WO2013058352A1 - Cristal semi-conducteur de nitrure du groupe iii - Google Patents

Cristal semi-conducteur de nitrure du groupe iii Download PDF

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WO2013058352A1
WO2013058352A1 PCT/JP2012/077054 JP2012077054W WO2013058352A1 WO 2013058352 A1 WO2013058352 A1 WO 2013058352A1 JP 2012077054 W JP2012077054 W JP 2012077054W WO 2013058352 A1 WO2013058352 A1 WO 2013058352A1
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region
crystal
plane
nitride semiconductor
group iii
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PCT/JP2012/077054
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Japanese (ja)
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達寛 大畑
創 松本
哲 長尾
泰宏 内山
久保　秀一
健史 藤戸
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三菱化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides

Definitions

  • the present invention relates to a group III nitride semiconductor crystal having specific properties.
  • Nitride semiconductors typified by gallium nitride have a large band gap, and the transition between bands is a direct transition type. Therefore, light emitting diodes such as ultraviolet, blue and green, semiconductor lasers and the like on the relatively short wavelength side It has been put to practical use as a light emitting element. Recently, with the development of crystal growth technology, the manufacture of gallium nitride substrates used in these devices has also been realized. In order to improve the characteristics of these elements, it is necessary to establish a technique capable of manufacturing a nitride semiconductor substrate having a low dislocation density.
  • An ELO method (Epitaxial Lateral Overgrowth) is known as a method for manufacturing a gallium nitride substrate having a low dislocation density.
  • the ELO method is a crystal growth method in which a mask layer is formed on a base substrate and laterally grown on the mask from an opening.
  • a layer with few crystal defects can be formed.
  • Patent Document 1 a method of forming a mask layer on a base substrate and performing facet growth has been proposed, and it has been reported that threading dislocations can be integrated at predetermined positions (see Patent Documents 2 and 3).
  • the group III nitride semiconductor crystal is generally subjected to a molding process such as slicing or polishing after growth, but the crystal may be cracked during the molding process. It was a factor that lowered the yield.
  • An object of the present invention is to improve the yield due to crystal cracking.
  • a part of the crystal includes a region (region X) having a basal plane dislocation density of 1.0 ⁇ 10 6 cm ⁇ 2 or more and a region (region Y) having a basal plane dislocation density of less than 1.0 ⁇ 10 6 cm ⁇ 2.
  • a group III nitride semiconductor crystal characterized by the above.
  • FIG. 3 is an SEM-CL image of a group III nitride semiconductor crystal obtained in Example 2, which is an image observed from the M-plane side (micrograph). It is a SEM-CL image of the group III nitride semiconductor crystal obtained in Example 3, which is an image observed from the M-plane side (micrograph). It is a SEM-CL image of the group III nitride semiconductor crystal obtained by the comparative example, and is an image observed from the M plane side (micrograph).
  • FIG. 6b is a graph plotting the difference (
  • the group III nitride semiconductor crystal of the present invention will be described in detail below, but is not limited to these contents unless it is contrary to the gist of the present invention.
  • the “main surface” of the group III nitride semiconductor crystal refers to the widest surface of the group III nitride semiconductor crystal and the surface on which crystal growth is to be performed.
  • the “C plane” is a ⁇ 0001 ⁇ plane in a hexagonal crystal structure (wurtzite crystal structure) and is a plane orthogonal to the c-axis. Such a plane is a polar plane.
  • the “+ C plane” is a group III plane (gallium plane in the case of gallium nitride), and the “ ⁇ C plane” is a nitrogen plane.
  • the “M plane” means (1-100) plane, (01-10) plane, ( ⁇ 1010) plane, ( ⁇ 1100) plane, (0-110) plane, or (10 ⁇ 10) A plane that is perpendicular to the m-axis. Such a surface is usually a cleavage plane.
  • a plane means (2-1-10) plane, (-12-10) plane, ( ⁇ 1-120) plane, ( ⁇ 2110) plane, (1-210) plane. Or (11-20) plane, a plane orthogonal to the a-axis.
  • the “semipolar plane” is not particularly limited as long as both the group III metal element and the nitrogen element are present on the crystal plane, and the abundance ratio thereof is not 1: 1.
  • ⁇ 20 -21 ⁇ plane, ⁇ 10-11 ⁇ plane, ⁇ 10-12 ⁇ plane, ⁇ 11-21 ⁇ plane, ⁇ 11-22 ⁇ plane, ⁇ 11-23 ⁇ plane, ⁇ 11-24 ⁇ plane, etc. when referring to the C, M, A, or specific index plane, a range having an off angle within 10 ° from each crystal axis measured with an accuracy within ⁇ 0.01 °. Including the inner face. The off angle is preferably within 5 °, more preferably within 3 °.
  • a numerical range expressed using “to” in this specification means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the group III nitride semiconductor crystal of the present invention has a region (region X) in which the basal plane dislocation density is a specific value or more and a region (region Y) in which the basal plane dislocation density is less than a specific value.
  • the inventors of the present invention have skillfully applied the internal stress generated in the crystal during crystal growth by including the region X having many basal plane dislocations and the region Y having few basal plane dislocations in the group III nitride semiconductor crystal. Succeeded in relaxing and improving processability.
  • the “basal plane dislocation” is a linear defect (dislocation) generated on the C-plane (basal plane), and the direction and length of the dislocation line is particularly limited as long as it is perpendicular to the c-axis. In FIG. 1, 3 corresponds to this.
  • the “region” does not mean a planar region, but means a three-dimensional region. That is, the basal plane dislocation in the region X means not only the basal plane dislocation existing on the crystal surface of the region X but also the basal plane dislocation existing in the crystal of the region X. ing.
  • the basal plane dislocation density in the present invention means a value calculated by the following calculation formula (1).
  • the number N of basal plane dislocations is measured by using, for example, a transmission electron microscope method (TEM method), a cathodoluminescence method (SEM-CL method), or a method of observing surface pits by etching with an AFM or an optical microscope. can do. These methods have different observable fields of view.
  • TEM method transmission electron microscope method
  • SEM-CL method cathodoluminescence method
  • the dislocation density is mainly 1 ⁇ 10 5 cm ⁇ 2 or more
  • the method of observing surface pits by etching with an AFM or an optical microscope is suitable when the dislocation density is mainly 1 ⁇ 10 3 to 1 ⁇ 10 6 cm ⁇ 2 .
  • the specific measurement conditions when using the SEM-CL method are not particularly limited, but the acceleration voltage is usually preferably 3 to 5 kV, and more preferably 3 kV.
  • the number N of basal plane dislocations can be measured by the method as described above, but the measured value varies depending on the direction from which the crystal is observed, and the cross-sectional area A is also derived from the surface to be observed.
  • the value to be Therefore, the value of the basal plane dislocation density ⁇ can also vary depending on the direction from which the crystal is observed. Therefore, in the present invention, the group III nitride semiconductor crystal is specified by utilizing the value of the basal plane dislocation density ⁇ particularly when the ⁇ 10-10 ⁇ plane is observed. That is, in the present specification, when simply referred to as “basal plane dislocation density ( ⁇ )”, the number N of basal plane dislocations observed mainly as points when the M plane intersecting the basal plane is observed is measured.
  • the specific value of the cross-sectional area A for calculating the basal plane dislocation density ⁇ is not particularly limited, but is usually 1 ⁇ m 2 or more, preferably 25 ⁇ m 2 or more, more preferably 100 ⁇ m 2 or more. 22500 ⁇ m 2 or less, preferably set to 14400Myuemu 2 or less, and more preferably set to 10000 2 below. Within the above range, the value of the basal plane dislocation density can be calculated with good reproducibility.
  • the cross-sectional area A is preferably a rectangular area close to a rectangle or a square.
  • the basal plane dislocation is observed as a line.
  • a unit distance (cm) is set in a direction crossing the basal plane dislocation observed as a line, and the unit distance per unit distance is set.
  • the number of intersecting basal plane dislocations is referred to as “basal plane dislocation frequency in the C plane” and is distinguished from the “basal plane dislocation density ( ⁇ )”.
  • the “basal plane dislocation frequency in the C plane” does not consider the number of basal plane dislocations in the depth direction corresponding to the c-axis direction.
  • the number of basal plane dislocations when the ⁇ 10-10 ⁇ plane or ⁇ 0001 ⁇ plane is observed is used.
  • the measurement is preferably performed after molding the crystal so that the crystal plane appears on the crystal surface and the basal plane dislocations are easily observed.
  • the basal plane dislocation in the present invention is not particularly limited in the direction and length of the dislocation line as long as it is perpendicular to the c-axis as described above, but the dislocation line length is 0.1 ⁇ m or more. It is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more.
  • the basal plane dislocation density when the ⁇ 10-10 ⁇ plane of the crystal is observed is 1.0 ⁇ 10 6 cm ⁇ 2 or more, and 1.0 ⁇ 10 7 cm ⁇ 2 or more. It is preferably 1.0 ⁇ 10 8 cm ⁇ 2 or more.
  • the upper limit of the basal plane dislocation density is usually 1.0 ⁇ 10 10 cm ⁇ 2 or less, preferably 1.0 ⁇ 10 9 cm ⁇ 2 or less.
  • the C-plane basal plane dislocation frequency is preferably 1.0 ⁇ 10 6 cm ⁇ 1 or more, and 1.0 ⁇ 10 7 cm ⁇ 1. More preferably.
  • the upper limit value of the basal plane dislocation frequency of the C plane is usually 1.0 ⁇ 10 10 cm ⁇ 1 or less, preferably 1.0 ⁇ 10 9 cm ⁇ 1 or less.
  • the basal plane dislocation density when the ⁇ 10-10 ⁇ plane of the crystal is observed is less than 1.0 ⁇ 10 6 cm ⁇ 2 and less than 6.0 ⁇ 10 5 cm ⁇ 2. Preferably, it is less than 4.0 ⁇ 10 5 cm ⁇ 2 .
  • the basal plane dislocation frequency of the C plane when the ⁇ 0001 ⁇ plane of the crystal is observed is preferably less than 1.0 ⁇ 10 6 cm ⁇ 1 , and 6.0 ⁇ 10 5 cm ⁇ 1. More preferably, it is more preferably less than 4.0 ⁇ 10 5 cm ⁇ 1 .
  • the region X in the present invention preferably has a region (region X ′) having a uniform basal plane dislocation density.
  • the basal plane dislocation density calculated from any 80 ⁇ m ⁇ 80 ⁇ m region including the region is 1.0 ⁇ 10 6 cm ⁇ 2 or more, and 1 / A region of 40 ⁇ m ⁇ 40 ⁇ m corresponding to the area of 4 is arbitrarily extracted, and a basal plane dislocation density calculated from the region and a basal plane dislocation density calculated from the region of 80 ⁇ m ⁇ 80 ⁇ m are within a 1.5-fold difference. Shall point to.
  • the region X and / or the region Y in the present invention contains a basal plane dislocation array arranged in a polygon.
  • the basal plane dislocation array arranged in a polygonal arrangement refers to an array of basal plane dislocations arranged at intervals of 50 nm or less.
  • the arrangement direction is not particularly limited, but is preferably arranged in the c-axis direction.
  • the length in the arrangement direction of the basal plane dislocation arrangement arranged in a polygon is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and preferably 20 mm or less, and 10 mm or less. It is more preferable that
  • the region X and the region Y in the present invention are not particularly limited as to the form, number, and distribution of the regions in the crystal as long as the basal plane dislocation density is in a specific range, but the ratio of the region X in the entire crystal is usually 1% or more, preferably 3% or more, more preferably 5% or more, more preferably 10% or more, usually 95% or less, preferably 80% or less, more preferably 70% or less, more preferably 50% or less, particularly Preferably it is 30% or less.
  • the ratio of the region Y to the entire crystal is usually 10% or more, preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, usually 99% or less, preferably 97% or less, more preferably Is 95% or less, more preferably 93% or less.
  • the ratio of the region X (or region Y) to the entire crystal means the ratio of the volume of the region X (or region Y) to the volume of the entire crystal. For example, as shown in FIG. In the case of a crystal, it can be calculated from the ratio of the short side of region X (a-axis direction) to the short side of region Y (a-axis direction).
  • the region Y usually has a size of 350 ⁇ m square or more, preferably a size of 400 ⁇ m square or more, and more preferably a size of 1 mm square or more. When it is in the above range, a size for producing a device or the like can be sufficiently secured. Further, the region X has a maximum length of preferably 100 ⁇ m or more, more preferably 300 ⁇ m or more, further preferably 500 ⁇ m or more, and preferably 21 cm or less, and 11 cm or less.
  • the region X is more preferably 5 mm or less, and particularly preferably 1 mm or less.
  • the region X is more preferably 5 mm or less, and particularly preferably 1 mm or less.
  • both the regions X and Y are widely distributed throughout the crystal.
  • the basal plane dislocation is a dislocation perpendicular to the c-axis as described above, the direction of the dislocation line is not particularly limited, but within the region X, when a plurality of basal plane dislocations face the same direction, This is preferable because the crystal forming process becomes easy.
  • the region X and the region Y are rectangular parallelepiped long in either direction,
  • the region X and the region Y are alternately and regularly arranged, that is, the region X and the region Y are arranged in a stripe shape, or the crystal shown in FIG.
  • the region X and the region Y are spread as a plane substantially perpendicular to the growth direction, and the region X and the region Y are alternately arranged, that is, the region X and the region Y are arranged in layers.
  • 5 is a basal plane dislocation
  • 6 is a region X
  • 7 is a region Y).
  • the long side direction of the region X arranged in a stripe shape is not particularly limited, but preferably extends in the m-axis direction, and the base existing in the region X It is preferable that the plane dislocation also extends in the m-axis direction.
  • the width (short side) of the region X is also not particularly limited, but is usually 10 to 500 ⁇ m, preferably 30 to 200 ⁇ m, more preferably 40 to 100 ⁇ m.
  • the width of the region Y is not particularly limited, but is usually preferably 100 ⁇ m or more, 200 ⁇ m or more, and more preferably 300 ⁇ m or more.
  • the long side direction of the region X arranged in a stripe shape is not particularly limited, but those extending in the a-axis direction are preferable.
  • the basal plane dislocation existing in the region X is also preferably extended in the a-axis direction.
  • the long side direction can be the a-axis direction and the short side direction can be the c-axis direction.
  • the width (short side) of the region X is also not particularly limited, but is usually 10 to 2000 ⁇ m, preferably 100 to 1000 ⁇ m, more preferably 200 to 750 ⁇ m.
  • the width of the region Y is not particularly limited, but is usually preferably 100 ⁇ m or more and 500 ⁇ m or more, more preferably 1000 ⁇ m or more, and particularly preferably 2000 ⁇ m or more. In such a group III nitride semiconductor crystal, internal stress is moderately dispersed and it is difficult to break, and a region with few basal plane dislocations can be sufficiently secured.
  • the region X arranged in a layered manner in the second embodiment is not particularly limited, even if it is a single layer or a plurality of regions.
  • the width of the region X (layer thickness) viewed from the M-plane direction is not particularly limited, but is usually 1 to 1000 ⁇ m, preferably 10 to 900 ⁇ m, more preferably 50 to 800 ⁇ m.
  • the width of the region Y (layer thickness) is not particularly limited, but is usually preferably 10 ⁇ m or more, 20 ⁇ m or more, and more preferably 50 ⁇ m or more.
  • Such a group III nitride semiconductor crystal is preferable because it periodically includes basal plane dislocations, so that internal stress is moderately dispersed, and it is difficult to break when the substrate is cut out.
  • the group III nitride semiconductor crystal of the present invention is not particularly limited in the density and distribution of other defects as long as it includes a region (region X and Y) in which the basal plane dislocation density is in a specific range. Since the region Y is a highly practical region as a semiconductor crystal, it is preferable that there are few or no threading dislocations (edge dislocations, screw dislocations) and planar defects.
  • the group III nitride semiconductor crystal of the present invention includes a region (region X and Y) in which the basal plane dislocation density is in a specific range, but the internal stress in the crystal is relaxed by the presence of such a region. It is characterized by.
  • the internal stress remaining in the crystal can be grasped by the residual strain, and the residual strain can be measured by, for example, a phase difference by a photoelastic method.
  • the measurement of the residual strain amount by the photoelastic method is performed using the following relational expression (2) (see APPL. Phys. Lett. 47 (1985) pp. 365-367).
  • the residual strain amount is the absolute value
  • ⁇ is the wavelength of light used for measurement
  • d is the thickness of the substrate used for measurement
  • n 0 is the refractive index
  • ⁇ is the phase difference caused by the birefringence of the sample
  • ⁇ is the main vibration azimuth
  • P 11 , P 12 , P44 is photoelastic constant
  • the specific numerical value of residual strain is not particularly limited.
  • the standard deviation of the phase difference ⁇ by the photoelastic method is preferably less than 0.1 nm, more preferably less than 0.09 nm.
  • the phase difference distribution if a portion where the value of the phase difference ⁇ is high or low is localized in the plane of the crystal, the residual strain is also unevenly distributed at a specific portion of the crystal. Therefore, in the group III nitride semiconductor crystal of the present invention, it is preferable that the phase difference distribution is uniformly dispersed in the plane. In another example, in the plane of the group III nitride semiconductor crystal, there are 10 or more consecutive sections where the difference ( ⁇ ) between two adjacent points at an interval of about 180 ⁇ m is 0.05 or more. It is preferable that there are more than 20 sections.
  • Examples of the group III nitride semiconductor crystal of the present invention include gallium nitride, aluminum nitride, indium nitride, and mixed crystals thereof.
  • the main surface of the group III nitride semiconductor crystal of the present invention includes a + C plane, a ⁇ C plane, an M plane, an A plane, or a semipolar plane, and a + C plane, an M plane, or a semipolar plane. It is preferable that it is an M plane or a semipolar plane.
  • the carrier concentration in the crystal is preferably 1 ⁇ 10 18 cm ⁇ 3 or more, and more preferably 1 ⁇ 10 19 cm ⁇ 3 .
  • the carrier concentration in the crystal can be measured using hole measurement by the van der Pauw method.
  • the group III nitride semiconductor crystal of the present invention includes the region X and the region Y, so that the warpage of the crystal plane of the main surface can be suppressed.
  • the curvature radius of curvature of the crystal face of the main surface is usually 3 m or more, preferably 3.5 m or more, more preferably 5 m or more, and further preferably 10 m or more. When it is within the above range, good quality can be ensured when used as a substrate.
  • any crystal axis substantially parallel to the crystal plane of the main surface is preferably within the above range.
  • the radius of curvature can be calculated from a tilt of the crystal axis measured by X-ray diffractometry or the like by a known method as an indication of the curvature of the crystal plane.
  • the group III nitride semiconductor crystal of the present invention contains the region X and the region Y, so that the a-axis direction and m There is a tendency that warpage in a direction other than the c-axis direction such as the axial direction is improved.
  • the group III nitride semiconductor crystal of the present invention is characterized by having regions (regions X and Y) having a basal plane dislocation density in a specific range.
  • regions X and Y regions having a basal plane dislocation density in a specific range.
  • the present inventors have the effect that the basal plane dislocations relieve the stress generated when the crystal plane is coreless by facet growth, and this effect makes the crystal difficult to break.
  • the inventors have also revealed that such basal plane dislocations have self-strain in the polar direction and perform a glide motion for relaxation of the self-strain during crystal growth.
  • basal plane dislocations occur randomly immediately before coreless (joining by lateral growth), but when coreless, the plane orientation of each crystal growth surface is fine. The deviation (off angle) becomes distortion, and the distortion is absorbed as basal plane dislocations along the mask. Even in a region where the core is not cored, the residual stress in the crystal becomes a driving force, and a glide motion is generated for optimal arrangement of the individual basal plane dislocations. Furthermore, according to the study by the present inventors, in the second aspect, it is presumed that basal plane dislocations are generated in layers due to a rapid change in the growth temperature or the like. By generating such stratified basal plane dislocations, the stress in the thickness direction is partially relieved, and if the position to be cut out is appropriately selected, the yield during processing can be increased.
  • the group III nitride semiconductor crystal of the present invention is not particularly limited in its production method as long as it includes a region (region X and Y) having a basal plane dislocation density in a specific range. Based on the method, the group III nitride semiconductor crystal of the present invention can be preferably produced.
  • a method for obtaining a semiconductor crystal in which the region X and the region Y according to the first embodiment are arranged in a stripe shape parallel to the m-axis in the group III nitride semiconductor crystal of the present invention will be specifically described below. explain.
  • semiconductor crystals arranged in stripes can be obtained by using the following method (A), (B), or (C).
  • a method in which a stripe mask parallel to the m-axis is placed on the base substrate, and a semiconductor crystal is facet grown in the c-axis direction that is, a method including the following steps).
  • A1 A step of forming a stripe mask parallel to the m-axis on the base substrate.
  • (A2) A step of performing facet growth in the c-axis direction from the exposed portion of the base substrate.
  • B A method in which a semiconductor crystal is facet grown in the c-axis direction using a group III nitride semiconductor substrate in which basal plane dislocations are aggregated in a line parallel to the m-axis obtained by the method of (A) as a base substrate ( That is, the method includes the following steps).
  • (B1) A step of preparing a group III nitride semiconductor substrate in which basal plane dislocations are aggregated in a line shape parallel to the m-axis.
  • B2 A step of facet growing a semiconductor crystal in the c-axis direction on the group III nitride semiconductor substrate.
  • (C) A method in which a semiconductor crystal is facet grown in a c-axis direction from a base substrate having a groove parallel to the m-axis.
  • (C1) A step of processing a plurality of grooves including recesses extending in the m-axis direction and forming a mask on the groove bottom surface.
  • (C2) A step of facet growing in the c-axis direction from the exposed portion of the convex portion (terrace) sandwiched between the grooves.
  • the growth surface in the case where the semiconductor crystal is facet grown is a facet surface (M-plane facet) appearing inclined from the M-plane.
  • FIG. 8 is a growth region from which growth starts
  • 9 is a region in which basal plane dislocations are aggregated (region X)
  • 10 is a crystal in which growth occurs.
  • the growth surface of each crystal enters the region 9 and the growth planes of adjacent crystals (M-plane facets) are angled. Collide with. Accordingly, the present inventors have found that when the growth planes of adjacent crystals collide approximately in the middle of the nine regions, the following drought process is taken.
  • basal plane dislocations are unlikely to occur, but in the case of collisions between grown crystals having different crystallographic orientations, the surface of each crystal growth surface at the time of coreless It can be inferred that a minute misalignment (off angle) of the orientation becomes a distortion, and the distortion is absorbed in the m-axis direction as a basal plane dislocation along the mask. That is, in order to obtain a semiconductor crystal having a stripe region X parallel to the m-axis (basal plane dislocations are also parallel to the m-axis), the occurrence of basal plane dislocations on the stripe mask or line is utilized.
  • a method for forming the M-plane facet is not particularly limited, and examples thereof include a temperature, a supply rate of the raw material, a supply amount, and a supply amount ratio (V / III ratio) between the group III raw material and the nitrogen raw material.
  • V / III ratio a supply amount ratio between the group III raw material and the nitrogen raw material.
  • an M-plane facet tends to be easily formed by performing initial growth at a temperature lower than that of main growth in the initial stage of growth.
  • the means is not limited to this as long as an M-plane facet can be formed.
  • the method for obtaining the semiconductor crystal in which the region X and the region Y according to the second embodiment are arranged in a layer shape approximately perpendicular to the growth direction will be specifically described below. explain.
  • a template substrate in which gallium nitride is grown by MOCVD on a heterogeneous substrate such as sapphire by about 15 ⁇ m is used as a base substrate for growth.
  • There is a method of growing a semiconductor crystal by exposing the C plane while periodically changing the crystal growth conditions. As a result, basal plane dislocations can be generated in a layered manner, and stress due to distortion with a different substrate can be released out of the crystal.
  • Examples of the growth conditions that are periodically changed include the temperature, the supply rate of the raw material, the supply amount, and the supply amount ratio (V / III ratio) of the group III raw material and the nitrogen raw material.
  • the means is not limited to this.
  • the preferred growth thickness of the semiconductor crystal is not particularly limited as long as it allows the substrate to be taken out, but it is preferably 1 mm or more.
  • the position to be cut out preferably includes a portion where basal plane dislocations are generated in a layered manner, and can be determined by the growth rate and growth conditions.
  • the crystal growth method for obtaining the group III nitride semiconductor crystal of the present invention is not particularly limited. Specifically, Hydride vapor phase epitaxy (HVPE method) 2. Metalorganic chemical vapor deposition (MOCVD) 3. Organometallic chloride vapor phase growth method (MOC method) 4).
  • HVPE method Hydride vapor phase epitaxy
  • MOCVD Metalorganic chemical vapor deposition
  • MOC method Organometallic chloride vapor phase growth method
  • a known vapor phase growth method such as a sublimation method can be appropriately employed. Among these, the HVPE method or the MOCVD method is preferable, and the HVPE method is particularly preferable.
  • the crystal growth method may be homoepitaxial growth or heteroepitaxial growth, and specific examples of the underlying substrate include silicon, sapphire, gallium arsenide, gallium nitride, aluminum nitride, and zinc oxide. Of these, gallium nitride is particularly preferred.
  • the mask pattern is not particularly limited, and either a dot shape or a stripe shape can be used.
  • a stripe mask When obtaining a group III nitride semiconductor crystal in which the regions X are arranged in stripes, it is preferable to use a stripe mask.
  • the pitch of the stripe mask is usually 100 ⁇ m to 3000 ⁇ m, preferably 200 ⁇ m to 2000 ⁇ m, more preferably 300 ⁇ m to 1000 ⁇ m.
  • the method for forming the mask is not particularly limited, and a mask layer is formed by appropriately adopting a known method such as a sputtering method, a CVD method (preferably a plasma CVD method), a vacuum deposition method, and the like, and then by a known photolithography method. Patterning and etching can be performed to form a mask having a desired shape.
  • the mask material is not particularly limited, and silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, tantalum oxide, zirconium oxide, hafnium oxide, or the like can be used.
  • the group III nitride semiconductor crystal of the present invention is obtained using a base substrate on which a stripe mask parallel to the m-axis is formed or a base substrate having a groove parallel to the m-axis
  • its manufacturing method is not particularly limited, For example, it can be obtained by the following operations (1) and (2).
  • a mask that inhibits crystal growth is formed on the main surface of the base substrate.
  • silicon oxide, silicon nitride, or the like can be used.
  • Hexamethyldisilazane is applied as a primer to this mask, and then a photoresist is applied. The photoresist is patterned by exposing and developing through a photomask having an arbitrary drawing.
  • a portion of the mask having no photoresist pattern is removed by etching.
  • the mask on the main surface of the base substrate is patterned.
  • the groove in the opening without the mask film by inductive coupling type reactive etching on the base substrate on which the mask is patterned, it is possible to form irregularities in a pattern parallel to the m-axis on the base substrate main surface.
  • a base substrate with deep grooves can be manufactured. If the growth conditions for epitaxially growing a semiconductor single crystal are conditions for promoting facet growth, a semiconductor crystal in which basal plane dislocations are aggregated in a line shape parallel to the m-axis can be produced on the underlying substrate.
  • a semiconductor crystal in which the regions X are arranged in stripes parallel to the m-axis can be obtained more easily.
  • a lift-off method, a self-alignment method using a photoresist, a method of performing dry etching or wet etching after forming a protective layer by patterning, etc. Is mentioned.
  • FIG. 4 the conceptual diagram of the manufacturing apparatus used for the manufacturing method which employ
  • the HVPE apparatus shown in FIG. 4 includes a susceptor 107 and a reservoir 105 for storing a raw material of a group III nitride semiconductor crystal to be grown in a reactor 100.
  • introduction pipes 101 to 104 for introducing gas into the reactor 100 and an exhaust pipe 108 for exhausting are installed.
  • a heater 106 for heating the reactor 100 from the side surface is installed.
  • quartz, sintered boron nitride, stainless steel, or the like can be used, but a preferable material is quartz.
  • the reactor 100 is filled with atmospheric gas in advance before starting the reaction.
  • the atmospheric gas include inert gases such as hydrogen, nitrogen, He, Ne, and Ar. These gases may be used alone or in combination.
  • the material of the susceptor 107 is preferably carbon, and more preferably one whose surface is coated with SiC.
  • the shape of the susceptor 107 is not particularly limited, but it is preferable that the structure does not exist in the vicinity of the crystal growth surface during crystal growth. If there is a structure that can grow near the crystal growth surface, polycrystals adhere to the structure, and HCl gas is generated as the product, which may adversely affect the crystal to be grown. is there.
  • the raw material of the III nitride semiconductor to be grown is put in the reservoir 105.
  • Ga, Al, In, etc. can be mentioned as a raw material used as a group III source.
  • a gas that reacts with the raw material put in the reservoir 105 is supplied from an introduction pipe 103 for introducing the gas into the reservoir 105.
  • HCl gas can be supplied from the introduction pipe 103.
  • the carrier gas may be supplied from the introduction pipe 103 together with the HCl gas.
  • the carrier gas include hydrogen, nitrogen, an inert gas such as He, Ne, and Ar. These gases may be used alone or in combination.
  • a source gas serving as a nitrogen source is supplied. Usually, NH 3 is supplied.
  • a carrier gas is supplied from the introduction pipe 101.
  • the carrier gas the same carrier gas supplied from the introduction pipe 104 can be exemplified. This carrier gas also has an effect of separating the source gas nozzle and preventing the polycrystal from adhering to the nozzle tip.
  • a dopant gas can also be supplied from the introduction pipe 102.
  • an n-type dopant gas such as oxygen, water, SiH 4 , SiH 2 Cl 2 , or H 2 S can be supplied.
  • the above gases supplied from the introduction pipes 101 to 104 may be exchanged with each other and supplied from different introduction pipes.
  • the source gas and the carrier gas serving as a nitrogen source may be mixed and supplied from the same introduction pipe.
  • a carrier gas may be mixed from another introduction pipe.
  • the gas exhaust pipe 108 can be installed on the top, bottom and side surfaces of the reactor inner wall. From the viewpoint of dust removal, it is preferably located below the crystal growth end, and more preferably a gas exhaust pipe 108 is installed on the bottom of the reactor as shown in FIG.
  • the temperature conditions for crystal growth are not particularly limited, but are usually preferably 800 ° C. to 1200 ° C., 850 ° C. to 1150 ° C., more preferably 900 ° C. to 1100 ° C., and even more preferably 970 ° C. to 1040 ° C.
  • the pressure in the reactor is not particularly limited, but is preferably 50 kPa to 120 kPa, and particularly preferably atmospheric pressure.
  • the growth rate of crystal growth varies depending on the growth method, growth temperature, raw material gas supply amount, crystal growth surface orientation, etc., but is generally in the range of 5 ⁇ m / h to 500 ⁇ m / h, and is 10 ⁇ m / h or more. Preferably, 50 ⁇ m / h or more is more preferable, 70 ⁇ m or more is further preferable, and 140 ⁇ m / h or more is particularly preferable.
  • the growth rate can be controlled by appropriately setting the type, flow rate, supply port-crystal growth end distance, etc. of the carrier gas.
  • the items to be changed periodically can be one type or a plurality of combinations.
  • the growth temperature, the ratio of nitrogen source to group III, and the type of carrier gas it is preferable to change the growth temperature, the ratio of nitrogen source to group III, and the type of carrier gas, alone or in combination.
  • a method for obtaining a crystal whose main surface is a nonpolar plane (M plane / A plane) or a semipolar plane the same method as described above can be employed.
  • a plurality of seed crystals arranged may be used as a base substrate.
  • the same method as described above can be adopted.
  • basal plane dislocations may be aggregated and generated in the crystal portion grown immediately above the junction between the seed crystals.
  • the production method for obtaining the group III nitride semiconductor crystal of the present invention may include a molding process (separation process and polishing process) described below.
  • the separation step is a step of separating the grown group III nitride semiconductor from the base substrate, and specifically includes a cutting operation and a slicing operation.
  • a slicing operation is particularly preferable.
  • a group III nitride semiconductor includes a part containing many threading dislocations from the seed crystal surface, it is preferable to remove the part, and the above-described cutting operation and slicing operation can be used. Examples of the slicing operation include wire slicing and inner peripheral edge slicing.
  • a polishing process is required to use the crystal as a semiconductor substrate.
  • the group III nitride semiconductor crystal according to the present invention can be used for various applications.
  • it is useful as a substrate for semiconductor devices such as light emitting diodes of ultraviolet, blue or green, etc., light emitting elements having relatively short wavelengths such as semiconductor lasers, and electronic devices.
  • Example 1 A single crystal gallium nitride (GaN) substrate was prepared as a base substrate.
  • This single crystal GaN substrate is a self-standing substrate having a disk shape with a thickness of 400 ⁇ m and a diameter of 50 mm, and having a ⁇ 0001 ⁇ plane (C plane).
  • About 0.1 ⁇ m of SiO 2 film was deposited on the surface of the GaN free-standing substrate by plasma CVD. This GaN free-standing substrate with SiO 2 film was subjected to ultrasonic cleaning for 10 minutes in each of acetone and methanol, and rinsed with pure water for 5 minutes.
  • HMDS Hexamethyldisilazane
  • Pre-baking is a process for fixing the resist.
  • the positive resist used is “OFPR-800” manufactured by Tokyo Ohka Kogyo Co., Ltd.
  • the resist was exposed using a Cr mask for exposure.
  • a stripe pattern having a line (Mask) / space (Window) of 50 ⁇ m / 400 ⁇ m is formed, and the stripe direction is ⁇ 1-100> on the surface of the GaN free-standing substrate as the base substrate.
  • Exposure was performed with a Cr mask set so as to be parallel to the m-axis.
  • the exposure time was 8 seconds, and post-baking was performed at 120 ° C. for 30 minutes after exposure.
  • the -C surface is in contact with the substrate holder and does not come into direct contact with the source gas.
  • the temperature of the reaction chamber was raised to 970 ° C., and the raw material was supplied from the + C plane direction of the base substrate to grow the initial growth for 15 minutes.
  • O-doped GaN was grown by raising the temperature of the reaction chamber to 1005 ° C. and supplying the raw material from the + C plane direction of the base substrate.
  • O-doping is realized by facet growth.
  • the growth pressure is set to 1.01 ⁇ 10 5 Pa
  • the partial pressure of NH 3 gas is 8.13 ⁇ 10 3 Pa
  • the partial pressure of N 2 gas is 1.17 ⁇ 10 4 Pa
  • GaCl gas The partial pressure was 7.00 ⁇ 10 2 Pa
  • the partial pressure of H 2 gas was 8.04 ⁇ 10 4 Pa
  • the raw material was introduced from the introduction tube.
  • the temperature was lowered to room temperature.
  • the shape of the obtained gallium nitride single crystal was a circular shape with irregularities whose surface maintained the facet growth of the line, and the film thickness in the C-axis direction was about 6.3 mm.
  • the area of the main surface (C surface) was 1963 mm 2 as an effective diameter of 50 mm as a result of using a 57 mm base substrate.
  • (13) The obtained gallium nitride single crystal was processed into a disk shape by outer peripheral processing, and then sliced so that the C-plane became a plate shape of the main surface, which was suitable for fluorescence microscope observation and SEM-CL observation Polishing was performed until the surface state was obtained, and the gallium nitride semiconductor crystal substrate 1 was obtained. Next, the radius of curvature of the gallium nitride semiconductor crystal substrate 1 was measured.
  • the radius of curvature can be calculated by a well-known method from the inclination of the crystal axis measured by X-ray diffraction measurement or the like as an indication of the curvature of the crystal plane.
  • the radius of curvature of the + C plane was measured with an X-ray diffractometer, the radius of curvature in the direction parallel to the line, that is, the direction parallel to the m-axis was 10.3 m, and the radius of curvature in the direction parallel to the a-axis was 3 0.0 m.
  • the basal plane dislocation distribution of the gallium nitride semiconductor crystal substrate 1 was observed by SEM-CL using a JSM-7000 scanning electron microscope manufactured by JEOL Ltd.
  • the acceleration voltage of the cathodoluminescence scanning electron microscope was adjusted to 3.0 kV. Information from the sample surface to a depth of 0.08 ⁇ m is detected by this acceleration voltage.
  • FIGS. 5a and 5b SEM-CL images are shown in FIGS. 5a and 5b.
  • FIG. 5 a is an image observed from the C-plane side of the crystal, and the black line-shaped one is the basal plane dislocation. From this, it was confirmed that the basal plane dislocations having a dislocation line length of 3 ⁇ m or more are concentrated in a line shape parallel to the m-axis.
  • FIG. 5b is an image observed from the M-plane side of the crystal, and the black dots are basal plane dislocations.
  • the gallium nitride semiconductor crystal substrate 1 contained 11% of the region X and 89% of the region Y. Further, from the SEM-CL image or the like, the region X and the region Y are arranged in a stripe shape in the gallium nitride semiconductor crystal substrate 1, the width (short side) of the region X is 50 ⁇ m, and the width of the region Y ( It was confirmed that the short side was 400 ⁇ m. Further, it was confirmed that the maximum length of the region X was 50 mm.
  • positioning of the basal plane dislocation was observed using the TECNAI G2F20 transmission electron microscope made from FEI Company.
  • the acceleration voltage of the transmission electron microscope was adjusted to 200 kV. With this acceleration voltage, information on the region from the edge to the thickness of 1000 nm is detected for the knife-edge thin film sample.
  • a transmission electron microscope image is shown in FIG. FIG. 6 is an image in the region Y observed from the M-plane side of the crystal, and the linear dark contrast is the basal plane dislocation.
  • a polygonal arrangement of basal plane dislocations was confirmed. Since the basal plane dislocation itself has polar self-strain, the state of being arranged in a line in the polarity direction in FIG. 6 can be interpreted as a dislocation theory as a mechanism for reducing internal residual stress.
  • Example 2 A rectangular parallelepiped having a length of 25 mm in the [-12-10] direction and 10 mm in the [0001] direction and having a thickness of 330 ⁇ m, the main surface is ⁇ 1 in the [0001] direction from the (10-10) plane.
  • Ten GaN free-standing substrates having a 0 ° off-angle in the [-12-10] direction were prepared and used as seed substrates.
  • Ten seed substrates were arranged so that the (0001) plane, the (000-1) plane, the (1-210) plane, and the (-12-10) plane of the seed substrate were bonded surfaces.
  • 10 seed substrates are arranged in 5 rows in the [0001] direction and 2 rows in the [-12-10] direction, and the cross section of the (0001) plane and the (000-1) plane of each seed substrate. They were arranged on the susceptor 107 so that the cross sections face each other and the cross section of the (1-210) plane and the cross section of the (-12-10) plane face each other.
  • the susceptor was placed in the reactor 100, the temperature of the reaction chamber was raised to 970 ° C., and growth of the GaN single crystal layer was started by the HVPE method. Simultaneously with the start of growth, the temperature in the reaction chamber was raised from 970 ° C. to 1020 ° C.
  • the growth pressure is 1.01 ⁇ 10 5 Pa from the start of growth to the end of growth
  • the partial pressure of GaCl gas is 5.96 ⁇ 10 2 Pa
  • the partial pressure of NH 3 gas is 5.34. ⁇ 10 3 Pa.
  • the temperature was lowered to room temperature to obtain a GaN crystal.
  • the temperature was lowered to room temperature to obtain a group III nitride crystal. In the region above the boundary region between adjacent seed substrates in the obtained crystal, the group III nitride crystal was grown in combination and grew 3.5 mm in the [10-10] direction.
  • the obtained group III nitride crystal was subjected to outer shape processing and surface polishing treatment, and then sliced and polished by the same method as in Example 1 to obtain (10-10) having a diameter of 2 inches and a thickness of 440 ⁇ m.
  • Three gallium nitride semiconductor crystal substrates 2 having a main surface as a main surface were produced.
  • the radius of curvature was measured in the same manner as in Example 1.
  • the curvature radius of the M plane was measured with an X-ray diffractometer, the curvature radius in the direction parallel to the a-axis of the crystal was 3.6 m.
  • the distribution of basal plane dislocations was observed using a SEM-CL apparatus, and the basal plane dislocation density ⁇ was calculated.
  • FIGS. 7A and 7B SEM-CL images of region X and region Y are shown in FIGS. 7A and 7B, respectively.
  • 7A and 7B are images of the crystal observed from the M-plane side. Furthermore, in the low-magnification SEM-CL image, it was confirmed that the basal plane dislocations were concentrated in a layer shape approximately parallel to the growth direction. Further, the distribution of basal plane dislocations was observed in the same manner as in Example 1, and the basal plane dislocation density ⁇ in the regions X and Y was calculated. The results are shown in Table 1.
  • the dislocation density value calculated from the 80 ⁇ m ⁇ 80 ⁇ m region and the 40 ⁇ m ⁇ 40 ⁇ m region corresponding to 1/4 of the region are arbitrarily extracted, and the dislocation density calculated therefrom is calculated. It was confirmed to have a region X ′ whose value is within 1.5 times the difference. Further, from the SEM-CL image, it was confirmed that the gallium nitride semiconductor crystal substrate 2 contained 10% of the region X and 90% of the region Y.
  • the region X and the region Y are arranged in a stripe shape in the gallium nitride semiconductor crystal substrate 2, and the width (short side, c-axis direction) of the region X is 500 ⁇ m. It was confirmed that the width of Y (short side, c-axis direction) was 4500 ⁇ m. Further, it was confirmed that the maximum length of the region X was 50 mm.
  • a template substrate was prepared by growing gallium nitride by about 15 ⁇ m by MOCVD on a sapphire substrate.
  • the base substrate was placed on the substrate holder on the HVPE device susceptor with the + C surface facing upward. At this time, the -C surface is in contact with the substrate holder and does not come into direct contact with the source gas.
  • the concentration in the reaction chamber was raised to 1080 ° C., and the raw material was supplied from the + C plane direction of the base substrate to grow for 45 minutes (hereinafter also referred to as region Y growth).
  • the temperature of the reaction chamber was raised to 1020 ° C., and the raw material was supplied from the + C plane direction of the base substrate to grow Si-doped gallium nitride for 6 hours (hereinafter also referred to as region X growth).
  • the growth pressure is set to 1.01 ⁇ 10 5 Pa
  • the partial pressure of NH 3 gas is 8.13 ⁇ 10 3 Pa
  • the partial pressure of N 2 gas is 1.17 ⁇ 10 4 Pa
  • the partial pressure was 7.00 ⁇ 10 2 Pa
  • the partial pressure of H 2 gas was 8.04 ⁇ 10 4 Pa
  • the partial pressure of dichlorosilane gas was 1.74 ⁇ 10 ⁇ 1 Pa
  • the raw material was introduced from the introduction tube.
  • the region Y growth (1080 ° C., 45 minutes) and the region X growth (1020 ° C., 6 hours) were periodically repeated four times.
  • the temperature was lowered to room temperature.
  • the shape of the obtained gallium nitride single crystal was a circular shape with a mirror surface, and the film thickness in the C-axis direction was about 3.6 mm.
  • the area of the main surface (C surface) of the obtained gallium nitride single crystal was 2043 mm 2 and the effective diameter was 51 mm.
  • the obtained gallium nitride single crystal was shaped into a disk shape by outer periphery processing in the same manner as in Example 1, and then the C surface was the main surface, and the plate shape including the predesigned region X as a layer
  • the gallium nitride semiconductor crystal substrate 3 was obtained by slicing and polishing until a surface state suitable for fluorescence microscope observation and SEM-CL observation was obtained.
  • the curvature radius of the obtained gallium nitride semiconductor crystal substrate 3 was measured in the same manner as in Example 1.
  • FIG. 8 is an image obtained by observing the crystal from the M-plane side, and in the low-magnification SEM-CL image, it was confirmed that the basal plane dislocations were concentrated in a layer shape approximately perpendicular to the growth direction.
  • Table 1 shows the results of the basal plane dislocation density ⁇ . Further, when examining the region X, the dislocation density value calculated from the 80 ⁇ m ⁇ 80 ⁇ m region and the 40 ⁇ m ⁇ 40 ⁇ m region corresponding to 1/4 of the region are arbitrarily extracted, and the dislocation density calculated therefrom is calculated. It was confirmed to have a region X ′ whose value is within 1.5 times the difference.
  • the gallium nitride semiconductor crystal substrate contained 88% region X and 12% region Y. Further, from the SEM-CL image or the like, the region X and the region Y are arranged in layers in the gallium nitride semiconductor crystal substrate, the width of the region X (layer thickness) is 700 ⁇ m, and the width of the region Y (layer) Thickness) was 100 ⁇ m. Further, it was confirmed that the maximum length of the region X was 50 mm.
  • a template substrate was prepared by growing gallium nitride by about 15 ⁇ m by MOCVD on a sapphire substrate.
  • the base substrate was placed on the substrate holder on the HVPE device susceptor with the + C surface facing upward. At this time, the -C surface is in contact with the substrate holder and does not come into direct contact with the source gas.
  • the initial growth was performed for 1 hour 30 minutes by raising the concentration in the reaction chamber to 970 ° C. and supplying the raw material from the + C plane direction of the base substrate.
  • the temperature of the reaction chamber was raised to 1020 ° C., and the raw material was supplied from the + C plane direction of the base substrate to grow undoped gallium nitride.
  • the growth pressure is set to 1.01 ⁇ 10 5 Pa
  • the partial pressure of NH 3 gas is 7.54 ⁇ 10 3 Pa
  • the partial pressure of N 2 gas is 8.88 ⁇ 10 3 Pa
  • the GaCl gas The partial pressure was 6.52 ⁇ 10 2 Pa
  • the partial pressure of H 2 gas was 8.39 ⁇ 10 4 Pa
  • the raw material was introduced from the introduction tube.
  • the temperature was lowered to room temperature.
  • the shape of the obtained gallium nitride single crystal was a circular shape with a mirror surface, and the film thickness in the c-axis direction was about 4.1 mm.
  • the area of the main surface (C surface) of the obtained gallium nitride single crystal was 2376 mm 2 and the effective diameter was 55 mm.
  • the obtained gallium nitride single crystal was shaped into a disk shape by outer periphery processing, and then the C surface was the main surface and the plate shape did not include the region X.
  • the gallium nitride semiconductor crystal substrate was obtained by slicing and polishing until a surface state suitable for fluorescence microscope observation and SEM-CL observation was obtained.
  • the radius of curvature of the obtained gallium nitride semiconductor crystal substrate was measured in the same manner as in Example 1.
  • the radius of curvature of the + C plane was measured with an X-ray diffractometer, the radius of curvature in the direction parallel to the a-axis was 2.5 m, and the radius of curvature in the direction parallel to the m-axis was 2.8 m.
  • the basal plane dislocation distribution was observed using the SEM-CL apparatus in the same manner as in Example 1, and the basal plane dislocation density ⁇ was calculated.
  • An SEM-CL image is shown in FIG. Table 1 shows the results of the basal plane dislocation density ⁇ .
  • the region X and the crystal whose basal plane dislocation density is 1.0 ⁇ 10 6 cm ⁇ 2 or more when the ⁇ 10-10 ⁇ plane of the crystal is observed includes a region Y that is less than 1.0 ⁇ 10 6 cm ⁇ 2 .
  • the radius of curvature of the crystal plane of the main surface of the gallium nitride semiconductor single crystal substrate of Examples 1, 2, and 3 can be measured in both the a-axis direction and the m-axis direction. It is clear that it has a radius of curvature of 3.0 m or more.
  • FIG. 10b shows a graph in which the phase difference ( ⁇ ) of points adjacent to each other at intervals of 181 ⁇ m in the diameter direction is plotted for the phase difference distributions of Examples 1 and 3 and Comparative Example 1 shown in FIG. 10a.
  • FIG. 10c shows a graph in which the difference (
  • III nitride semiconductor crystal of the present invention is a crystal in which internal stress is uniformly dispersed within the crystal and cracking is less likely to occur during molding.

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Abstract

Étant donné qu'un cristal semi-conducteur de nitrure du groupe III tel que le nitrure de gallium subit parfois une fissuration pendant un traitement tel que le tranchage ou le polissage, le cristal semi-conducteur de nitrure du groupe III a été un facteur qui abaisse le rendement de production d'un substrat ou analogue. Par la présence d'une région (région X) où la densité de dislocation dans le plan basal n'est pas inférieure à une valeur spécifique et d'une région (région Y) où la densité de dislocation dans le plan basal est inférieure à la valeur spécifique, la tension interne dans le cristal est dispersée, un cristal semi-conducteur de nitrure du groupe III devient moins sensible à la fissuration pendant un traitement tel que le tranchage ou le polissage.
PCT/JP2012/077054 2011-10-21 2012-10-19 Cristal semi-conducteur de nitrure du groupe iii WO2013058352A1 (fr)

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CN108291329B (zh) * 2015-12-11 2019-03-01 日本碍子株式会社 13族元素氮化物结晶基板及功能元件
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JP2019112261A (ja) * 2017-12-22 2019-07-11 昭和電工株式会社 ＳｉＣ単結晶の加工方法及びＳｉＣインゴットの製造方法

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