends on 70)

The process as claimed in claim 70, wherein the substrate is a ZnO substrate having a plane with a surface roughness Ra of 3 nm or less.

### Claim 83 (depends on 72)

The process as claimed in claim 72, wherein the substrate is a ZnO substrate having a plane with a surface roughness Ra of 3 nm or less.

### Claim 84 (depends on 73)

The process as claimed in claim 73, wherein the substrate is a ZnO substrate having a plane with a surface roughness Ra of 3 nm or less.

### Claim 85 (depends on 70)

A process for manufacturing a laminated structure comprising further depositing, on the Group III-V nitride layer formed by the process as claimed in claim 70, an additional layer comprising at least a lattice-matched layer by a deposition process selected from the group consisting of VPE, CVD, MBE, sputtering, evaporation and a combination of two or more of these.

### Claim 86 (depends on 82)

A process for manufacturing a laminated structure comprising further depositing, on the Group III-V nitride layer formed by the process as claimed in claim 82, an additional layer comprising at least a lattice-matched layer by a deposition process selected from the group consisting of VPE, CVD, MBE, sputtering, evaporation and a combination of two or more of these.

### Claim 87 (depends on 83)

A process for manufacturing a laminated structure comprising further depositing, on the Group III-V nitride layer formed by the process as claimed in claim 83, an additional layer comprising at least a lattice-matched layer by a deposition process selected from the group consisting of VPE, CVD, MBE, sputtering, evaporation and a combination of two or more of these.

### Claim 88 (depends on 84)

A process for manufacturing a laminated structure comprising further depositing, on the Group III-V nitride layer formed by the process as claimed in claim 84, an additional layer comprising at least a lattice-matched layer by a deposition process selected from the group consisting of VPE, CVD, MBE, sputtering, evaporation and a combination of two or more of these.

### Claim 89

A Group III-V nitride layer belonging to hexagonal crystal formed by growing on a substrate having a different lattice constant,
wherein
the substrate is a ZnO substrate having a nonpolar plane as a principal surface,
is grown by pulse laser deposition where a Group III element and nitrogen radicals are supplied, and
has a composition represented by InxAlyGa(1-x-y)N wherein x and y are numbers satisfying the conditions of 0≦x≦1, 0≦y≦1 and 0≦x+y≦1, and
wherein at least one of the following conditions (i) to (v) is met:
(i) a growth-plane is a plane perpendicular to {0001} (hereinafter, referred to as a “nonpolar plane”) and a full width at half maximum b1 of angle dependence of X-ray diffraction intensity in a plane perpendicular to the growth-plane and parallel to c-axis [0001] upon X ray incident angle from a direction parallel to the growth-plane satisfies the condition of 0.01°≦b1≦0.5°;
(ii) a growth-plane is a nonpolar plane and a full width at half maximum b2 of angle dependence of a X-ray diffraction intensity in {0001} plane upon X-ray incident angle from a direction parallel to the growth-plane satisfies the condition of 0.01°≦b2≦0.5°;
(iii) a growth-plane is a nonpolar plane, and when a diffraction plane is {1-100} plane or {11-20} plane which forms an angle of 60° or more and less than 90° with the growth-plane, a full width at half maximum b3 of angle dependence of X-ray diffraction intensity in the diffraction plane upon X-ray incident angle from a direction parallel to a plane perpendicular to the diffraction plane and parallel to c-axis [0001] satisfies the condition of 0.01°≦b3≦0.5°;
(iv) a growth-plane is a nonpolar plane and when, assuming that the growth-plane orientation is represented by {ijk0}, a diffraction plane is {ijk2} plane tilted from the growth-plane only to [0001] and [000-1] directions, a full width at half maximum b4 of angle dependence of X-ray diffraction intensity in the diffraction plane upon X-ray incident angle from a direction parallel to a plane formed by tilting {0001} plane by an angle equal to a tilt angle from the growth-plane to the diffraction plane in the same direction satisfies the condition of 0.01°≦b4≦0.5°; and
(v) a growth-plane is a nonpolar plane and a full width at half maximum a1 of angle dependence of X-ray diffraction intensity of the growth-plane upon X-ray incident angle from a direction parallel to a plane perpendicular to the growth-plane and parallel with c-axis satisfies the condition of 0.01°≦a1≦0.25°.

### Claim 90

A process for growing a Group III-V nitride layer belonging to hexagonal crystal on a substrate having a different lattice constant, with the proviso that a substrate containing Li as a principal constituent element is excluded,
the process comprising growing steps of:
(a) providing a substrate having a hexagonal nonpolar plane or a plane having a lattice structure identical to that of the hexagonal nonpolar plane,
(b) growing the Group III-V nitride layer on the principal surface of the substrate at least in two steps, comprising
(b-1) a first sub-growing step of growing a first layer on the principal surface of the substrate at a growth temperature of lower than 500° C. while intermittently supplying a Group III element with a supply stop period in the range of 0.001 sec to 10 sec, and
(b-2) a second sub-growing step of growing a second layer on the first layer at a growth temperature of 400° C. or higher and higher than the growth temperature in the first sub-growing step.

### Claim 91

A process for growing a Group III-V nitride layer belonging to hexagonal crystal on a substrate having a different lattice constant, with the proviso that a substrate containing Li as a principal constituent element is excluded,
the process comprising the growing steps of:
(a) providing a substrate having a hexagonal nonpolar plane or a plane having a lattice structure identical to that of the hexagonal nonpolar plane,
(b) growing the Group III-V nitride layer on the principal surface of the substrate at least in two steps, comprising
(b-1) a first sub-growing step of growing a first layer on the principal surface of the substrate at a growth temperature of lower than 500° C. and a growth rate of more than 10 nm/hr and less than 300 nm/hr while intermittently supplying a Group III element with a supply stop period in the range of 0.001 sec to 10 sec, and
(b-2) a second sub-growing step of growing a second layer on the first layer at a growth temperature of 400° C. or higher and higher than the growth temperature in the first sub-growing step.