JP2014001137A - GaN SINGLE CRYSTAL SUBSTRATE AND METHOD OF MANUFACTURING THE SAME, AND GaN-BASED SEMICONDUCTOR DEVICE AND METHOD OF MANUFACTURING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a GaN single crystal substrate which has a large diameter and in which surface orientation of a principal surface has a value other than (0001) and (000-1) and dislocation density within the principal surface is substantially uniform, and a method of manufacturing the substrate.SOLUTION: In the GaN single crystal substrate 20p, an area of a principal surface 20pm is 10 cmor more, surface orientation of the principal surface 20pm is inclined by 65° or more and 85° or less to a (0001) surface or a (000-1) surface 20c, and distribution of dislocation density within the principal surface 20pm is substantially uniform, that is, dispersion of dislocation density to average dislocation density within the principal surface 20pm is within ±100%, for example.

Description

  The present invention provides a GaN single crystal substrate having a large diameter, a plane orientation of the principal plane other than (0001) and (000-1) (ie {0001}), and a substantially uniform distribution of dislocation density in the principal plane; It relates to the manufacturing method. The present invention also relates to a GaN-based semiconductor device in which at least one GaN-based semiconductor layer is formed on the main surface of the GaN single crystal substrate and a method for manufacturing the same.

  Group III nitride crystals suitably used for light emitting devices, electronic devices, semiconductor sensors, etc. are usually vapor phase methods such as HVPE (hydride vapor phase epitaxy) and MOCVD (metal organic chemical vapor deposition), flux methods The crystal is grown on a main surface such as a sapphire substrate having a (0001) principal surface or a (111) A principal surface by a liquid phase method. For this reason, the group III nitride crystal usually obtained has a main surface with a plane orientation of {0001}.

  A light-emitting device in which a light-emitting layer having an MQW (multiple quantum well) structure is formed on a main surface of a group III nitride crystal having a main surface of {0001} in the plane orientation has a group III nitride crystal < Since the polarization in the 0001> direction causes spontaneous polarization in the light emitting layer, the blue shift of light emission becomes large and the light emission efficiency decreases. For this reason, a group III nitride crystal having a principal surface with a plane orientation other than {0001} is desired.

  In order to respond to such a request, Japanese Patent Application Laid-Open No. 2008-143772 (hereinafter referred to as Patent Document 1) describes {1-10X} (where X is an integer equal to or greater than 0), {11-2Y} (where Y Is an integer greater than or equal to 0) and {HK− (H + K) 0} (where H and K are integers other than 0), the plane orientation with an off angle of 5 ° or less, specifically { 1-100}, {11-20}, {1-102}, {11-22}, {12-30}, and a group III nitride crystal having a principal plane of any one of {23-50} The manufacturing method is disclosed.

  However, even when the manufacturing method disclosed in Patent Document 1 is used, the group III nitride crystal grown on the principal plane having the {1-100}, {11-20} or {23-50} plane orientation is partially Therefore, there is a problem that it is difficult to obtain a large-diameter single crystal substrate. Further, a crystal growth surface of a group III nitride crystal grown on a {1-102}, {11-22} principal plane has a facet of {0001} and a plane other than {0001}. Orientation facets arise. Here, the dislocations of the portion that grows with the facet of {0001} plane orientation as the crystal growth plane propagate in the direction perpendicular to the {0001} plane (that is, <0001> direction), and facet of plane orientation other than {0001}. The dislocations in the portion that grows as a crystal growth plane propagate in a direction parallel to the {0001} plane. Since the variation in dislocation density on the main surface of the grown group III nitride crystal is large, there is a problem that the variation in characteristics of a semiconductor device using such a substrate becomes large.

  Japanese Patent Laid-Open No. 2006-052102 (hereinafter referred to as Patent Document 2) discloses a III-V nitride semiconductor substrate (specifically, a GaN free-standing substrate) having a substantially uniform dislocation density distribution and a method for manufacturing the same. Is disclosed. However, Patent Document 2 discloses that a group III-V nitride semiconductor substrate having a main surface with a plane orientation of (0001) is first grown while providing unevenness on the growth interface to flatten the growth interface. Although it has been disclosed that the distribution of dislocation density is substantially uniform by growing at a flattened growth interface, a III-V nitride system having a principal plane with a plane orientation other than {0001} is disclosed. There is no description or suggestion that the dislocation density distribution is substantially uniform for the semiconductor substrate.

JP 2008-143772 A JP 2006-052102 A

  The present invention solves the above-described problem, and has a large diameter, the orientation of the principal plane is other than (0001) and (000-1), and the distribution of dislocation density in the principal plane is substantially uniform. And it aims at providing the manufacturing method. Another object of the present invention is to provide a GaN-based semiconductor device having at least one GaN-based semiconductor layer formed on the main surface of the GaN single crystal substrate and having a uniform characteristic distribution and a method for manufacturing the same. .

In the present invention, the area of the main surface is 10 cm ² or more, the surface orientation of the main surface is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane, This is a GaN single crystal substrate having a substantially uniform dislocation density distribution. Here, the dispersion of the dislocation density in the main surface can be within ± 100% with respect to the average dislocation density in the main surface.

In the GaN single crystal substrate according to the present invention, the dislocation density in the main surface can be 5 × 10 ⁶ cm ⁻² or less. Moreover, the direction of the inclination of the surface orientation of the main surface with respect to the (0001) plane or the (000-1) plane can be the <10-10> direction. Moreover, the half width of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with respect to the (0002) plane and the (20-20) plane or the (22-40) plane can be 300 arcsec or less over the entire main surface.

The present invention is also a method for producing the above GaN single crystal substrate, wherein the main surface has an area of 10 cm ² or more and the main surface has a plane orientation of 65 with respect to the (0001) plane or the (000-1) plane. A step of preparing a GaN seed crystal substrate inclined at an angle of not less than 85 ° and not more than 85 °, a step of growing a GaN single crystal on the main surface of the GaN seed crystal substrate, and a GaN single crystal on the main surface of the GaN seed crystal substrate And a step of cutting a parallel plane to form a GaN single crystal substrate.

  The present invention is also a GaN-based semiconductor device including the GaN single-crystal substrate and at least one GaN-based semiconductor layer formed on the main surface of the GaN single-crystal substrate.

  The present invention also provides a method for manufacturing a GaN-based semiconductor device, comprising: preparing the GaN single-crystal substrate as described above; and growing at least one GaN-based semiconductor layer on the main surface of the GaN single-crystal substrate. It is.

  According to the present invention, there is provided a GaN single crystal substrate having a large diameter, a plane orientation of the main surface other than (0001) and (000-1), and a substantially uniform distribution of dislocation density in the main surface, and a method for manufacturing the same. Can be provided. In addition, it is possible to provide a GaN-based semiconductor device having at least one GaN-based semiconductor layer formed on the main surface of the GaN single crystal substrate and having a uniform characteristic distribution and a method for manufacturing the same.

It is the schematic which shows an example of the GaN single crystal substrate concerning this invention. It is the schematic which shows an example of the process of preparing the GaN seed crystal substrate in the manufacturing method of the GaN single crystal substrate concerning this invention. Here, (A) shows a sub-step of cutting out a plurality of GaN mother crystal pieces from the GaN mother crystal, and (B) shows a sub-step of arranging the plurality of GaN mother crystal pieces adjacent to each other in the lateral direction. C) shows a sub-process for growing a GaN seed crystal, and (D) shows a sub-process for forming a GaN seed crystal substrate. It is a schematic sectional drawing which shows an example of the manufacturing method of the GaN single crystal substrate concerning this invention. Here, (A) shows a step of preparing a GaN seed crystal substrate, (B) shows a step of growing a GaN single crystal, and (C) shows a step of forming a GaN single crystal substrate. It is a schematic diagram which shows the condition of the inclination of the surface orientation of the main surface with respect to (0001) plane or (000-1) plane in the GaN single crystal substrate concerning this invention. Here, (A) shows the case where the surface orientation of the main surface is {20-21}, (B) shows the case where the surface orientation of the main surface is {20-2-1}, and (C) shows the main surface orientation. The case where the surface orientation of the surface is {22-42} is shown, and (D) shows the case where the surface orientation of the main surface is {22-4-2}. 1 is a schematic sectional view showing an example of a GaN-based semiconductor device according to the present invention.

  In crystal geometry, a display (mirror display) such as (hkl) or (hkil) is used to indicate the plane orientation of the crystal plane. The plane orientation of the crystal plane in a hexagonal crystal such as a group III nitride crystal forming a GaN seed crystal substrate and a GaN single crystal substrate is represented by (hkil). Here, h, k, i and l are integers called Miller indices and have a relationship of i = − (h + k). The plane having the plane orientation (hkil) is referred to as the (hkil) plane. The direction perpendicular to the (hkil) plane (the normal direction of the (hkil) plane) is referred to as the [hkil] direction. Also, {hkil} means a generic plane orientation including individual plane orientations equivalent to (hkil) and its crystal geometry, and <hkil> is equivalent to [hkil] and its crystal geometry It means a generic direction including individual directions.

  Here, in a group III nitride crystal such as a GaN seed crystal and a GaN single crystal, group III element atomic planes such as gallium (Ga) atomic planes and nitrogen (N) atomic planes are alternately arranged in the <0001> direction. , <0001> direction is polar. In the present application, the crystal axes are set so that the group III element atomic plane such as the gallium atomic plane is the (0001) plane and the nitrogen atomic plane is the (000-1) plane.

[GaN single crystal substrate]
(Embodiment 1)
Referring to FIG. 1, a GaN single crystal substrate 20p according to an embodiment of the present invention has an area of a main surface 20pm of 10 cm ² or more, and the surface orientation of the main surface 20pm is a (0001) plane or (000-1). ) It is inclined at 65 ° or more and 85 ° or less with respect to the surface 20c, and the distribution of dislocation density in the main surface 20pm is substantially uniform.

The GaN single crystal substrate 20p of the present embodiment has a large diameter with an area of the main surface 20pm of 10 cm ² or more. Moreover, since the plane orientation of the main surface 20pm has an inclination angle α of 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane 20c, the GaN single crystal substrate 20p is used. For GaN-based semiconductor devices, the blue shift of light emission is suppressed, and the decrease in light emission efficiency is suppressed. From such a viewpoint, the plane orientation of the main surface 20pm preferably has an inclination angle α of 70 ° or more and 80 ° or less with respect to the (0001) plane or the (000-1) plane 20c, and is 72 ° or more. More preferably, it has an inclination angle α of 78 ° or less. In addition, since the dislocation density distribution in the main surface 20pm is substantially uniform, the distribution of device characteristics in the main surface of the GaN-based semiconductor device using the GaN single crystal substrate 20p is substantially uniform. Become.

  In the GaN single crystal substrate 20p of the present embodiment, the distribution of dislocation density in the main surface 20pm is substantially uniform means that the distribution of device characteristics in the main surface of a GaN-based semiconductor device using the same is substantially uniform. For example, it means that the variation in dislocation density in the main surface 20 pm is within ± 100% of the average dislocation density in the main surface 20 pm. From the viewpoint of making the distribution of the device characteristics in the main surface of the GaN-based semiconductor device more uniform, the variation in the dislocation density in the main surface 20pm is -100 to + 70% with respect to the average dislocation density in the main surface 20pm. Is preferably within -100%, more preferably within -100 to + 50%. Here, the dislocation density in the main surface 20pm of the GaN single crystal substrate 20p is measured by a CL (cathode luminescence) method, for example, at a measurement area of 100 μm × 100 μm at a pitch of 2 mm in the two-dimensional direction in the main surface 20pm. be able to.

From the viewpoint of epitaxially growing a highly crystalline GaN-based semiconductor layer in the GaN single crystal substrate 20p of the present embodiment, the dislocation density in the main surface 20pm is 5 × 10 ⁶ cm ⁻² or less even at the highest dislocation density. Preferably, it is 1 × 10 ⁶ cm ⁻² or less.

  In the GaN single crystal substrate 20p of this embodiment, from the viewpoint of stably epitaxially growing a highly crystalline GaN-based semiconductor layer, the inclination of the plane orientation of the main surface 20pm with respect to the (0001) plane or the (000-1) plane 20c is increased. The direction is preferably the <10-10> direction.

  From the viewpoint of epitaxially growing a highly crystalline GaN-based semiconductor layer in the GaN single crystal substrate 20p of this embodiment, X-ray diffraction rocking curve measurement on the (0002) plane and the (20-20) plane or the (22-40) plane. The half width of the X-ray diffraction peak at is preferably 300 arcsec or less over the entire main surface of 20 pm. The half width of the X-ray diffraction peak means that the smaller the value, the higher the crystallinity.

The diffraction crystal plane in the X-ray diffraction rocking curve measurement is, for example, (0002) for the GaN single crystal substrate 20p whose principal plane 20pm has a plane orientation of {h0kl} (where h, k and l are integers other than 0). And a (20-20) plane, and the plane orientation of the main surface 20pm is {hikl} (where h, k, i and l are integers other than 0), It can be a (22-40) plane. The X-ray diffraction rocking curve measurement on the entire main surface 20pm of the GaN single crystal substrate 20p can be performed, for example, with an X-ray irradiation area of 1 mm 2 at intervals of ² mm in the two-dimensional direction in the main surface 20pm.

[Method of manufacturing GaN single crystal substrate]
(Embodiment 2)
2 and 3, the method for manufacturing a GaN single crystal substrate according to one embodiment of the present invention is a method for manufacturing GaN single crystal substrate 20p according to Embodiment 1, and the area of main surface 10pm is 10 cm. A step of preparing a GaN seed crystal substrate 10p having a surface orientation of ² or more and an inclination of 65 to 85 ° with respect to the (0001) plane or the (000-1) plane 1c (FIG. 2 ( A) to (D), FIG. 3A), a step of growing the GaN single crystal 20 on the main surface 10pm of the GaN seed crystal substrate 10p (FIG. 3B), and the GaN single crystal 20 as a GaN seed. And a step (FIG. 3C) of forming a GaN single crystal substrate by cutting the crystal substrate 10p along planes 20u and 20v parallel to the main surface 10pm. The manufacturing method of the GaN single crystal substrate of this embodiment can efficiently manufacture the GaN single crystal substrate of Embodiment 1 by including such steps.

(Preparation process of GaN seed crystal substrate)
Referring to FIG. 2, the step of preparing the GaN seed crystal substrate of the present embodiment is not particularly limited. For example, a sub-step of cutting a plurality of GaN mother crystal pieces from the GaN mother crystal (FIG. 2A) And a sub-process for arranging a plurality of GaN mother crystal pieces adjacent to each other in the lateral direction (FIG. 2B), and a sub-process for growing a GaN seed crystal on the main surface of the plurality of GaN mother crystal pieces (FIG. 2 (C)) and a sub-process (FIG. 2D) for forming a GaN seed crystal substrate from the GaN seed crystal.

  First, referring to FIG. 2A, in a sub-process of cutting out a plurality of GaN mother crystal pieces 1p, from GaN mother crystal 1 to (0001) plane or (000-1) plane 1c of GaN mother crystal 1 A plurality of GaN mother crystal pieces 1p are cut out on a plane parallel to the plane orientation {hkil} inclined at an inclination angle α of 65 ° to 85 ° (a plane perpendicular to the <hkil> direction). By such a sub-process, a plurality of GaN mother crystal pieces 1p having a principal plane 1pm of a plane orientation inclined at an inclination angle α of 65 ° or more and 85 ° or less with respect to the (0001) plane or (000-1) plane 1c. Is obtained. Here, the inclination angle α can be measured by an X-ray diffraction method.

  The GaN mother crystal 1 used in the sub-process is not particularly limited, and is a usual method, that is, a vapor phase method such as HVPE (hydride vapor phase epitaxy) method, MOCVD (metal organic chemical vapor deposition) method, or flux method. It is sufficient to be produced by crystal growth on a main surface such as a sapphire substrate having a (0001) main surface or a GaAs substrate having a (111) A main surface by a liquid phase method. Therefore, although this GaN mother crystal 1 is not particularly limited, it usually has a (0001) main surface. This GaN mother crystal 1 has facets formed on the crystal growth surface (crystal growth surface) as disclosed in JP-A-2001-102307 from the viewpoint of reducing dislocation density and increasing crystallinity. The crystal growth is preferably performed without embedding the facet, and the growth is preferably performed by a facet growth method.

  Moreover, there is no restriction | limiting in particular in the method of cutting out the some GaN mother crystal piece 1p from the GaN mother crystal 1, Various methods, such as a wire saw, an inner peripheral blade, an outer peripheral blade, or a laser, can be used.

  Further, from the viewpoint of growing the highly crystalline GaN seed crystal 10, the average roughness Ra of the main surface 1pm and the side surfaces of the plurality of GaN mother crystal pieces 1p is preferably 50 nm or less, and more preferably 5 nm or less. The average surface roughness Ra means the arithmetic average roughness Ra specified in JIS B 0601-1994. Specifically, the surface is extracted by a reference length in the direction of the average line from the roughness curve, and This is the value obtained by summing the distances from the average line to the roughness curve (absolute value of deviation) and averaging them with the reference length. The average surface roughness Ra can be measured using an AFM (Intermolecular Force Microscope) or the like.

  In order to set the average roughness Ra of the main surface 1pm and side surfaces of the plurality of GaN mother crystal pieces 1p to preferably 50 nm or less, more preferably 5 nm or less, the plurality of GaN mother crystal pieces 1p that are cut out are It is preferable that the surface 1pm and the side surface are ground and / or polished. Polishing includes mechanical polishing, CMP (chemical mechanical polishing), and the like.

  Next, referring to FIG. 2B, in the sub-process of arranging the plurality of GaN mother crystal pieces adjacent to each other in the lateral direction, the plurality of GaN mother crystal pieces 1p that are cut out are the mother crystal pieces. Are arranged adjacent to each other in the lateral direction so that their main faces 1pm are parallel to each other and their mother crystal pieces have the same [0001] direction.

  The plurality of GaN mother crystal pieces 1p have a principal surface 1pm of their mother crystal pieces unless the angle between the principal surface 1pm of those mother crystal pieces and the crystal axis is uniform within the principal surface 1pm of these mother crystal pieces. Since the chemical composition of the GaN seed crystals grown on the surface becomes non-uniform in a plane parallel to the main surface 1 pm of the mother crystal pieces, the main surfaces 1 pm of the mother crystal pieces are laterally aligned so as to be parallel to each other. Arranged in the direction. It is sufficient that the main surfaces 1pm of these mother crystal pieces are parallel to each other, and they do not necessarily have to be on the same plane. However, the height difference ΔT (not shown) between the main surfaces 1pm of two adjacent GaN mother crystal pieces 1p is preferably 0.1 mm or less, and more preferably 0.01 mm or less.

  Further, from the viewpoint of achieving more uniform crystal growth by making the crystal orientations of the mother crystal pieces the same, the plurality of GaN mother crystal pieces 1p are arranged so that the [0001] directions of the mother crystal pieces are the same. Arranged in the direction. The plurality of GaN mother crystal pieces 1p are arranged adjacent to each other because there is a gap between the substrates and the crystallinity of crystals growing on the gaps is reduced.

  Through the above sub-processes, the main surfaces 1pm of the plurality of GaN mother crystal pieces 1p are arranged in parallel to each other so that the [0001] directions of the mother crystal pieces are the same. In addition, a plurality of GaN mother crystal pieces 1p having an inclination angle of 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane 1c is obtained.

  Next, referring to FIG. 2C, in the step of growing the GaN seed crystal 10 on the main surface 1pm of the plurality of GaN mother crystal pieces 1p, the method for growing the GaN seed crystal 10 is not particularly limited. However, from the viewpoint of epitaxially growing the GaN seed crystal, a gas phase method such as HVPE method or MOCVD method, a liquid phase method such as flux method, or the like is preferably used. Among the crystal growth methods, the HVPE method is preferable from the viewpoint of high crystal growth rate.

  When the GaN seed crystal 10 is grown on the main surface 1pm of the plurality of GaN mother crystal pieces 1p, the crystal growth surface 10g of the GaN seed crystal 10 is macroscopically formed on the main surface 1pm of the plurality of GaN mother crystal pieces 1p. A plurality of facets 10fa and 10fb that are parallel but are not parallel to the main surface 1pm of the plurality of GaN mother crystal pieces 1p when viewed microscopically are formed. The plurality of facets 10fa and 10fb have different plane orientations. That is, the GaN seed crystal 10 grows using a plurality of facets 10fa and 10fb having different plane orientations as the crystal growth surface 10g.

  Here, in the crystal growth surface 10g, the facet 10fa and the facet 10fb have different plane orientations, and therefore the arrangement of crystal constituent elements in the plane is different from each other. The direction of dislocation propagation differs from the portion grown with 10 fb as the crystal growth surface.

  For this reason, in the GaN seed crystal 10 grown on the main surface 1pm of the plurality of GaN mother crystal pieces 1p, variation occurs in the dislocation density in a plane parallel to the main surface 1pm of the mother crystal piece.

  At this time, if the inclination with respect to the (0001) plane or the (000-1) plane 1c in the plane orientation of the main surface 1pm of the plurality of GaN mother crystal pieces 1p is small, for example, if the inclination angle α is smaller than 65 °, the main A facet 10fa having a plane orientation of (0001) or (000-1) and a facet 10fb having a plane orientation different from that of the facet 10fa are generated on the crystal growth plane 10g of the GaN seed crystal 10 grown on the plane 1pm. Here, the dislocation of the portion grown with the facet 10fa having a plane orientation of (0001) or (000-1) as the crystal growth plane is in a direction perpendicular to (0001) or (000-1) (that is, <0001> direction). The dislocations in the portion that grows with facets having plane orientations other than (0001) and (000-1) as crystal growth planes propagate in a direction inclined from the <0001> direction. For this reason, since the variation in the dislocation density in the main surface 10pm of the GaN seed crystal 10 grown on the main surface 1pm and the GaN seed crystal substrate 10p obtained from the GaN seed crystal 10p increases, the variation in the characteristics of the semiconductor device using such a substrate varies. growing.

  Further, when the inclination with respect to the (0001) plane or the (000-1) plane 1c in the plane orientation of the principal surface 1pm of the plurality of GaN mother crystal pieces 1p increases and approaches a right angle, for example, when the inclination angle α is greater than 85 ° On the crystal growth surface 10g of the GaN seed crystal 10 grown on the main surface 1pm, the generation of the facet 10fb whose plane orientation is perpendicular to (0001) is dominant, and the growing GaN seed crystal 10 is partially As a result, the GaN seed crystal 10 is cracked.

  From the above viewpoint, in order to manufacture the GaN seed crystal substrate 10p, the inclination angle α of the plane orientation of the principal surface 1pm of the plurality of GaN mother crystal pieces 1p with respect to the (0001) plane or the (000-1) plane 1c is 65 It is necessary that the angle be from 85 ° to 85 °, preferably from 70 ° to 80 °, and more preferably from 72 ° to 78 °.

  Next, referring to FIGS. 2C and 2D, the GaN seed crystal 10 is cut out by planes 10u and 10v parallel to the main surface 1pm of the plurality of GaN mother crystal pieces 1p to form a GaN seed crystal substrate 10p. In the step, the method for cutting the GaN seed crystal substrate 10p from the GaN seed crystal 10 is not particularly limited, and various methods such as a wire saw, an inner peripheral blade, an outer peripheral blade, or a laser can be used.

  From the viewpoint of growing a highly crystalline GaN single crystal, the average roughness Ra of the main surface 10pm of the GaN seed crystal substrate 10p is preferably 50 nm or less, and more preferably 5 nm or less. The definition and measurement method of the average roughness Ra of the surface are the same as described above. In order to set the average roughness Ra of the main surface 10pm of the GaN seed crystal substrate 10p to preferably 50 nm or less, more preferably 5 nm or less, the cut GaN seed crystal substrate 10p is ground on its main surface 10pm and side surfaces. And / or is preferably polished. Polishing includes mechanical polishing, CMP (chemical mechanical polishing), and the like.

2D and 3A, the main surface 10pm has an area of 10 cm ² or more, and the main surface 10pm has a plane orientation of (0001) plane or (000-1). ) A GaN seed crystal substrate 10p inclined by 65 ° or more and 85 ° or less with respect to the surface 10c is prepared.

When a very thick GaN mother crystal is obtained, the GaN mother crystal is replaced by 65 ° or more with respect to the (0001) plane or the (000-1) plane of the GaN mother crystal instead of the above sub-process. By cutting out a plane parallel to the plane orientation {hkil} inclined at an inclination angle α of 85 ° or less (a plane perpendicular to the <hkil> direction), and grinding and / or polishing the main surface, the main surface 10 pm and the area of 10 cm ² or more, is ready GaN seed crystal substrate 10p to the plane orientation of main surface 10pm is inclined at (0001) plane or (000-1) 85 ° 65 ° or more to the surface below .

(GaN single crystal growth process)
Next, referring to FIG. 3B, in the step of growing the GaN single crystal 20 on the main surface 10pm of the GaN seed crystal substrate 10p, the method for growing the GaN single crystal 20 is not particularly limited. From the viewpoint of epitaxially growing a GaN single crystal, a gas phase method such as HVPE method or MOCVD method, a liquid phase method such as flux method, or the like is preferably used. Among the crystal growth methods, the HVPE method is preferable from the viewpoint of high crystal growth rate.

  When the GaN single crystal 20 is grown on the main surface 10pm of the GaN seed crystal substrate 10p, the crystal growth surface 20g of the GaN single crystal 20 is parallel to the main surface 10pm of the GaN seed crystal substrate 10p when viewed macroscopically. When viewed microscopically, a plurality of facets 20fa and 20fb that are not parallel to the main surface 10pm of the GaN seed crystal substrate 10p are formed. The plurality of facets 20fa and 20fb have different plane orientations. That is, the GaN single crystal 20 grows using a plurality of facets 20fa and 20fb having different plane orientations as the crystal growth surface 20g.

  Here, in the crystal growth surface 20g, the facet 20fa and the facet 20fb have different plane orientations, and therefore the arrangement of crystal constituent elements in the plane is different from each other. The direction of dislocation propagation differs from the portion grown with 20 fb as the crystal growth surface.

  For this reason, in the GaN single crystal 20 grown on the main surface 10pm of the GaN seed crystal substrate 10p, the dislocation density varies in a plane parallel to the main surface 10pm of the GaN seed crystal substrate 10p.

  At this time, if the inclination with respect to the (0001) plane or the (000-1) plane 10c in the plane orientation of the main surface 10pm of the GaN seed crystal substrate 10p is small, for example, if the inclination angle α is smaller than 65 °, the main surface 10pm. A facet 20fa having a plane orientation of (0001) or (000-1) and a facet 20fb having a plane orientation different from that of the facet 20fa are generated on the crystal growth surface 20g of the GaN single crystal 20 grown thereon. Here, the dislocation of the portion grown with the facet 20fa having a plane orientation of (0001) or (000-1) as a crystal growth plane is in a direction perpendicular to (0001) or (000-1) (that is, <0001> direction). The dislocations in the portion that grows with facets having plane orientations other than (0001) and (000-1) as crystal growth planes propagate in a direction inclined from the <0001> direction. For this reason, since the variation in the dislocation density in the main surface 20pm of the GaN single crystal 20 grown on the main surface 10pm and the GaN single crystal substrate 20p obtained from the main surface 10pm increases, the variation in the characteristics of the semiconductor device using the substrate varies. growing.

  Further, when the inclination with respect to the (0001) plane or the (000-1) plane 10c in the plane orientation of the main surface 10pm of the GaN seed crystal substrate 10p increases and approaches a right angle, for example, when the inclination angle α is greater than 85 °, On the crystal growth surface 20g of the GaN single crystal 20 grown on the main surface 10pm, the generation of the facet 20fb whose plane orientation is perpendicular to (0001) becomes dominant, and the GaN single crystal 20 that grows partially partially. Crystallization causes cracks in the GaN single crystal 20.

  From the above viewpoint, in order to manufacture a GaN single crystal substrate 20p having a substantially uniform dislocation density distribution on the main surface 20pm, the plane orientation of the main surface 10pm of the GaN seed crystal substrate 10p is (0001) plane or ( 000-1) The inclination angle α with respect to the surface 1c needs to be 65 ° or more and 85 ° or less, preferably 70 ° or more and 80 ° or less, and more preferably 72 ° or more and 78 ° or less. .

(Process for forming GaN single crystal substrate)
Next, referring to FIGS. 3B and 3C, a step of cutting GaN single crystal 20 along planes 20u and 20v parallel to main surface 10pm of GaN seed crystal substrate 10p to form GaN single crystal substrate 20p. The method for cutting out the GaN single crystal substrate 20p from the GaN single crystal 20 is not particularly limited, and various methods such as a wire saw, an inner peripheral blade, an outer peripheral blade, or a laser can be used.

  From the viewpoint of growing a highly crystalline GaN-based semiconductor layer, the average roughness Ra of the main surface 20pm of the GaN single crystal substrate 20p is preferably 50 nm or less, and more preferably 5 nm or less. The definition and measurement method of the average roughness Ra of the surface are the same as described above. In order to set the average roughness Ra of the main surface 20pm of the GaN single crystal substrate 20p to preferably 50 nm or less, more preferably 5 nm or less, the cut GaN single crystal substrate 20p is ground on its main surface 20pm and side surfaces. And / or is preferably polished. Polishing includes mechanical polishing, CMP (chemical mechanical polishing), and the like.

By the above process, the area of the main surface 20pm is 10 cm ² or more, and the surface orientation of the main surface 20pm is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane 20c. The dislocation density distribution in the main surface 20pm is substantially uniform (for example, the variation in dislocation density in the main surface 20pm is within ± 100% of the average dislocation density in the main surface 20pm). A substrate 20p is obtained.

[GaN-based semiconductor devices]
(Embodiment 3)
Referring to FIG. 5, a GaN-based semiconductor device 100 according to an embodiment of the present invention includes at least one GaN single crystal substrate 20p according to the first embodiment and a main surface 20pm of the GaN single crystal substrate 20p. GaN-based semiconductor layer 130 as a layer.

In the GaN-based semiconductor device 100 of this embodiment, the GaN single crystal substrate 20p has an area of the main surface 10pm of 10 cm ² or more, and the surface orientation of the main surface 10pm is the (0001) plane or the (000-1) plane 1c. However, the distribution of dislocation density in the main surface 10pm is substantially uniform (for example, variation in dislocation density in the main surface 20pm is the average dislocation density in the main surface 20pm). Within ± 100%). The GaN-based semiconductor layer 130 formed by epitaxial growth on the GaN single crystal substrate 20p has an area of the main surface of 10 cm ² or more, and the surface orientation of the main surface is the (0001) plane or (000-1). The distribution of the dislocation density in the principal plane is substantially uniform (for example, the dislocation density variation in the principal plane is an average dislocation within the principal plane 20 pm). Within ± 100% of the density). For this reason, the GaN-based semiconductor device of the present embodiment has a substantially uniform distribution of device characteristics in the main surface and high device characteristics.

Referring to FIG. 5, the GaN-based semiconductor device 100 of this embodiment specifically includes at least one GaN-based layer on one main surface 20pm of a GaN single crystal substrate 20p having a diameter of 50 mm and a thickness of 500 μm. The semiconductor layer 130 has a multiple quantum well structure composed of an n-type GaN layer 131 having a thickness of 2 μm doped with Si, six pairs of In _0.01 Ga _0.99 N barrier layers, and an In _0.1 Ga _0.9 N well layer. A light emitting layer 132 having a thickness of 100 nm, a p-type Al _0.18 Ga _0.82 N layer 133 having a thickness of 20 nm doped with Mg, and a p-type GaN layer 134 having a thickness of 50 nm doped with Mg are sequentially stacked. Further, a Ni / Au electrode of 0.2 mm × 0.2 mm × thickness 0.5 μm, which is a p-side electrode 141, is formed on a part of the p-type GaN layer 134. A Ti / Al electrode having a thickness of 1 μm, which is an n-side electrode 142, is formed on the other main surface 20pn of the GaN single crystal substrate 20p.

[Method of manufacturing GaN-based semiconductor device]
(Embodiment 4)
Referring to FIG. 5, the manufacturing method of GaN-based semiconductor device 100 according to one embodiment of the present invention includes a step of preparing GaN single crystal substrate 20p of Embodiment 1, and a main surface 20pm of GaN single crystal substrate 20p. And a step of growing at least one GaN-based semiconductor layer 130.

In the manufacturing method of the GaN-based semiconductor device 100 of this embodiment, the area of the main surface 20pm is 10 cm ² or more, and the plane orientation of the main surface 20pm is 65 ° with respect to the (0001) plane or the (000-1) plane. It is inclined at 85 ° or less and the distribution of dislocation density in the main surface 20pm is substantially uniform (for example, the dispersion of dislocation density in the main surface 20pm is ±± of the average dislocation density in the main surface 20pm). At least one GaN-based semiconductor layer 130 is epitaxially grown on the GaN single crystal substrate 20p (within 100%). The crystal orientation of the epitaxially grown GaN-based semiconductor layer 130 is the same as the crystal orientation of the GaN single crystal substrate 20p. Therefore, the grown GaN-based semiconductor layer 130 has an area of the main surface of 10 cm ² or more, and the surface orientation of the main surface is 65 ° or more and 85 ° with respect to the (0001) plane or the (000-1) plane. It is inclined below, and the distribution of dislocation density in the main surface is substantially uniform (for example, variation in dislocation density in the main surface is within ± 100% of the average dislocation density in the main surface). is there. For this reason, the method for manufacturing a GaN-based semiconductor device according to this embodiment provides a GaN-based semiconductor device having a substantially uniform distribution of device characteristics in the main surface and high device characteristics.

  The GaN single crystal substrate 20p of the first embodiment, that is, the plane orientation of the main surface 20pm is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane, and within the main surface 20pm. A step of preparing a GaN single crystal substrate 20p having a dislocation density distribution that is substantially uniform (for example, variation in dislocation density in the main surface 20pm is within ± 100% of the average dislocation density in the main surface 20pm). For example, this is performed by the method for manufacturing the GaN single crystal substrate 20p of the second embodiment.

  The method for growing at least one GaN-based semiconductor layer 130 on the main surface 20pm of the GaN single crystal substrate 20p is not particularly limited, but from the viewpoint of epitaxially growing the highly crystalline GaN-based semiconductor layer 130, the HVPE method, MOCVD method, MBE method, etc. are preferably used. From the viewpoint of high productivity and reliability, the MOCVD method is more preferably used.

Referring to FIG. 5, the step of forming at least one GaN-based semiconductor layer 130 on GaN single crystal substrate 20p includes, for example, one main surface 20pm of GaN single crystal substrate 20p having a diameter of 50 mm and a thickness of 0.4 mm. Further, by MOCVD, as an at least one GaN-based semiconductor layer 130, a Si-doped n-type GaN layer 131 having a thickness of 2 μm, six pairs of an In _0.01 Ga _0.99 N barrier layer and an In _0.1 Ga _0.9 N well 100 nm thick light emitting layer 132 having a multiple quantum well structure composed of layers, Mg doped p-type Al _0.18 Ga _0.82 N layer 133 and Mg doped p-type 50 nm thick A GaN layer 134 is grown in order.

  Further, a Ni / Au electrode having a thickness of 0.5 μm, which is the p-side electrode 141, is formed on a part of the p-type GaN layer 134 by vacuum evaporation. On the other main surface 20pn of the GaN single crystal substrate 20p, a Ti / Al electrode having a thickness of 1 μm as the n-side electrode 142 is formed by vacuum deposition.

  Next, a wafer having at least one GaN-based semiconductor layer 130 formed on the GaN single crystal substrate 20p is divided into chips having a predetermined size, whereby a light emitting device having a predetermined size is obtained.

[Preparation of GaN mother crystal]
The GaN mother crystal was produced as follows. A plurality of openings having a diameter of 2 μm are planarly formed at a pitch of 4 μm on the main surface of the (111) A surface of a GaAs substrate (underlying substrate) having a diameter of 50 mm and a thickness of 0.8 mm by photolithography and etching. A 100 nm thick SiO layer (mask layer) arranged in a hexagonal close-packed manner was formed. Next, a GaN low temperature layer having a thickness of 80 nm is grown at 500 ° C. on a main surface on which a SiO layer having a plurality of openings is formed on a GaAs substrate, and then a thickness of 60 μm at 950 ° C. After growing the GaN intermediate layer, a GaN mother crystal having a thickness of 5 mm was grown at 1050 ° C. Next, the GaAs substrate was removed from the GaN mother crystal by etching using aqua regia to obtain a GaN mother crystal having a diameter of 50 mm and a thickness of 3 mm. The dislocation density on the main surface of the GaN mother crystal was measured by a CL (cathode luminescence) method at a measurement area of 100 μm × 100 μm at 2 mm pitches in two directions orthogonal to each other in the main surface 20 pm. The average dislocation density was 3.1 × 10 ⁶ cm ⁻² , the minimum dislocation density was 0.7 × 10 ⁶ cm ⁻² , and the maximum dislocation density was 5.5 × 10 ⁶ cm ⁻² .

Example 1
1. Preparation of GaN Seed Crystal Substrate Referring to FIG. 2 (A), the (0001) plane and (000-1) plane, which are both main surfaces of GaN mother crystal 1, are ground and polished to obtain both main surfaces. The average roughness Ra was 5 nm. Here, the average roughness Ra of the surface was measured by AFM.

  Next, referring to FIG. 2A, a GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is formed in a plane parallel to the {20-21} plane (perpendicular to the <20-21> direction). A plurality of GaN mother crystal pieces 1p having a {20-21} main surface were cut out.

  Subsequently, four surfaces of each cut GaN mother crystal piece 1p that were not ground and polished were ground and polished, and the average roughness Ra of these four surfaces was set to 5 nm. Thus, a plurality of GaN mother crystal pieces 1p having an average roughness Ra of the main surface of {20-21} of 5 nm were obtained. Among the GaN mother crystal pieces 1p, there was a crystal piece whose plane orientation of the main surface did not completely match {20-21}. The surface orientation was within ± 0.1 ° with respect to {20-21}. Here, the inclination angle was measured by an X-ray diffraction method.

  Next, referring to FIG. 2B, the {20-21} main surfaces 1pm of the plurality of GaN mother crystal pieces 1p are parallel to each other, and [0001] of those GaN mother crystal pieces 1p. The GaN mother crystal pieces 1p were arranged adjacent to each other in the lateral direction so that the directions were the same, and a part of the outer peripheral portion was removed to make the diameter 50 mm.

  Next, referring to FIG. 2C, the {20-21} main surface 1pm of the plurality of GaN mother crystal pieces 1p is mixed with 10% by volume of hydrogen chloride gas and 90% by volume of nitrogen gas. Then, after treatment at 800 ° C. for 2 hours, the GaN seed crystal 10 was grown on the main surface 1 pm at a crystal growth temperature of 1050 ° C. at a growth rate of 80 μm / hr by HVPE for 50 hours.

  2 (C), (D) and FIG. 3 (A), the GaN seed crystal 10 is parallel to the {20-21} main surface 1pm of the plurality of GaN mother crystal pieces 1p. By slicing at 10u and 10v, a GaN seed crystal substrate 10p having a principal surface 10pm of {20-21}, a diameter of 50 mm, and a thickness of 0.5 mm was obtained. In the GaN seed crystal substrate 10p, the main surface 10pm was further ground and polished so that the average roughness Ra of the main surface 10pm was 5 nm. The {20-21} main surface 10pm of the GaN seed crystal substrate 10p has an inclination angle α of 75 ° with respect to the (0001) plane.

The dislocation density in the main surface 10pm of the GaN seed crystal substrate 10p formed as described above is 2 mm in two directions orthogonal to each other from the center toward the outer periphery in the main surface 10pm by the CL (cathode luminescence) method. Measurement was performed at a measurement area of 100 μm × 100 μm at 400 measurement points excluding the measurement points on the outer periphery from the measurement points of the pitch. The average dislocation density was 1.5 × 10 ⁶ cm ⁻² , the minimum dislocation density was 1.0 × 10 ⁶ cm ⁻² , and the maximum dislocation density was 3.5 × 10 ⁶ cm ⁻² . Therefore, the variation of the dislocation density with respect to the average dislocation density in the main surface was as large as −33% to + 133%. This is because a GaN seed crystal substrate 10p is prepared using a plurality of GaN mother crystal pieces 1p, so that in the GaN seed crystal substrate 10p, a dislocation of a portion of the GaN seed crystal substrate 10p grown on an adjacent portion of the GaN mother crystal piece 1p. This is thought to be due to the higher density.

2. Growth of GaN Single Crystal Referring to FIG. 3 (B), the main surface 10pm of {20-21} of the GaN seed crystal substrate 10p is a mixed gas of 10% by volume hydrogen chloride gas and 90% by volume nitrogen gas. After treatment at 800 ° C. for 2 hours in an atmosphere, the GaN single crystal 20 was grown on the main surface 10 pm at a crystal growth temperature of 1050 ° C. for 50 hours at a growth rate of 80 μm / hr by the HVPE method.

3. Formation of GaN Single Crystal Substrate Next, referring to FIGS. 3B and 3C, the GaN single crystal 20 is converted into a surface 20u parallel to the {20-21} main surface 10pm of the GaN seed crystal substrate 10p. By slicing at 20v, a GaN single crystal substrate 20p having a main surface 20pm surface orientation of {20-21}, a diameter of 50 mm, and a thickness of 0.5 mm was obtained. In the GaN single crystal substrate 20p, the main surface 20pm was further ground and polished so that the average roughness Ra of the main surface 20pm was 5 nm. Referring to FIG. 4A, {20-21} main surface 20pm of GaN single crystal substrate 20p has an inclination angle α of 75 ° with respect to the (0001) plane.

The dislocation density in the main surface 20pm of the GaN single crystal substrate 20p formed as described above is measured at 2 mm pitches in two directions perpendicular to each other from the center to the outer periphery in the main surface 20pm by the CL method. Measured at a measurement area of 100 μm × 100 μm at 400 measurement points excluding the measurement points on the outer periphery. The average dislocation density was 5.4 × 10 ⁵ cm ⁻² , the minimum dislocation density was 2.9 × 10 ⁵ cm ⁻² , and the maximum dislocation density was 7.5 × 10 ⁵ cm ⁻² . Therefore, the variation of the dislocation density with respect to the average dislocation density in the main surface was −46.3% to + 38.9%.

Further, the full width at half maximum of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with the (0002) plane and the (22-40) plane as the diffraction crystal plane is 30 arcsec to the entire main surface 20pm of the GaN single crystal substrate 20p. The crystallinity of the main surface 20pm of the GaN single crystal substrate 20p was high, as small as 100 arcsec. Here, the X-ray diffraction rocking curve measurement is performed using the Philip X'Pert Pro MRD to measure the outer peripheral portion from the measurement point of 2 mm pitch in each of two directions orthogonal to each other from the center to the outer periphery on the main surface 20 pm. Measurement was performed at an X-ray irradiation area of 1 mm ² at 400 measurement points excluding the point.

4). Production of GaN-based semiconductor device Next, on one main surface 20pm of the GaN single crystal substrate 20p (diameter 50 mm × thickness 0.4 mm), at least one GaN-based semiconductor layer 130 is formed by MOCVD. Multiple layers composed of an n-type GaN layer 131 (carrier concentration: 2 × 10 ¹⁸ cm ⁻³ ) doped with Si, doped with Si, six pairs of In _0.01 Ga _0.99 N barrier layers and In _0.1 Ga _0.9 N well layers Light emitting layer 132 having a quantum well structure with a thickness of 100 nm, Mg-doped p-type Al _0.18 Ga _0.82 N layer 133 (carrier concentration: 3 × 10 ⁷ cm ⁻² ) and Mg-doped thickness A p-type GaN layer 134 (carrier concentration: 1 × 10 ¹⁸ cm ⁻³ ) having a thickness of 50 nm was grown in order.

  Next, a 0.2 mm × 0.2 mm × 0.5 μm thick Ni / Au electrode is formed as the p-side electrode 141 at a pitch of 1 mm in two directions orthogonal to each other on the p-type GaN layer 134 by vacuum deposition. Formed. Further, a Ti / Al electrode having a thickness of 1 μm was formed as the n-side electrode 142 on the other main surface 20pn of the GaN single crystal substrate 20p by a vacuum deposition method.

  Next, a wafer on which the at least one GaN-based semiconductor layer 130 is formed on the GaN single crystal substrate 20p so that each p-side electrode is positioned at the center of each chip is formed on the GaN single crystal substrate 20p. Except for the outer peripheral portion where the distribution of carrier concentration and specific resistance in the main surface 20 pm was not measured, the chip was divided (chiped) into a plurality of 1 mm × 1 mm chips, that is, GaN-based semiconductor devices. The GaN-based semiconductor device 100 thus obtained was an LED (light emitting diode) having an emission peak wavelength of 450 nm.

  The luminance on the main surface of the LED (GaN-based semiconductor device 100) manufactured as described above was measured for the above-mentioned 1600 LED chips using a luminance measurement integrating sphere. The average luminance obtained with the LED of Example 1 was defined as the average relative luminance 1.0, and the average relative luminance and the sample variance of the relative luminance of each example were expressed. The average relative luminance was as large as 1.0, and the sample variance of the relative luminance was as small as 0.12. The results are summarized in Table 1.

(Example 2)
In the preparation of the GaN seed crystal substrate 10p, the GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is formed in a plane parallel to the {20-2-1} plane (perpendicular to the <20-2-1> direction). A plurality of GaN mother crystal pieces 1p having a {20-2-1} main surface, and grinding and polishing the main surfaces to average roughness of the main surfaces. A GaN seed crystal substrate 10p having a principal plane 10pm of {20-2-1} and a principal plane 20pm in the same manner as in Example 1 except that the GaN mother crystal piece 1p with Ra of 5 nm was used. A GaN single crystal substrate 20p having a plane orientation of {20-2-1} was formed. Referring to FIG. 4B, the {20-2-1} main surface 20pm of the GaN single crystal substrate 20p has an inclination angle α of 75 ° with respect to the (000-1) plane.

Regarding the dislocation density in the main surface 10pm of the obtained GaN seed crystal substrate 10p, the average dislocation density is 1.1 × 10 ⁶ cm ⁻² , the minimum dislocation density is 7.8 × 10 ⁵ cm ⁻² , and the maximum dislocation density is It was 2.4 × 10 ⁶ cm ⁻² . Therefore, the variation of the dislocation density with respect to the average dislocation density in the main surface was as large as -29% to + 118%.

On the other hand, regarding the dislocation density in the main surface 20pm of the obtained GaN single crystal substrate 20p, the average dislocation density is 3.2 × 10 ⁵ cm ⁻² and the minimum dislocation density is 0.0 × 10 ⁵ cm ^−2. The highest dislocation density was 4.2 × 10 ⁵ cm ⁻² . Therefore, the variation in carrier concentration with respect to the average carrier concentration in the main surface was as small as −100% to + 31.3%. Further, the full width at half maximum of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with the (0002) plane and the (22-40) plane as the diffraction crystal plane is 30 arcsec to the entire main surface 20pm of the GaN single crystal substrate 20p. The crystallinity of the main surface 20pm of the GaN single crystal substrate 20p was high, as small as 100 arcsec.

  Further, using this GaN single crystal substrate 20p, an LED which is a GaN-based semiconductor device was manufactured in the same manner as in Example 1. Regarding the luminance on the main surface of the manufactured LED (GaN-based semiconductor device 100), the average relative luminance was as large as 1.2, and the sample variance of the relative luminance was as small as 0.11. The results are summarized in Table 1.

(Example 3)
In the preparation of the GaN seed crystal substrate 10p, the GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is a plane parallel to the {22-42} plane (a plane perpendicular to the <22-42> direction). By slicing, a plurality of GaN mother crystal pieces 1p having a {22-42} main surface are cut out, and the main surfaces are ground and polished so that the average roughness Ra of the main surfaces is 5 nm. The surface orientation of the GaN seed crystal substrate 10p whose principal plane 10pm is {22-42} and the principal plane 20pm is {22-42] in the same manner as in Example 1 except that the mother crystal piece 1p is used. }, A GaN single crystal substrate 20p was formed. Referring to FIG. 4C, the {22-42} main surface 20pm of the GaN single crystal substrate 20p has an inclination angle α of 73 ° with respect to the (0001) plane.

Regarding the dislocation density in the main surface 10pm of the obtained GaN seed crystal substrate 10p, the average dislocation density is 1.6 × 10 ⁶ cm ⁻² , the minimum dislocation density is 1.2 × 10 ⁶ cm ⁻² , and the maximum dislocation density is It was 3.9 × 10 ⁶ cm ⁻² . Therefore, the variation of the dislocation density with respect to the average dislocation density in the main surface was as large as −25% to + 144%.

On the other hand, regarding the dislocation density in the main surface 20pm of the obtained GaN single crystal substrate 20p, the average dislocation density is 6.9 × 10 ⁵ cm ⁻² and the minimum dislocation density is 3.5 × 10 ⁵ cm ^−2. The highest dislocation density was 9.8 × 10 ⁵ cm ⁻² . Therefore, the carrier concentration variation with respect to the average carrier concentration in the main surface was as small as −49.3% to + 42.0%. The full width at half maximum of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with the (0002) plane and the (20-20) plane as the diffraction crystal plane is 30 arcsec to the entire surface of the main surface 20pm of the GaN single crystal substrate 20p. The crystallinity of the main surface 20pm of the GaN single crystal substrate 20p was high, as small as 100 arcsec.

  Further, using this GaN single crystal substrate 20p, an LED which is a GaN-based semiconductor device was manufactured in the same manner as in Example 1. Regarding the luminance on the main surface of the manufactured LED (GaN-based semiconductor device 100), the average relative luminance was as large as 0.9, and the sample variance of the relative luminance was as small as 0.14. The results are summarized in Table 1.

Example 4
In the preparation of the GaN seed crystal substrate 10p, the GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is formed on a plane parallel to the {22-4-2} plane (perpendicular to the <22-4-2> direction). A plurality of GaN mother crystal pieces 1p having {22-4-2} main surfaces, and grinding and polishing the main surfaces to average roughness of the main surfaces. A GaN seed crystal substrate 10p having a principal plane 10pm of {22-4-2} and a principal plane 20pm in the same manner as in Example 1 except that the GaN mother crystal piece 1p with Ra of 5 nm was used. A GaN single crystal substrate 20p having a plane orientation of {22-4-2} was formed. Referring to FIG. 4D, the {22-4-2} main surface 20pm of the GaN single crystal substrate 20p has an inclination angle α of 73 ° with respect to the (000-1) plane.

Regarding the dislocation density in the main surface 10pm of the obtained GaN seed crystal substrate 10p, the average dislocation density is 2.2 × 10 ⁶ cm ⁻² , the minimum dislocation density is 1.4 × 10 ⁶ cm ⁻² , and the maximum dislocation density is It was 5.5 × 10 ⁶ cm ⁻² . Therefore, the variation of the dislocation density with respect to the average dislocation density in the main surface was as large as −36% to + 150%.

On the other hand, regarding the dislocation density in the main surface 20pm of the obtained GaN single crystal substrate 20p, the average dislocation density is 8.9 × 10 ⁵ cm ⁻² and the minimum dislocation density is 3.8 × 10 ⁵ cm ^−2. The highest dislocation density was 1.5 × 10 ⁶ cm ⁻² . Therefore, the variation of the carrier concentration with respect to the average carrier concentration in the main surface was as small as −57.3% to + 68.5%. The full width at half maximum of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with the (0002) plane and the (20-20) plane as the diffraction crystal plane is 30 arcsec to the entire surface of the main surface 20pm of the GaN single crystal substrate 20p. The crystallinity of the main surface 20pm of the GaN single crystal substrate 20p was high, as small as 100 arcsec.

  Further, using this GaN single crystal substrate 20p, an LED which is a GaN-based semiconductor device was manufactured in the same manner as in Example 1. Regarding the luminance on the main surface of the manufactured LED (GaN-based semiconductor device 100), the average relative luminance was as large as 0.86, and the sample variance of the relative luminance was as small as 0.14. The results are summarized in Table 1.

(Comparative Example 1)
For preparation of the GaN seed crystal substrate 10p, a GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is formed on a plane parallel to the {10-10} plane (a plane perpendicular to the <10-10> direction). ), A plurality of GaN mother crystal pieces 1p having {10-10} main surfaces are cut out, and the main surfaces are ground and polished, and the average roughness Ra of the main surfaces is 5 nm. The GaN seed crystal 10 was grown in the same manner as in Example 1 except that the GaN mother crystal piece 1p was used. The GaN seed crystal 10 was partially polycrystallized and cracked starting from the polycrystallized portion. Therefore, a GaN seed crystal substrate could not be obtained, and a GaN single crystal substrate and a system semiconductor device could not be manufactured. The results are summarized in Table 1.

(Comparative Example 2)
In preparation for the GaN seed crystal substrate 10p, a GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is formed on a plane parallel to the {11-20} plane (a plane perpendicular to the <11-20> direction). ), A plurality of GaN mother crystal pieces 1p having a {11-20} main surface are cut out, the main surfaces are ground and polished, and the average roughness Ra of the main surfaces is 5 nm. The GaN seed crystal 10 was grown in the same manner as in Example 1 except that the GaN mother crystal piece 1p was used. The GaN seed crystal 10 was partially polycrystallized and cracked starting from the polycrystallized portion. Therefore, a GaN seed crystal substrate could not be obtained, and a GaN single crystal substrate and a GaN-based semiconductor device could not be manufactured. The results are summarized in Table 1.

(Comparative Example 3)
In preparation of the GaN seed crystal substrate 10p, a GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is a plane parallel to the {10-11} plane (a plane perpendicular to the <10-11> direction). By slicing, GaN mother crystal pieces 1p having a {10-11} main surface are cut out, and the main surfaces are ground and polished so that the average roughness Ra of the main surfaces is 5 nm. The GaN seed crystal substrate 10p whose principal plane 10pm has a {10-11} plane orientation and the principal plane 20pm has a {10-11 plane orientation, except that the mother crystal piece 1p is used. }, A GaN single crystal substrate 20p was formed. The {10-11} main surface 20pm of the GaN single crystal substrate 20p has an inclination angle α of 62 ° with respect to the (0001) plane.

Regarding the dislocation density in the principal surface 10pm of the obtained GaN seed crystal substrate 10p, the average dislocation density is 4.0 × 10 ⁶ cm ⁻² , the minimum dislocation density is 2.2 × 10 ⁶ cm ⁻² , and the maximum dislocation density is It was 9.5 × 10 ⁶ cm ⁻² . Therefore, the variation of the dislocation density with respect to the average dislocation density in the main surface was as large as -45% to + 138%.

Further, regarding the dislocation density in the main surface 20pm of the obtained GaN single crystal substrate 20p, the average dislocation density is 3.2 × 10 ⁶ cm ⁻² , the lowest dislocation density is 1.1 × 10 ⁶ cm ⁻² , and the highest dislocation. The density was 7.5 × 10 ⁶ cm ⁻² . Therefore, the variation of the carrier concentration with respect to the average carrier concentration in the main surface was as large as -65.7% to + 134%. Further, the full width at half maximum of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with the (0002) plane and the (22-40) plane as the diffraction crystal plane is 120 arcsec to the entire surface of the main surface 20pm of the GaN single crystal substrate 20p. It was as large as 350 arcsec, and the crystallinity on the main surface 20pm of the GaN single crystal substrate 20p was low.

  Further, using this GaN single crystal substrate 20p, an LED which is a GaN-based semiconductor device was manufactured in the same manner as in Example 1. Regarding the luminance on the main surface of the manufactured LED (GaN-based semiconductor device 100), the average relative luminance was as small as 0.55, and the sample variance of the relative luminance was as large as 0.35. The results are summarized in Table 1.

(Comparative Example 4)
In the preparation of the GaN seed crystal substrate 10p, the GaN mother crystal 1 having an average roughness Ra of both main surfaces of 5 nm is a plane parallel to the {11-22} plane (a plane perpendicular to the <11-22> direction). By slicing, a plurality of GaN mother crystal pieces 1p having a {11-22} main surface are cut out, and the main surfaces are ground and polished so that the average roughness Ra of the main surfaces is 5 nm. The surface orientation of the GaN seed crystal substrate 10p whose principal plane 10pm is {11-22} and the principal plane 20pm is {11-22] in the same manner as in Example 1 except that the mother crystal piece 1p is used. }, A GaN single crystal substrate 20p was formed. The {11-22} main surface 20pm of the GaN single crystal substrate 20p has an inclination angle α of 58 ° with respect to the (0001) plane.

Regarding the dislocation density in the main surface 10pm of the obtained GaN seed crystal substrate 10p, the average dislocation density is 4.7 × 10 ⁶ cm ⁻² , the minimum dislocation density is 2.8 × 10 ⁶ cm ⁻² , and the maximum dislocation density is It was 9.8 × 10 ⁶ cm ⁻² . Therefore, the variation of the dislocation density with respect to the average dislocation density in the main surface was as large as −40% to + 109%.

Further, regarding the dislocation density in the main surface 20pm of the obtained GaN single crystal substrate 20p, the average dislocation density is 4.6 × 10 ⁶ cm ⁻² , the lowest dislocation density is 2.2 × 10 ⁶ cm ⁻² , and the highest dislocation. The density was 9.3 × 10 ⁶ cm ⁻² . Therefore, the variation in carrier concentration with respect to the average carrier concentration in the main surface was as large as −52.2% to + 102%. Further, the full width at half maximum of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with the (0002) plane and the (20-20) plane as the diffraction crystal plane is 120 arcsec to the entire main surface 20pm of the GaN single crystal substrate 20p. It was as large as 350 arcsec, and the crystallinity on the main surface 20pm of the GaN single crystal substrate 20p was low.

  Further, using this GaN single crystal substrate 20p, an LED which is a GaN-based semiconductor device was manufactured in the same manner as in Example 1. Regarding the luminance on the main surface of the manufactured LED (GaN-based semiconductor device 100), the average relative luminance was as small as 0.41, and the sample variance of the relative luminance was as large as 0.31. The results are summarized in Table 1.

  As is apparent from Table 1, the plane orientation of the main surface is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane, and the distribution of dislocation density in the main plane is substantial. Use of a GaN single crystal substrate that is uniformly uniform (dispersion of the dislocation density with respect to the average dislocation density in the main surface is within ± 100%), the distribution of the emission intensity is substantially uniform with a large average emission intensity on the main surface. A GaN-based semiconductor device was obtained (the sample dispersion of the relative luminance with respect to the average relative luminance in the main surface was 0.2 or less and the variation in the emission intensity with respect to the average emission intensity was small).

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

1 GaN mother crystal 1c, 10c, 20c (0001) plane or 000 (000-1) plane 1p GaN mother crystal piece 1pm, 10pm, 20pm, 20pn Main surface 10 GaN seed crystals 10g, 20g Crystal growth surface 10p GaN seed crystal substrate 20 GaN single crystal 10fa, 10fb, 20fa, 20fb Facet 20p GaN single crystal substrate 10u, 10v, 20u, 20v Parallel plane 100 GaN-based semiconductor device 130 GaN-based semiconductor layer 131 n-type GaN layer 132 Light-emitting layer 133 p-type Al _0.18 Ga _0.82 N layer 134 p-type GaN layer 141 p-side electrode 142 n-side electrode

In the present invention, the area of the main surface is 10 cm ² or more, the surface orientation of the main surface is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane, This is a GaN single crystal substrate obtained by a hydride vapor phase growth method in which the variation in dislocation density is within ± 100% of the average dislocation density in the main surface . In the GaN single crystal substrate according to the present invention, the dislocation density in the main surface can be 5 × 10 ⁶ cm ⁻² or less. Moreover, the direction of the inclination of the surface orientation of the main surface with respect to the (0001) plane or the (000-1) plane can be the <10-10> direction. Moreover, the half width of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement with respect to the (0002) plane and the (20-20) plane or the (22-40) plane can be 300 arcsec or less over the entire main surface.

In the present invention, the area of the main surface is 10 cm. ² The plane orientation of the main surface is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane, and the (0002) plane and the (20-20) plane or (22 A GaN single crystal substrate obtained by a hydride vapor phase growth method in which the half width of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement on the −40) plane is 300 arcsec or less over the entire main surface. In the GaN single crystal substrate according to the present invention, the variation in the dislocation density in the main surface can be within ± 100% with respect to the average dislocation density in the main surface. Also, the dislocation density in the main surface is 5 × 10 ⁶ cm ^-2 It can be as follows. Moreover, the direction of the inclination of the surface orientation of the main surface with respect to the (0001) plane or the (000-1) plane can be the <10-10> direction.

The present invention is also a method for producing the above GaN single crystal substrate, wherein the main surface has an area of 10 cm ² or more and the main surface has a plane orientation of 65 with respect to the (0001) plane or the (000-1) plane. Preparing a GaN seed crystal substrate inclined at an angle of not less than 85 ° and not more than 85 °; a step of growing a GaN single crystal on a main surface of the GaN seed crystal substrate by a hydride vapor phase growth method; And a step of cutting a plane parallel to the main surface of the crystal substrate to form a GaN single crystal substrate.

Claims (8)

The area of the main surface is 10 cm ² or more,
The principal plane is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane,
A GaN single crystal substrate having a substantially uniform dislocation density distribution in the main surface.   2. The GaN single crystal substrate according to claim 1, wherein a variation in dislocation density in the main surface is within ± 100% with respect to an average dislocation density in the main surface. 3. The GaN single crystal substrate according to claim 1, wherein a dislocation density in the main surface is 5 × 10 ⁶ cm ⁻² or less.   The GaN unit according to any one of claims 1 to 3, wherein a direction of inclination of a plane orientation of the main surface with respect to the (0001) plane or (000-1) plane is a <10-10> direction. Crystal substrate.   The half width of the X-ray diffraction peak in the X-ray diffraction rocking curve measurement for the (0002) plane and the (20-20) plane or the (22-40) plane is 300 arcsec or less over the entire main surface. The GaN single crystal substrate according to any one of 4 to 4. A method for producing a GaN single crystal substrate according to claim 1,
A step of preparing a GaN seed crystal substrate having a principal surface area of 10 cm ² or more and an orientation of the principal surface that is inclined at 65 ° or more and 85 ° or less with respect to the (0001) plane or the (000-1) plane. When,
Growing a GaN single crystal on the main surface of the GaN seed crystal substrate;
Cutting the GaN single crystal along a plane parallel to the main surface of the GaN seed crystal substrate to form the GaN single crystal substrate.   A GaN-based semiconductor device comprising the GaN single-crystal substrate of claim 1 and at least one GaN-based semiconductor layer formed on the main surface of the GaN single-crystal substrate. Preparing the GaN single crystal substrate of claim 1;
And a step of growing at least one GaN-based semiconductor layer on the main surface of the GaN single crystal substrate.

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