JP5328999B2 - Method for manufacturing group III nitride semiconductor substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method of a group III nitride crystal producible of the group III nitride crystal having uniform region of low dislocation density over a wide range at low cost. <P>SOLUTION: There is disclosed a production method of a group III nitride semiconductor crystal by growing the group III nitride semiconductor crystal on a seed crystal by a vapor-phase epitaxial method, in which growth surfaces of the group III nitride semiconductor crystal are configured with only a plurality of surfaces not orthogonal to the growing direction on the seed crystal, and the method includes a convex growth step in which the growth surfaces composed of the plurality of surfaces grow while forming a convex shape as a whole. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a group III nitride crystal and a method for producing a group III nitride semiconductor substrate.

  Group III nitride semiconductors such as gallium nitride (GaN), indium gallium nitride (InGaN), and gallium aluminum nitride (AlGaN) are attracting attention as materials for blue light-emitting diodes (LEDs) and laser diodes (LDs). Yes. Furthermore, Group III nitride semiconductors have also begun to be applied to electronic device elements, taking advantage of their good heat resistance and environmental resistance.

  In order to improve the performance of the device as described above, it is important to reduce crystal defects in the epitaxial layer. In recent years, high-quality GaN substrates by the HVPE method have been developed and are becoming popular mainly for laser diode applications for next-generation DVDs.

  As a method for reducing the dislocation density of the GaN substrate, a method using FIELO (Facet Initiated Epitaxial Lateral Overgrowth) is well known (for example, see Non-Patent Document 1). In this method, when GaN is grown while forming inclined facets, dislocations that meet the facets are bent, so that dislocation propagation in the growth direction can be suppressed. Dislocation reduction technology that more actively applies the principle of FIELO has been disclosed (for example, see Non-Patent Document 2). In this method, a tilted facet surface is maintained, a thick film is grown on an uneven facet surface, and dislocations are swept up to a specific site, and other portions are locally reduced.

A. Usui, H. Sunakawa, A. Sakai and A. A. Yamaguchi: Jpn. J. Appl. Phys., 36 (1997), L899 K. Motoki, T. Okahisa, N. Matsumoto, M. Matsushima, H. Kimura, H. Kasai, K. Takemoto, K. Uematsu, T. Hirano, M. Nakayama, S. Nakahata, M. Ueno, D. Hara, Y. Kumagai, A. Koukitu and H. Seki: Jpn. J. Appl. Phys., 40 (2001), L140

  However, the GaN substrate according to the conventional method still leaves much room for improvement. Reducing manufacturing costs is one of the biggest challenges. This is because it is necessary to prepare a base substrate every time in order to produce one GaN substrate, resulting in high costs. In order to solve this problem, a method of growing GaN at a high speed, growing a large number of GaN, or growing a thick bulk ingot of GaN and then cutting out a large number of GaN substrates at a stretch (bulk method) has been studied. Among these, the bulk method is highly expected because it can produce a substrate having an arbitrary crystal plane other than the C plane currently on the market.

  However, growing GaN ingots is not easy. In particular, the problem of cracks is serious. When a GaN crystal is grown thickly, fine cracks begin to occur during the growth, resulting in a very rough surface. GaN grown on such a rough surface has a very high defect density and is not practical. Such a tendency becomes more remarkable as the growth rate increases. At a relatively slow growth rate of about 100 μm / h, the problem of microcracks is not so noticeable. In fact, the production of a crack-free GaN ingot having a thickness of about 5.8 mm and a diameter of 2 inches has been reported (Kubo et al. 2nd International Symposium on Growth of III-Nitrides (2008), publication number I-Tu-5, “Bulk GaN crystals grown by HVPE”). However, at higher growth rates it becomes a big problem. Since it is ingot growth, it grows very thick, so it is a very troublesome problem to grow as fast as possible from an economic point of view.

In addition, reduction of dislocation density is an important issue. At present, the dislocation density of GaN substrates on the market is about 10 ⁶ cm ^-2 . In order to further extract the potential of the nitride device, it is necessary to further reduce the dislocation density. It is known that the dislocation density decreases as GaN grows thicker. This dislocation reduction is thought to be due to the fact that dislocations having different Burgers vectors attract each other during the thick film growth, gradually approach each other, and coalesce and disappear. The rate of reduction of the dislocation density by this mechanism is remarkably slowed as the dislocation density is reduced. This is presumably because when the dislocation density decreases, the distance between dislocations increases and the attractive interaction between dislocations weakens.
On the other hand, as another method for reducing the dislocation density, there are methods according to Non-Patent Documents 1 and 2 described above. Although GaN having a low dislocation density region of about 10 ⁴ to 10 ⁵ cm ⁻² is obtained, the width of the low dislocation region is as narrow as about 0.5 mm, and is between the high dislocation density regions. For this reason, there is a problem that device fabrication needs to be performed with precise positioning, and the size of devices that can be fabricated is limited.

  An object of the present invention is to provide a method for producing a group III nitride crystal and a method for producing a group III nitride semiconductor substrate capable of producing a group III nitride crystal having a uniform low dislocation density region over a wide range at a low cost. It is to provide.

  One embodiment of the present invention is a method for producing a group III nitride semiconductor crystal in which a group III nitride semiconductor crystal is grown on a seed crystal by a vapor deposition method, and is not perpendicular to the growth direction on the seed crystal. A growth surface of the group III nitride semiconductor crystal is formed only by a plurality of surfaces, and the growth surface composed of the plurality of surfaces includes a convex surface growth step of growing while forming a convex surface shape as a whole. An object of the present invention is to provide a method for producing a group III nitride semiconductor crystal.

  In the above embodiment, a seed crystal substrate is used as the seed crystal, and the growth surface is inclined with respect to the main surface of the seed crystal substrate at the outer peripheral portion of the group III nitride semiconductor crystal grown on the main surface of the seed crystal substrate. And the group III nitride parallel to the main surface of the seed crystal substrate on the center side of the seed crystal substrate is grown so as to expand the inclined growth surface toward the center side of the seed crystal substrate. A flat surface disappearance growth step for eliminating the flat surface of the semiconductor crystal, and in the flat surface disappearance growth step, the group III nitride semiconductor crystal being grown is slow crystal growth that does not generate cracks, and the flat surface After the disappearance growth step, it is preferable to perform the convex growth step of growing the group III nitride semiconductor crystal on a convex growth surface consisting of only the inclined growth surface.

  Further, in the above aspect, a seed crystal substrate is used as the seed crystal, and the growth is inclined with respect to the main surface of the seed crystal substrate on the outer peripheral portion of the group III nitride semiconductor crystal grown on the main surface of the seed crystal substrate. Forming a plane and growing the inclined growth surface so as to expand to the center side of the seed crystal substrate, and the group III nitride parallel to the main surface of the seed crystal substrate on the center side of the seed crystal substrate A flat surface disappearance growth step of eliminating the flat surface of the semiconductor crystal, and in the flat surface disappearance growth step, a mask having an opening is formed on a main surface to be a growth surface of the seed crystal substrate, The group III nitride semiconductor crystal is grown on the main surface of the opening portion so as to coincide with a predetermined crystal orientation of the main surface, and after the flat surface disappearance growth step, only from the inclined growth surface. On the growth surface of the convex shape, the group III It is preferred to carry out the convex surface growing step of growing a compound semiconductor crystal.

  A mask having an opening is overlaid on the main surface to be a growth surface of the seed crystal substrate so that the opening coincides with a predetermined crystal orientation of the main surface, and the group III nitride is formed on the main surface of the opening portion. It is preferable to perform the flat surface disappearance growth step by growing a physical semiconductor crystal.

  The growth rate of the group III nitride semiconductor crystal in the convex surface growth step is preferably 300 μm / h or more.

  In the above aspect, the plurality of surfaces are all surfaces other than the C surface, and the surfaces other than the plurality of C surfaces are six equivalent {10-1m} surfaces (where m is a natural number) and / or It is preferable to include six equivalent {1-12n} planes (where n is a natural number).

  It is preferable that the convex growth step is performed by using, as the seed crystal, a top portion including the convex growth surface portion obtained by cutting the group III nitride semiconductor crystal having the convex growth surface.

  One embodiment of the present invention includes a group III step of producing a group III nitride semiconductor substrate by cutting the group III nitride semiconductor crystal obtained by the method for producing a group III nitride semiconductor crystal of the above embodiment. An object of the present invention is to provide a method for manufacturing a nitride semiconductor substrate.

  According to the present invention, a group III nitride crystal having a uniform low dislocation density region over a wide range can be produced at low cost.

It is process drawing which shows the manufacturing process of the manufacturing method of the GaN crystal which concerns on one Example of this invention, and the manufacturing method of a GaN substrate. It is process drawing which shows the manufacturing process of the manufacturing method of the GaN crystal which concerns on one Example of this invention, and the manufacturing method of a GaN substrate. It is process drawing which shows the manufacturing process of the manufacturing method of the GaN crystal which concerns on a comparative example. It is process drawing which shows the manufacturing process of the manufacturing method of the GaN crystal which concerns on a comparative example, and the manufacturing method of a GaN substrate.

  The outline of the method for producing a group III nitride crystal and the method for producing a group III nitride semiconductor substrate according to the present invention will be described below. In the following description, GaN will be described as a representative example of a group III nitride semiconductor.

As described above, a problem in growing a GaN ingot at high speed is the generation of cracks. As a result of careful observation of such a cracked GaN ingot, the present inventor has found that a very high density crack is generated on the C plane ((0001) plane), resulting in a poor surface state. However, it was noticed that no cracks were generated in the side facet portion that spontaneously occurs adjacent to the C-plane.
That is, for example, when GaN ingot growth is performed using a disk-shaped C-plane GaN substrate as a seed crystal, depending on the growth conditions, as the C-plane becomes thicker, the inclined side is adjacent to the C-plane. Facets develop (the area of the C plane decreases accordingly). When the growth rate is high, cracks are likely to occur on the C-plane, but even when very high-density cracks are generated, the side facets are almost always sound. From this, the present inventor has come up with the idea that, if crystal growth is performed without a C-plane on the GaN ingot surface, crack-free can be easily achieved even if high-speed growth is performed. Considering the acquisition efficiency of the C-plane substrate, it is common knowledge to devise growth so as to suppress the reduction of the C-plane as much as possible, but the present invention is just the idea of reversal.

As a specific method for performing crystal growth without a C-plane, first, there is a method of growing a thick C-plane GaN substrate as a seed crystal. Select growth conditions that facilitate the development of side facets and actively reduce the C-plane. However, if the diameter of the seed crystal substrate is large, it is necessary to grow it considerably thick until the C-plane disappears. Therefore, in the process up to that point, crystal growth is performed at a low speed in order to avoid the occurrence of cracks. There is a need. However, in order to eliminate the C-plane, it is usually necessary to grow it to the same thickness as the radius of the seed crystal substrate, so that slow growth takes time.
As a method for avoiding this, it is also effective to use a seed crystal substrate having a predetermined diameter that can eliminate the C-plane within a thickness that does not cause cracks. Alternatively, it is also effective that the side wall surface of the seed crystal is surrounded by a low index surface such as a {10-12} surface. Specifically, for example, a seed crystal substrate having a predetermined crystal plane as a side wall surface is used, or a mask having an opening of a predetermined shape is overlaid on the seed crystal substrate with a predetermined crystal orientation, and through the opening. This can also be realized by crystal growth.

  Once the C-plane disappears, a crack-free ingot can be grown at a high speed thereafter. Therefore, a GaN crystal can be manufactured efficiently and at low cost. In addition to crystal growth in the C-axis direction, the ingot can be expanded in the diameter direction (direction perpendicular to the C-axis direction) by devising a growth condition and a substrate holder for holding the seed crystal substrate. Is possible. After the growth is completed, the GaN substrate is manufactured by slicing the ingot parallel to the C plane, etc., but the C plane disappears and the entire growth surface is a convex ingot top portion as a seed crystal for the next ingot growth. It is also effective to use.

  The present invention is an effective technique for obtaining GaN having a low defect density. That is, dislocations are bent by growing in a state where the entire growth surface of the ingot is covered with facets inclined with respect to the growth direction of the ingot, so that the dislocation density is reduced. Although the typical dislocation reduction method using the bending effect of dislocations by facets has already been described (Non-Patent Documents 1 and 2), the difficulty of those prior arts is that there is always a valley portion of the facet, This is because the bent dislocations gather at the valley (recess). That is, a region where the dislocation density is high and a region where the dislocation density is low can be formed, and the micro density of the dislocation density can be obtained. In the present invention, since the entire growth surface has a convex shape, the bent dislocations are exclusively discharged to the side surface of the crystal and do not collect at a specific location. Therefore, it is possible to achieve both low dislocation density and uniformity of dislocation density at a high level. The boundary between micro and macro is generally not clearly defined, but here, the term micro is used to mean a size below the optical microscope scale, for example, a size of 1 mm or less. On the other hand, the term macro is used to mean a scale of 1 cm or more so as to describe the distribution over the entire wafer surface.

  In the above description, GaN is described as the group III nitride crystal, but the present invention is applicable to other group III nitride semiconductors such as AlN and AlGaN and mixed crystals thereof besides GaN. In the above description, the crystal growth in the C-axis direction has been described. However, the present invention is not limited to the C-axis direction, and can be applied to growth in the A-axis direction, the M-axis direction, and other directions.

  Next, an embodiment of a method for producing a group III nitride crystal and a method for producing a group III nitride substrate according to the present invention will be described.

In the method for producing a group III nitride crystal according to the present embodiment, the growth surface of the group III nitride semiconductor crystal is formed on the seed crystal only by a plurality of surfaces that are not perpendicular to the growth direction, and the plurality of surfaces A method of manufacturing a group III nitride semiconductor crystal including a convex surface growth step in which the growth surface composed of:
By making the growth surface of the group III nitride semiconductor crystal a convex surface while growing it into a convex shape, a group III nitride crystal that has no cracks and has a uniform low dislocation density region over a wide area is obtained. Can be manufactured. Furthermore, since high-speed growth can be realized, a group III nitride semiconductor crystal can be manufactured at low cost.

  It is preferable that the growth is performed so that no concave portion exists in the convex growth surface constituted by the plurality of surfaces. This is in order to avoid dislocations bent at the convex growth surface from gathering in the concave portion and generating a high dislocation density region.

The growth direction of the group III nitride semiconductor crystal is preferably the C-axis direction, and all of the plurality of surfaces are preferably surfaces other than the C surface. The growth direction of the group III nitride semiconductor crystal is not limited to the C axis, and can be arbitrarily selected from the M axis and the A axis.
The planes other than the plurality of C planes preferably include six equivalent {10-1m} planes (where m is a natural number). In particular, m = 1, 2, or 3 is preferable. That is, any of six equivalent {10-11} planes, six equivalent {10-12} planes, and six equivalent {10-13} planes may be included.
Further, it is preferable that the planes other than the plurality of C planes include six equivalent {1-12n} planes (where n is a natural number). In particular, n = 1, 2, or 3 is preferable.
The planes other than the plurality of C planes include six equivalent {10-1m} planes (where m is a natural number) and six equivalent {1-12n} planes (where n is a natural number). It is preferable that it is composed of a total of 12 surfaces. In particular, either m = 1, 2, 3 or n = 1, 2, 3 is preferable.

  From the viewpoint of productivity, the diameter of the group III nitride semiconductor crystal grown in the convex growth process (diameter perpendicular to the growth direction) is 10 mm or more, and the group III nitride semiconductor crystal in the convex growth process The growth rate is preferably 300 μm / h or more. By adopting the convex growth, high-speed growth of 300 μm / h or more is possible without generating cracks. The diameter of the group III nitride semiconductor crystal grown in the convex growth process is more preferably 25 mm or more, and further preferably 40 mm or more. In addition, the growth rate of the group III nitride semiconductor crystal in the convex growth step is preferably 500 μm / h or more, and more preferably 1000 μm / h or more.

  When a seed crystal substrate is used as the seed crystal, a growth surface inclined with respect to the main surface of the seed crystal substrate is formed on the outer periphery of the group III nitride semiconductor crystal that grows on the main surface of the seed crystal substrate. A flat surface that grows so that the inclined growth surface expands toward the center side of the seed crystal substrate, and the flat surface of the group III nitride semiconductor crystal parallel to the main surface of the seed crystal substrate at the center side of the seed crystal substrate disappears. Plane disappearance growth. Thereby, a convex growth surface consisting only of the inclined growth surface is formed. A convex growth of a group III nitride semiconductor crystal may be performed on the convex growth surface.

  As the seed crystal substrate, it is preferable to use a seed crystal substrate having a side wall surface inclined with respect to the main surface. In the case where the main surface of the seed crystal substrate is a C plane and a group III nitride semiconductor crystal is grown in the C-axis direction, there are six equivalent {10 −1m} plane (m should be a natural number, especially m = 1, 2, 3) or six equivalent {1-12n} planes (n is a natural number, especially n = 1, 2, 3 is preferred).

  Further, a mask having a polygonal opening is overlaid on the main surface, which is a growth surface of the seed crystal substrate, so that each side of the opening coincides with a predetermined crystal orientation of the main surface, and the main portion of the opening portion is overlapped. Flat surface disappearance growth may be performed by growing a group III nitride semiconductor crystal on the surface. For example, if a mask having a regular hexagonal opening is used so that each side of the regular hexagon coincides with <11-20>, a {10-1m} plane grows on the outer periphery of the grown crystal, or a regular hexagonal If each side is made to coincide with <10-10>, a {11-2n} plane grows on the outer periphery of the grown crystal.

  In the flat surface disappearance growth process, it is preferable to perform low-speed crystal growth in which no cracks are generated in the growing group III nitride semiconductor crystal, and in the convex surface growth process, high-speed crystal growth of 300 μm / h or more is preferable. The HVPE (Hydride Vapor Phase Epitaxy) method is preferably used for crystal growth of group III nitride semiconductors, particularly for high-speed crystal growth of 300 μm / h or more.

  It is preferable to perform the convex growth by using the top portion including the convex growth surface portion obtained by cutting the group III nitride semiconductor crystal having the convex growth surface as the seed crystal. In this case, the top portion including the convex growth surface portion can be reused, and flat surface disappearance growth can be omitted.

A group III nitride semiconductor substrate (wafer) is obtained by cutting a group III nitride semiconductor crystal (ingot) manufactured by the above-described method for manufacturing a group III nitride semiconductor crystal.
A large number of group III nitride semiconductor wafers can be obtained at once from the group III nitride semiconductor crystal ingot. In addition, since an ingot is obtained, it is possible to manufacture a wafer having an arbitrary crystal plane other than a plane (for example, a C plane) perpendicular to the growth direction of the group III nitride semiconductor crystal.

  Next, specific examples of the present invention will be described.

Example 1
A method for producing a GaN crystal and a method for producing a GaN substrate of Example 1 according to the present invention will be described with reference to FIG. FIG. 1 is a process diagram showing a manufacturing process, in which FIGS. 1 (a) and (c) are plan views (top views), and the upper portions in FIGS. 1 (b), (d) and (e) are plan views. The figure (top view) and the lower part are side views.

First, a disc-shaped C-plane GaN substrate 11 having a diameter of 2 inches and a thickness of 430 μm was prepared as a seed crystal (FIG. 1A). The dislocation density of the GaN substrate 11 was measured by a CL (Cathodoluminescence) method. The observation visual field was 1 mm square. The average in-plane dislocation density of the GaN substrate 11 was 5 × 10 ⁶ cm ⁻² , good uniformity within the observed scale, and the in-plane distribution was substantially uniform.

This GaN substrate 11 was set in a substrate holder of an HVPE furnace, and a GaN crystal (GaN ingot) 12 was homoepitaxially grown as a group III nitride semiconductor crystal on the Ga polar surface of the GaN substrate 11. GaCl and NH ₃ were used as raw materials. A mixed gas of H ₂ and N ₂ was used as the carrier gas. The partial pressures of GaCl and NH ₃ were 0.3 kPa and 16 kPa, respectively. The growth temperature was 1050 ° C. Growth was carried out at about normal pressure. At this time, the growth rate in the C-axis direction was about 150 μm / h.

The shape of the GaN ingot 12 in the initial stage of growth is substantially a truncated cone as a whole, the upper surface 12a of the GaN ingot 12 is a C plane, and the side surface of the GaN ingot 12 is an inclined surface composed of a flat surface portion 12b and a conical surface portion 12c. It was. The flat surface portion 12b is a {10-11} surface, and appeared at six locations every 60 degrees along the inclined side surface of the truncated cone. That is, the GaN ingot 12 has a shape in which a truncated cone-shaped side surface (conical surface) is cut off by a flat surface ({10-11} surface) at six locations. The conical surface portion 12c looks like a conical surface with the naked eye, but when magnified and observed with a microscope, the conical surface portion 12c has a jagged surface in which {10-11} surfaces and {11-22} surfaces are finely and alternately arranged. It was.
On the inclined side surface, as the growth proceeds, the flat surface portion 12b composed of the {10-11} plane gradually develops and expands. When the thickest portion of the GaN ingot 12 reaches about 5 mm, the conical surface portion 12c becomes the upper surface 12a. Only the flat surface portion 12b was in contact with the outer periphery of the upper surface 12a, and the shape of the upper surface 12a made of the C surface was a hexagon. The growth was continued as it was, and the growth was stopped when the thickest part of the ingot 12 reached about 6 mm (FIG. 1 (b)).

  When a sample was taken out from the HVPE furnace, an ingot 12 having a hexagonal C surface as a main surface (upper surface 12a) was formed. Cracks did not occur. The hexagonal C-plane GaN substrate 13 having a thickness of about 1 mm was cut out from the outermost surface (upper surface 12a) of the ingot 12 at a position of about 1 mm (FIG. 1 (c)). In the GaN substrate 13, the upper surface 13a is a C surface, and the six side surfaces 13b are {10-11} surfaces.

The hexagonal GaN substrate 13 was again set as a seed crystal in an HVPE furnace, and a GaN ingot 14 was homoepitaxially grown on the GaN substrate 13. The partial pressures of GaCl and NH ₃ were 0.7 kPa and 16 kPa, respectively. The growth temperature was 1010 ° C. At this time, the growth rate in the C-axis direction was about 330 μm / h. If the growth is continued under these conditions, six {10-13} side surfaces are developed adjacent to the C-plane of the upper surface of the GaN ingot 14, and the C-plane is gradually reduced to a hexagonal frustum shape. The top (not shown) of was made. Further, a hexagonal columnar straight body portion 14b composed of six {10-10} planes adjacent to the side surface of the {10-13} plane appeared at the lower part of the top of the hexagonal truncated cone shape. When the thickest part of the GaN ingot 14 reached about 19 mm, the C plane completely disappeared to form a hexagonal pyramid apex 14a. The hexagonal pyramidal apex 14a becomes a convex growth surface in the convex growth step of the present invention. Further, the growth was continued, and the growth was stopped when the thickest part became 25 mm (FIG. 1 (d)).

  When the sample was taken out from the HVPE furnace, the ingot 14 had a hexagonal pyramidal apex portion 14a consisting of a {10-13} plane, and a hexagonal columnar straight barrel portion 14b consisting of a {10-10} plane below the apex portion 14a. And consisted of Cracks did not occur. The straight body portion 14b of the ingot 14 was sliced in parallel with the C surface, and a plurality of GaN wafer blanks were cut out. Both surfaces of these GaN wafer blanks were polished to obtain a hexagonal C-plane GaN substrate 15 having a thickness of 430 μm and a diameter (diagonal length that is the diameter of a circumscribed circle of a regular hexagon) of about 46 mm (FIG. 1 ( e)). The top portion 14a of the ingot 14 was not processed and was used as a seed crystal in Example 2 described later.

Of the obtained GaN substrate 15, the dislocation density distribution was examined by the CL method with respect to what was cut from the vicinity of the upper end of the straight body portion 14 b. The observation field of view was 1 mm square, and multiple locations were photographed. As a result, in the portion within 20 mm from the center of the GaN substrate 15, it was a good value of about 1 × 10 ⁶ cm ⁻² . In addition, the outer peripheral part showed an even better value of about 5 × 10 ⁵ cm ⁻² . All regions had good uniformity within the observed scale. The reason why the dislocation density in the outer peripheral portion is lower than the dislocation density in the vicinity of the center is that the outer peripheral portion is grown on an inclined facet plane ({10-13} plane). This is thought to be due to the suppression of propagation to.

(Example 2)
A second embodiment related to the present invention will be described with reference to FIG. FIG. 2 is a process diagram showing a manufacturing process of a GaN crystal and a GaN substrate. In each of FIGS. 2A, 2B, and 2C, the upper part is a plan view (top view), and the lower part is a side view. It is.

The hexagonal pyramidal apex of the {10-13} plane remaining in Example 1 was used as the seed crystal 21 of Example 2 (FIG. 2A). This hexagonal pyramidal seed crystal 21 was set in an HVPE furnace, and a GaN ingot 22 was homoepitaxially grown on the seed crystal 21. The partial pressures of GaCl and NH ₃ were 2.5 kPa and 49 kPa, respectively. The growth temperature was 1010 ° C. At this time, the growth rate in the C-axis direction was about 1200 μm / h. During the growth, the top portion 23 made of the {10-13} plane of the ingot 22 maintains the hexagonal pyramid shape as it is, and the hexagonal columnar straight body portion 24 made of the {10-10} plane is formed below the top portion 23. As a result, the length of the straight body portion 24 is increased. When the length of the straight body portion 24 reached 12 mm, the growth was stopped, and the grown ingot 22 was taken out from the growth furnace (FIG. 2B).

  The straight body portion 24 of the ingot 22 taken out was sliced in parallel with the C surface to obtain a plurality of wafer blanks. Both surfaces of these GaN wafer blanks were polished to obtain a hexagonal C-plane GaN substrate 25 having a thickness of 430 μm and a diameter (diagonal length) of about 46 mm (FIG. 2C).

Of the obtained GaN substrate 25, the dislocation density distribution was examined by the CL method for the one cut from the vicinity of the upper end of the straight body portion 24. The observation field of view was 1 mm square, and multiple locations were photographed. The in-plane average dislocation density of the GaN substrate 25 was 1 × 10 ⁵ cm ⁻² , good uniformity within the observed scale, and the in-plane distribution was substantially uniform. Compared with Example 1, the macroscopic uniformity of dislocation density in Example 2 was further improved because the ingot 22 was formed thickly by the convex growth, and the portion where the dislocation was lowered by the inclined facet was the straight body part 24. It is thought that it was expanded to the center of.

(Comparative Example 1)
Comparative Example 1 according to the present invention will be described with reference to FIG. FIG. 3 is a process diagram showing a manufacturing process of a GaN crystal. FIG. 3A is a plan view (top view), FIG. 3B is a plan view (top view), and a lower part is a side view. is there.

First, a disk-shaped C-plane GaN substrate 31 having a diameter of 2 inches and a thickness of 430 μm, as in Example 1, was prepared (FIG. 3A). The GaN substrate 31 was set in an HVPE furnace, and GaN homoepitaxial growth was performed on the Ga polar surface of the GaN substrate 31. GaCl and NH3 were used as raw materials. The partial pressures of GaCl and NH ₃ were 2.5 kPa and 49 kPa, respectively, as in Example 2. The growth temperature was 1010 ° C. Growth was carried out at about normal pressure. At this time, the growth rate in the C-axis direction was about 1200 μm / h. After growing for 10 hours, an ingot 32 having a thickness of about 12 mm was obtained (FIG. 3B).

  The upper surface 32a of the ingot 32 is a flat C surface, and the periphery thereof is basically conical. However, it seems that the {10-11} surface is scraped off at six locations on the conical side surface. The flat surface part 32b was formed. The cross-sectional shape of the truncated conical ingot 32 was gradually approaching a hexagon. Innumerable fine cracks were generated starting from a portion adjacent to the conical conical surface portion 32c. Fine cracks were generated during the growth, and GaN was further grown thereon, so that the surface irregularities were very severe.

(Comparative Example 2)
A comparative example according to the present invention will be described with reference to FIG. FIG. 4 is a cross-sectional view showing each manufacturing process of the GaN crystal and the GaN substrate.

  First, a C-plane sapphire substrate 41 having a diameter of 2 inches was prepared (FIG. 4A). A GaN thin film 42 having a thickness of 1 μm was grown on the sapphire substrate 41 by using a MOVPE (metal-organic vapor phase epitaxy) method to obtain a GaN template (FIG. 4B). A Pt (platinum) stripe mask 43 was formed on the GaN template by photolithography (FIG. 4C). The thickness of the mask 43 was 100 nm and the width was 1 μm. The interval between the masks 43 was 500 μm, and the stripe direction was <11-20>.

This masked template was set in an HVPE furnace, and GaN was grown. GaCl and NH ₃ were used as raw materials. The partial pressures of GaCl and NH ₃ were 2.5 kPa and 49 kPa, respectively. The growth temperature was 1080 ° C. Growth was carried out at about normal pressure. At this time, the growth rate in the C-axis direction was about 1000 μm / h. The growth of GaN started from the mask opening 44, and first, a GaN 45 having a mountain-shaped triangular cross section where two {10-11} planes intersect each other was formed (FIG. 4D).
If the growth is continued, the triangular cross-sections of GaN 45 generated in the adjacent mask openings 44 collide with each other on the mask 43, and a valley of the GaN ingot 47 is formed in the collision portion on the mask 43 covering the mask 43. As a whole, the surface 46 of the laundry plate cross-sectional shape (triangular wave shape) having an irregularity of about 500 μm was obtained (FIG. 4E).

After that, even if the growth was continued, the surface 46 was not flattened, and the film thickness was increased while the original triangular wave shape was maintained. The growth was stopped when the thickest part of the GaN ingot 47 reached about 10 mm, and the grown GaN ingot 47 was taken out of the furnace (FIG. 4 (f)). Probably because the GaN ingot 47 was more rigid than the sapphire substrate 41, the sapphire substrate 41 was broken and naturally separated during the temperature drop after the growth was completed.
The straight body portion of the ingot 47 taken out was sliced in parallel with the C surface to obtain a plurality of wafer blanks. Both surfaces of these GaN wafer blanks were polished to obtain a C-plane GaN substrate 48 having a thickness of 430 μm (FIG. 4G).

Of the obtained GaN substrate 48, the dislocation density distribution was examined by the CL method for the one cut out from the top of the ingot 47. The observation visual field was 1 mm square, and a plurality of locations were photographed. The distribution of dislocations was substantially uniform on the macro scale, but the micro scale showed the density of the dislocation density with a period of about 500 μm. That is, the portion that was a convex portion (peak) during growth had a good dislocation density of 3 × 10 ⁵ cm ⁻² , but in the portion that was a valley during growth, there was dislocation at the bottom of the valley. A high dislocation density region of 1 × 10 ⁸ cm ⁻² or more was formed.

  In the above embodiment, only the GaN ingot grown by the HVPE method is described, but it is obvious that other growth methods such as a flux method and an ammonothermal method are also effective. In addition to GaN, the present invention can also be applied to other group III nitride semiconductors such as AlN and mixed crystals thereof. In the above embodiment, the growth direction of the ingot is described only in the C axis direction and the slice is only in the direction parallel to the C plane. However, the growth direction and the slice plane can be arbitrarily selected such as the M axis and the M plane. .

11 C-plane GaN substrate 12 GaN ingot 12 a Top surface 12 b Flat surface portion 12 c Conical surface portion 13 C-plane GaN substrate 14 GaN ingot 14 a Top portion 14 b Straight body portion 15 C-plane GaN substrate 21 Seed crystal 22 GaN ingot 23 Top portion 24 Straight body portion 25 C surface GaN substrate

Claims (6)

On the seed crystal, and a step of manufacturing a step of Ru by growing a group III nitride semiconductor crystal by vapor deposition, a group III nitride semiconductor substrate by cutting the grown Group III nitride semiconductor crystal In the method for manufacturing a group III nitride semiconductor substrate ,
The group III nitride semiconductor crystal growth step includes forming a growth surface of the group III nitride semiconductor crystal only on a plurality of surfaces that are not perpendicular to the growth direction on the seed crystal, and configured from the plurality of surfaces. look including a convex surface growing step of the growth surface grows while forming a convex shape as a whole to be,
A diameter of the group III nitride semiconductor crystal grown in the convex growth step is 25 mm or more;
The plurality of surfaces are all surfaces other than the C surface,
A surface other than the plurality of C-plane, the six equivalent {10-1m} plane (where, m is a natural number) and / or six equivalent {1-12n} plane (where, n is a natural number) including the A method for producing a group III nitride semiconductor substrate , comprising: A seed crystal substrate is used as the seed crystal, and a growth surface that is inclined with respect to the main surface of the seed crystal substrate is formed on the outer periphery of the group III nitride semiconductor crystal that grows on the main surface of the seed crystal substrate. The inclined growth surface is grown so as to expand to the center side of the seed crystal substrate, and the group III nitride semiconductor crystal parallel to the main surface of the seed crystal substrate on the center side of the seed crystal substrate is flattened. Having a flat surface disappearance growth step of disappearing the surface,
In the flat surface disappearance growth step, the group III nitride semiconductor crystal being grown is slow crystal growth that does not generate cracks,
2. The convex surface growth step of growing the group III nitride semiconductor crystal on a convex growth surface consisting only of the inclined growth surface is performed after the flat surface disappearance growth step. The manufacturing method of the group III nitride semiconductor substrate of description. A seed crystal substrate is used as the seed crystal, and a growth surface that is inclined with respect to the main surface of the seed crystal substrate is formed on the outer periphery of the group III nitride semiconductor crystal that grows on the main surface of the seed crystal substrate. The inclined growth surface is grown so as to expand to the center side of the seed crystal substrate, and the group III nitride semiconductor crystal parallel to the main surface of the seed crystal substrate on the center side of the seed crystal substrate is flattened. Having a flat surface disappearance growth step of disappearing the surface,
In the flat surface disappearance growth step, a mask having an opening is overlaid on a main surface to be a growth surface of the seed crystal substrate so that the opening coincides with a predetermined crystal orientation of the main surface, and the opening portion While growing the group III nitride semiconductor crystal on the main surface,
2. The convex surface growth step of growing the group III nitride semiconductor crystal on a convex growth surface consisting only of the inclined growth surface is performed after the flat surface disappearance growth step. The manufacturing method of the group III nitride semiconductor substrate of description. A mask having an opening is overlaid on the main surface to be a growth surface of the seed crystal substrate so that the opening coincides with a predetermined crystal orientation of the main surface, and the group III nitride is formed on the main surface of the opening portion. 3. The method for producing a group III nitride semiconductor substrate according to claim 2, wherein the flat surface disappearance growth step is performed by growing a nitride semiconductor crystal . 5. The method for producing a group III nitride semiconductor substrate according to claim 1, wherein a growth rate of the group III nitride semiconductor crystal in the convex surface growth step is 300 μm / h or more. Performing the convex surface growth step using a top portion including the convex surface-shaped growth surface portion obtained by cutting the group III nitride semiconductor crystal having the convex surface as a seed crystal. A method for producing a group III nitride semiconductor substrate according to any one of claims 1 to 5 .

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