SiC single crystal substrate

Abstract

To provide an SiC single crystal substrate that has small SORI change on ion injection.SOLUTION: An SiC single crystal substrate 1 has OFF angles of 0 to 6° in a <11-20> direction and 0 to 0.5°in a <1-100> direction that a principal surface has to a (0001) plane, and includes non-MP defects, wherein etch pits include non-MP defective pits, as pits identified as the non-MP defects, that appear within a range of 0.1 to 50 pieces / cm2, and also have a density NA {pieces / cm2]of non-MP defective pits in the center part region and a density NB {pieces / cm2] of non-MP defective pits in the outside region that satisfy 0.01<NP<0.5 (where NP={NA / (NA+NB)}) when the substrate is divided into the center part region within a range of r / 2 from the center and the outside region located outside it, and diameters range from 145 to 155 mm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a SiC single crystal substrate. [Background technology]

[0002] Silicon carbide (SiC) has a dielectric breakdown field that is an order of magnitude larger and a band gap that is three times larger than that of silicon (Si). Furthermore, SiC has properties such as a thermal conductivity that is approximately three times higher than that of silicon (Si). Therefore, SiC is expected to have applications in power devices, high-frequency devices, and high-temperature operating devices. For this reason, SiC epitaxial wafers have recently come into use in semiconductor devices such as those mentioned above.

[0003] SiC epitaxial wafers are obtained by stacking SiC epitaxial layers on the surface of a SiC single crystal substrate. Hereinafter, the substrate before stacking the SiC epitaxial layers will be referred to as a SiC single crystal substrate, and the substrate after stacking the SiC epitaxial layers will be referred to as a SiC epitaxial wafer. SiC single crystal substrates are cut from SiC single crystal ingots.

[0004] While the current market for SiC single-crystal substrates is dominated by 6-inch (150mm) diameter substrates, development is underway for the mass production of 8-inch (200mm) SiC single-crystal substrates, and full-scale mass production is beginning. The increased diameter from 6 inches to 8 inches is expected to improve production efficiency and reduce costs, leading to further widespread adoption of SiC power devices as a key energy-saving technology.

[0005] When manufacturing the next-generation large-diameter SiC single crystal substrate, even if the manufacturing conditions optimized for the production of the SiC single crystal substrate with the current diameter are applied, the same level of quality cannot be obtained. This is because new problems arise according to the new size. For example, in Patent Document 1, when manufacturing a 6-inch SiC single crystal substrate, if the manufacturing technology of a 4-inch SiC single crystal substrate is applied, thermal decomposition frequently occurs around the outer peripheral side of the seed crystal, and macro defects occur due to this thermal decomposition, so a single crystal with high crystal quality cannot be obtained with a good yield. Patent Document 1 describes an invention that solves this problem by using a seed crystal with a predetermined thickness. Thus, it is necessary to establish the manufacturing conditions for the SiC single crystal substrate of the new size while solving the new problems that have occurred according to the new size.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] The SiC single crystal substrate is obtained through the SiC single crystal ingot manufacturing process and the SiC single crystal substrate process of manufacturing the SiC single crystal substrate from the SiC single crystal ingot. To establish the manufacturing technology of an 8-inch SiC single crystal substrate, it is necessary to solve the new problems unique to the 8-inch substrate for each of the SiC single crystal ingot manufacturing process and the SiC single crystal substrate process.

[0008] Here, new challenges unique to 8-inch substrates include, for example, obtaining an 8-inch substrate with the same dislocation density as that of a 6-inch substrate in the process of manufacturing a SiC single crystal ingot. When manufacturing an 8-inch substrate by simply applying the manufacturing technology of SiC single crystal substrates optimized for the production of 6-inch substrates, an 8-inch substrate with a dislocation density higher than that of a 6-inch substrate will be produced. This is because the hurdle for obtaining the same quality increases significantly as the size increases. Therefore, in evaluating the manufacturing technology of 8-inch SiC single crystal substrates, the starting point is the dislocation density of the 8-inch substrate obtained by simply applying the manufacturing technology of SiC single crystal substrates optimized for the production of 6-inch substrates, and the technical value should be evaluated based on how much improvement has been made relative to the starting point dislocation density. On the other hand, the yield of 8-inch SiC single crystal substrates in mass production is determined by evaluation criteria similar to or even stricter than those for 6-inch SiC single crystal substrates. Step-by-step improvements will lead to the establishment of the manufacturing technology of 8-inch SiC single crystal substrates.

[0009] As a result of intensive studies, the inventor has discovered a new type of defect that has not been reported so far in SiC single crystal substrates, and has found that when having this new type of defect at a density within a predetermined range, the change in SORI before and after ion implantation is small.

[0010] The present invention has been made in view of the above circumstances, and an object thereof is to provide a SiC single crystal substrate with a small change in SORI before and after ion implantation.

Means for Solving the Problems

[0011] In order to solve the above problems, the present invention provides the following means.

[0012] Aspect 1 of the present invention has an off-angle in the range of 0° to 6° in the <11-20> direction and 0° to 0.5° in the <1-100> direction with respect to the (0001) plane. When etched with molten KOH at 500°C for 15 minutes with respect to the Si plane, the etch pits that appear are hexagonal and have no core. Furthermore, the observed etch pit area is 10% or more larger than the etch pit area of the TSD etch pits and 110% or less of the etch pit area of the micro-pipe (MP) etch pits, and it can be distinguished from the transmission X-ray topography image of the micro-pipe (MP) in the transmission X-ray topography image. It contains non-MP defects, and among the etch pits, the non-MP defect pits, which are the pits identified as the non-MP defects, are 0.1 per cm 2 ~50 per cm 2 appear within the range, and when the radius r of the substrate is divided into a central region within the range of r / 2 from the center and an outer region located outside the central region, the density NA [per cm 2 of the non-MP defect pits in the central region and the density NB [per cm 2 of the non-MP defect pits in the outer region satisfy the relationship of 0.01 < NP < 0.5 (where NP = {NA / (NA+NB)}), and it is a SiC single crystal substrate with a diameter in the range of 145 mm to 155 mm.

[0013] Aspect 2 of the present invention has an off-angle in the range of 0° to 6° in the <11-20> direction and 0° to 0.5° in the <1-100> direction with respect to the (0001) plane. When etched with molten KOH at 500°C for 15 minutes with respect to the Si plane, the etch pits that appear are hexagonal and have no core. Furthermore, the observed etch pit area is 10% or more larger than the etch pit area of the TSD etch pits and 110% or less of the etch pit area of the micro-pipe (MP) etch pits, and it can be distinguished from the transmission X-ray topography image of the micro-pipe (MP) in the transmission X-ray topography image. It contains non-MP defects, and among the etch pits, the non-MP defect pits, which are the pits identified as the non-MP defects, are 0.1 per cm 2 ~50 per cm 2appears within the range. When the radius r of the substrate is divided into a central region within the range of r / 2 from the center and an outer region located outside the central region, the density NA [number / cm 2 of non-MP defect pits in the central region and the density NB [number / cm 2 of non-MP defect pits in the outer region satisfy the relationship 0.01 < NP < 0.5 (where NP = {NA / (NA + NB)}), and it is a SiC single crystal substrate with a diameter in the range of 190 mm to 205 mm.

[0014] Aspect 3 of the present invention is a SiC single crystal substrate according to Aspect 1 or Aspect 2, wherein the non-MP defect pits, which are the pits identified as the non-MP defects among the etch pits, appear within the range of 0.1 number / cm 2 ~20 number / cm 2 .

[0015] Aspect 4 of the present invention is a SiC single crystal substrate according to Aspect 1 or Aspect 2, wherein the non-MP defect pits, which are the pits identified as the non-MP defects among the etch pits, appear within the range of 0.1 number / cm 2 ~10 number / cm 2 .

[0016] Aspect 5 of the present invention is a SiC single crystal substrate according to Aspect 1 or Aspect 2, wherein the non-MP defect pits, which are the pits identified as the non-MP defects among the etch pits, appear within the range of 1 number / cm 2 ~50 number / cm 2 .

[0017] Aspect 6 of the present invention is a SiC single crystal substrate according to Aspect 1 or Aspect 2, wherein the non-MP defect pits, which are the pits identified as the non-MP defects among the etch pits, appear within the range of 1 number / cm 2 ~20 number / cm 2 .

[0018] Aspect 7 of the present invention is a SiC single crystal substrate according to Aspect 1 or Aspect 2, wherein the non-MP defect pits, which are the pits identified as the non-MP defects among the etch pits, appear within the range of 1 number / cm 2 ~10 number / cm 2It appears within the range.

[0019] Aspect 8 of the present invention is a SiC single crystal substrate according to aspect 1 or aspect 2, wherein the number of non-MP defect pits, which are identified as non-MP defects, is 1.5 per cm² in the etch pits. 2 ~50 pieces / cm 2 It appears within the range.

[0020] Aspect 9 of the present invention is a SiC single crystal substrate according to aspect 1 or aspect 2, wherein the number of non-MP defect pits, which are identified as non-MP defects, is 1.5 per cm² in the etch pits. 2 ~20 pieces / cm 2 It appears within the range.

[0021] Aspect 10 of the present invention is a SiC single crystal substrate according to aspect 1 or aspect 2, wherein the number of non-MP defect pits, which are identified as non-MP defects, is 1.5 per cm² in the etch pits. 2 ~9.8 pieces / cm 2 It appears within the range.

[0022] Aspect 11 of the present invention is a SiC single crystal substrate in any one of aspects 1 to 10, wherein the NP is 0.051 to 0.469.

[0023] Aspect 12 of the present invention is a SiC single crystal substrate in any one of aspects 1 to 10, wherein the NP is 0.137 to 0.213. [Effects of the Invention]

[0024] The present invention provides a SiC single crystal substrate in which the change in SORI is small before and after ion implantation. [Brief explanation of the drawing]

[0025] [Figure 1] This is a schematic plan view of a SiC single crystal substrate according to this embodiment. [Figure 2]This is a schematic diagram showing the plane orientation of a SiC single crystal substrate. (a) is a perpendicular cross-sectional view taken perpendicular to the main plane, and (b) is a schematic plan view taken from a direction perpendicular to the main plane. [Figure 3] This is an optical microscope image of etch pits on a SiC single crystal substrate. [Figure 4] This is a transmission X-ray topography image of a SiC single crystal substrate. [Figure 5] This is a schematic plan view of a SiC single crystal substrate according to this embodiment. [Figure 6] This is a schematic cross-sectional view of an annealing crucible used for the substrate annealing process. [Figure 7] The image on the right shows an XRT image of a SiC single crystal substrate (g(1-100)), the lower left shows an optical microscope image of a sample without substrate annealing after molten KOH etching, and the upper left shows an optical microscope image of a sample with substrate annealing after molten KOH etching. [Figure 8] This is a schematic cross-sectional view of a SiC single crystal manufacturing apparatus. [Figure 9] This is a schematic cross-sectional view of another example of a SiC single crystal fabrication apparatus. [Figure 10] This is a schematic cross-sectional view of the drive mechanism for moving the thermal insulation material up and down in a SiC single crystal manufacturing apparatus. [Figure 11] This shows the positional relationship between the bottom surface of the insulating material and the surface of the single crystal, and its relationship to the isothermal surface near the single crystal. [Figure 12] This diagram schematically shows the shape of an isothermal surface near a single crystal during crystal growth. [Modes for carrying out the invention]

[0026] The present invention will be described in detail below, with appropriate reference to the drawings. The drawings used in the following description may be enlarged for convenience to clearly illustrate the features of the present invention, and the dimensional ratios of each component may differ from those of the actual components. The materials, dimensions, etc., exemplified in the following description are examples only, and the present invention is not limited to them. It is possible to modify and implement the invention as appropriate within the scope of achieving its effects. Furthermore, in each drawing, components other than those described in that drawing, which are well known to those skilled in the art, may be omitted. In the crystallographic descriptions within this specification, individual orientations are indicated by [], collective orientations by <>, individual planes by (), and collective planes by {}. While crystallographic conventions dictate that negative exponents are represented by a "-" (bar) above the number, in this specification, the negative sign is placed before the number.

[0027] (SiC single crystal substrate) Figure 1 is a schematic plan view of a SiC single crystal substrate according to this embodiment. Figure 2 is a schematic diagram showing the plane orientation of the SiC single crystal substrate, where (a) is a perpendicular cross-sectional view taken perpendicular to the main plane, and (b) is a schematic plan view viewed from a direction perpendicular to the main plane.

[0028] The SiC single crystal substrate 1 shown in Figure 1 has a main surface with an off-angle of 0° to 6° in the <11-20> direction and 0° to 0.5° in the <1-100> direction relative to the (0001) plane. The etch pits that appear when the Si surface is etched with molten KOH at 500°C for 15 minutes are hexagonal in shape and have no core. Furthermore, the observed etch pit area is 10% or more larger than the etch pit area of ​​TSD etch pits and 110% or less of the etch pit area of ​​micropipe (MP) etch pits, and contains non-MP defects that are distinguishable from the transmitted X-ray topography image of the micropipe (MP). The inclusion of non-MP defects in the SiC single-crystal substrate suppresses changes in SORI before and after ion implantation during the device fabrication process, thereby improving yield. This is thought to be due to the reduction of stress relaxation and damage caused by ion implantation by the inclusion of non-MP defects.

[0029] There are no particular restrictions on the external shape of the SiC single crystal substrate 1; various flat plate shapes and thicknesses can be used, although it is typically disc-shaped. The thickness of the SiC single crystal substrate can be, for example, in the range of 300 to 650 μm.

[0030] The size of the SiC single crystal substrate 1 is not limited as long as it does not produce non-MP defects, but it can be, for example, 6 inches (in the range of 145 mm to 155 mm in diameter) or 8 inches (in the range of 190 mm to 205 mm in diameter).

[0031] The SiC single crystal substrate 1 is preferably 4H-SiC. Although SiC exists in various polytypes, 4H-SiC is the one mainly used for fabricating practical SiC devices.

[0032] The SiC single crystal substrate 1 has an off-angle of 0° to 6° in the <11-20> direction and 0° to 0.5° in the <1-100> direction relative to the (0001) plane. A larger off-angle results in fewer wafers being obtained from a SiC single-crystal ingot; therefore, a smaller off-angle is preferable from a cost reduction perspective.

[0033] In this specification, "non-MP defects" refer to defects that exhibit characteristics common to micropipes (MPs) in etch pits revealed by molten KOH etching, but can be distinguished from micropipes by transmission X-ray topography. Specifically, the hexagonal shape of the etch pits revealed by molten KOH etching at 500°C for 15 minutes on the Si surface is common to both MPs and TSDs (see Figure 3). While a core is visible in the center of the pits of TSDs, no core is visible in the pits of MPs and non-MP defects (see Figure 3). This is thought to be due to the large depth making it difficult to focus with a microscope. The observed etch pit area is more than 10% larger than the area of ​​TSD etch pits and less than 110% of the area of ​​MP etch pits. Furthermore, while micropipes can be detected by transmission X-ray topography, non-MP defects are either not detected by transmission X-ray topography or show very weak contrast compared to micropipes. Here, the "etch pit area" of each defect can be measured based on a microscopic image taken with an optical microscope or the like of the substrate surface where etch pits have been exposed by molten KOH etching. For example, the microscopic image can be imported into a computer and calculated using image analysis software, or it can be measured using a commercially available wafer defect analysis device. The "etch pit area" is calculated by averaging the area of ​​etch pits observed in a 1.2 × 1.4 mm square area at five or more points in the radial direction, including the in-plane center, on the surface of the substrate where the etch pits have been exposed, and using that as the area per pit. Similarly, the number of etch pits and the etch pit density of each defect can also be measured based on a microscopic image taken with an optical microscope or the like in the same manner.

[0034] Molten KOH etching is a type of defect-selective etching that selectively forms surface depressions (etch pits) around crystal defects by corroding the crystal surface. Etch pits caused by corrosion are selectively etched in areas of the crystal surface with relatively high chemical potential. Therefore, the shape of the etch pit is determined by the type of dislocation defect, the direction of the dislocation line, and the symmetry of the crystal, and the type of defect can be determined from its shape.

[0035] Micropipes are hollow through-defects with a diameter of several micrometers to tens of micrometers that penetrate the crystal in the growth direction (c-axis direction), and their cause is thought to be the strain relaxation of through-helical dislocations. In other words, through-helical dislocations are relaxed during crystal growth, accompanied by the formation of micropipe defects, and as a result, they are formed as hollow through-defects with a hollow core, and are considered to be a type of dislocation.

[0036] The type of dislocation (including micropipes) can be determined from the shape of the etch pits revealed by molten KOH etching using an optical microscope, electron microscope (SEM), etc. Generally, large hexagonal etch pits without a core correspond to micropipes (MPs), medium hexagonal etch pits with a core correspond to through-helix dislocations (TSDs), small hexagonal etch pits with a core correspond to through-edge dislocations (TEDs), and elliptical (shell-shaped) etch pits correspond to basal plane dislocations (BPDs). Since BPDs extend into the c-plane, BPD etch pits have a shell-like shape that spreads toward the off-direction of the substrate. TSD etch pits and TED etch pits are formed by preferential etching of areas with weak bonds (dislocation cores).

[0037] Micropipe (MP) etch pits (hereinafter sometimes referred to as "MP etch pits"), through-spirular dislocation (TSD) etch pits (hereinafter sometimes referred to as "TSD etch pits"), and through-edge dislocation (TED) etch pits (hereinafter sometimes referred to as "TED etch pits") all share a hexagonal shape, but TSD etch pits and TED etch pits differ from MP etch pits in that they have a core and in their size. If the size of a hexagonal etch pit is defined as the diameter of the longest diagonal among the diagonals of the anisotropic hexagon of the etch pit, then MP etch pits are approximately 5-50 μm, TSD etch pits are approximately 1-10 μm, and TED etch pits are approximately 1-10 μm.

[0038] Figure 3 shows typical optical microscope images of each etch pit after molten KOH etching at 500°C for 15 minutes. (a) is an etch pit corresponding to a non-MP defect (hereinafter sometimes referred to as "non-MP etch pit"), (b) is an MP etch pit, and (c) is a TSD etch pit. The non-MP etch pit shown in (a) has a hexagonal shape and does not have a core. Similarly, the MP etch pit shown in (b) also has a hexagonal shape and is similar to the non-MP etch pit in that it does not have a core. On the other hand, the TSD etch pit shown in (c) also has a hexagonal shape, but differs from the non-MP etch pit in that it has a core. Furthermore, the area of ​​non-MP etch pits within the same sample plane (S nMP ) is TSD Etpit (S TSD ) is 10% or more larger than the area of ​​{(S nMP -S TSD ) / S TSD ) × 100} ≥ 10), MP Etching Pit (S nMP ) less than 110% (i.e., (S nMP / S MP ) × 100 ≤ 110).

[0039] The density of non-MP etch pits (non-MP etch pits) that appear on the Si surface of the SiC single crystal substrate 1 after melt KOH etching at 500°C for 15 minutes is 0.01 pits / cm³. 2 ~50 pieces / cm 2 It is preferable that the range is within this range. That is, the non-MP density of the SiC single crystal substrate 1 is 0.01 particles / cm³. 2 ~50 pieces / cm 2 It is preferable that it be within the range of [specify range]. The non-MP density of SiC single crystal substrate 1 is 0.1 particles / cm³. 2 ~20 pieces / cm 2 It is more preferable that it be within that range. The non-MP density of SiC single crystal substrate 1 is 1 particle / cm². 2 ~10pcs / cm 2 It is even more preferable that it be within the range of [a certain range].

[0040] X-ray topography (XRT) utilizes the fact that in X-ray diffraction, if there are imperfect regions with disordered lattices (crystal defects) in a crystal, the intensity of diffracted X-rays increases near these imperfect regions. An X-ray topographic image is a two-dimensional image obtained by irradiating a sample with X-rays under black conditions and converting the intensity of the diffracted X-rays into grayscale (contrast). Around crystal defects, the intensity of diffracted X-rays increases due to distortion of the crystal lattice, and the color density becomes darker in the XRT image. Information about the shape and distribution of defects can be obtained from this grayscale pattern. Reflected X-ray topography provides defect information for a few μm to 20 μm of the surface layer, while transmitted X-ray topography provides defect information for the entire thickness of the sample plate.

[0041] Figure 4(a) shows a transmission X-ray topography image (g(1-100)) of a SiC single crystal substrate according to this embodiment. Figure 4(b) is an optical microscope image of the surface of the same SiC single crystal substrate after obtaining a transmission X-ray topography image and then exposing etch pits by molten KOH etching at 500°C for 15 minutes. The areas indicated by arrows A to C in Figure 4(a) correspond to the areas indicated by arrows A to C in Figure 4(b). In the transmission X-ray topography image in Figure 4(a), arrow A indicates the XRT image of a micropipe (MP), while arrows B and C indicate the XRT images of non-MP defects. The contrast between the XRT images of micropipes and non-MP defects is clearly different. The XRT images of non-MP defects show almost no contrast, and their presence could be detected by comparing them with the optical microscope image of etch pits in Figure 4(b).

[0042] Around crystal defects, the lattice planes are distorted, so even X-rays of wavelengths that did not diffract in the perfect crystal region satisfy the diffraction conditions, increasing the diffracted X-ray intensity. It is thought that the XRT image of a micropipe is darker than that of a perfect crystal region. In contrast, the fact that the XRT image of a non-MP defect shows weaker contrast (weaker diffracted X-ray intensity) or almost no contrast (almost no diffracted X-ray intensity) compared to the XRT image of a micropipe indicates that the non-MP defect has a different structure from that of a micropipe. Further research is needed to determine how the structure differs, but we have found that the presence of these non-MP defects can have advantageous effects in subsequent device fabrication processes, and thus completed the present invention.

[0043] The newly discovered "non-MP defects" are similar to micropipes in that their etch pits are hexagonal in shape and lack a core, and many are of similar size, making them difficult to detect solely through optical microscope observation of etch pits. Furthermore, "non-MP defects" have almost no contrast in XRT images, making them difficult to detect solely through transmission X-ray topography observation. Moreover, even if research and development had been conducted using both optical microscope observation of etch pits and transmission X-ray topography observation, it would have been difficult to detect them because the existence of "non-MP defects" itself was not known. The inventors of this invention discovered these defects by chance while carefully examining each step of the manufacturing process for 6-inch SiC single-crystal substrates during the research and development of high-quality 8-inch SiC single-crystal substrates. As shown in the examples, these "non-MP defects" are not unique to 8-inch SiC single-crystal substrates but can also be found in 6-inch SiC single-crystal substrates.

[0044] Figure 5 is a schematic plan view of a SiC single crystal substrate according to this embodiment, showing a case where the density distribution of non-MP etch pits differs between the central region and the surrounding outer region of the SiC single crystal substrate. In the SiC single crystal substrate 1 of this embodiment, when the substrate is divided into a central region 1A in the range of r / 2 from the center and an outer region 1B located outside the central region 1A as the radius r of the substrate, the density NA [number / cm 2 of non-MP defect etch pits (non-MP etch pits) in the central region 1A and the density NB [number / cm 2 of non-MP defect etch pits in the outer region 1B satisfy NP < 0.5 (where NP = {NA / (NA + NB)}) . That is, it is preferable that the density of non-MP etch pits is higher in the outer region 1B than in the central region 1A. Since the density of non-MP etch pits is higher in the outer region 1B than in the central region 1A, the stress is sufficiently relaxed, and the damage caused by ion implantation is moderately reduced.

[0045] Also, it is preferable that 0.01 < NP < 0.5. When NP is within this range, the stress relaxation effect and the damage reduction effect by ion implantation are large. As a result, the change in SORI before and after ion implantation in the device fabrication process is sufficiently suppressed, and the yield is improved.

[0046] More preferably, NP is 0.05 to 0.5.​​​​​​​​​​​​​​​​​The main surface (hereinafter sometimes referred to as the "front surface") of the SiC single crystal substrate 1 is mirror-finished. This is because the front surface of the SiC single crystal substrate is necessary to form a SiC epitaxial layer by epitaxial growth of a SiC single crystal in order to fabricate various SiC devices. Therefore, the front surface is formed by cutting the substrate (the portion that will become the substrate) from a SiC single crystal ingot manufactured using a sublimation method or the like, and then mirror-finishing the surface of the cut substrate. The other side (hereinafter sometimes referred to as the "back side") does not have to be mirror-finished, but a SiC single crystal substrate with a mirror-finished front side but not a mirror-finished back side has a problem in that a difference in residual stress occurs between the front and back sides, causing the substrate to warp to compensate for the residual stress (Twyman effect). By making the back side mirror-finished as well, the warping of the substrate caused by the Twyman effect can be suppressed. Even when the front side is mirror-finished and the back side is not, a method has been developed to produce a SiC single crystal substrate with little warping (see, for example, Patent Document 2).

[0050] The SiC single crystal substrate 1 has notches 2 that serve as indicators of crystal orientation, but it may also have OF (orientation flat) instead of notches 2.

[0051] SORI is one of the parameters that indicates the degree of warping of a substrate. When the substrate is supported on its back surface and measured without changing its original shape, it is expressed as the sum of the normal distances from the lowest squares plane, which is calculated using the least squares method with all the data on the substrate surface, to the highest and lowest points on the substrate surface.

[0052] <Relationship between processed and altered layers and SORI> The SiC single crystal substrate is produced by slicing a SiC single crystal ingot and flattening the surface. When such mechanical processing is performed, processing strain is introduced to the surface of the substrate. The portion where processing strain occurs on the surface of the SiC single crystal substrate is called the processed altered layer. When the front surface and the back surface have the processed altered layer, a difference in processing strain occurs on the front surface and the back surface, a difference in residual stress also occurs, and the substrate warps due to the Twyman effect. The shape (warp) of the substrate is determined by the balance of the stress states exerted by the processed altered layers on both sides of the substrate.

[0053] In FIG. 14 of Patent Document 3, the relationship between the depth of the processed altered layer and SORI of a single crystal SiC wafer is shown. According to this graph, the deeper the depth of the processed altered layer, the larger the value of SORI. Also, when comparing a 6-inch SiC single crystal substrate and a 4-inch SiC single crystal substrate, the 6-inch SiC single crystal substrate is more susceptible to the influence of the processed altered layer and the SORI is larger. From this, it is presumed that when comparing an 8-inch SiC single crystal substrate and a 6-inch SiC single crystal substrate, the 8-inch SiC single crystal substrate is more susceptible to the influence of the processed altered layer and the SORI becomes even larger. Therefore, for an 8-inch SiC single crystal substrate, it is more important to remove the processed altered layer to reduce warping than for a 6-inch SiC single crystal substrate.

[0054] (Manufacturing method of SiC single crystal substrate) Regarding the manufacturing method of the SiC single crystal substrate according to this embodiment, particularly the manufacturing method of an 8-inch diameter SiC single crystal substrate, it will be described by dividing it into the manufacturing process of the SiC single crystal ingot and the process of manufacturing the SiC single crystal substrate from the ingot. In order to adjust the generation amount and distribution of non-MP defects in the SiC single crystal ingot, any one or two or more of the following treatments are performed: (i) cooling under predetermined conditions after the growth of the SiC single crystal ingot, (ii) annealing under predetermined conditions after the growth of the SiC single crystal ingot, (iii) annealing under predetermined conditions after slicing the SiC single crystal ingot.

[0055] <Manufacturing process of SiC single crystal ingot> Through diligent research, the inventors discovered that, in the production of 8-inch diameter SiC single crystal ingots, more precise control of the radial and perpendicular (crystal growth direction) temperature gradients is key compared to 6-inch diameter SiC single crystal ingots. They then found that more precise control of the radial and perpendicular (crystal growth direction) temperature gradients can be achieved by applying the method disclosed in Patent Document 4. Specifically, a SiC single crystal manufacturing apparatus can be used that has a heat insulating material that can move along the extension direction of the guide member on the outside of the guide member that guides crystal growth. It should be noted that the method for more precise control of the radial and perpendicular (crystal growth direction) temperature gradients is not limited to the method disclosed in Patent Document 4.

[0056] During the transition to larger diameter SiC single crystal ingots, a problem arises where applying the same manufacturing methods as for previous diameter SiC single crystal ingots does not yield large-diameter SiC single crystal ingots with similar crystal quality. For example, during the transition from 4-inch diameter SiC single crystal ingots to 6-inch diameter SiC single crystal ingots, the following problems occurred (see Patent Document 1).

[0057] In the growth of SiC single crystals using the sublimation recrystallization method with seed crystals, one of the growth conditions for achieving high crystal quality is to ensure that the surface shape of the single crystal ingot during growth is approximately convex in the direction of growth. This is, for example, in the case of 4H-type SiC single crystals used in power devices. <0001> When growing SiC single crystals roughly parallel to the axis, i.e., the c-axis direction of the crystal, the growth is carried out by the progression of spiral steps ejected from through-helical dislocations. Therefore, it is said that by making the growth surface roughly convex, the step supply source on the growth surface becomes essentially one location, which improves polytype stability. If the growth surface is concave or has multiple vertices, there will be multiple sources of growth steps, resulting in areas where different steps ejected from each source collide. In such cases, not only do defects such as dislocations occur at the collision points, but the atomic stacking state in the c-axis direction, which is characteristic of 4H-type polytypes, becomes more easily disrupted, leading to the generation of different polytypes with different stacking structures, such as 6H-type and 15R-type, and the formation of micropipe defects.

[0058] Therefore, for example, in order to stabilize a 4H-type polytype suitable for power devices and grow a so-called single polytype crystal consisting solely of the 4H-type polytype, it is important to make the growth surface shape of the grown crystal roughly convex. Specifically, the convex shape of the grown crystal is achieved by optimizing the temperature of the center of the grown crystal in terms of growth rate, and by controlling the temperature distribution during growth, i.e., the isotherm shape, so that it is roughly convex. It was thought that a SiC single crystal ingot grown under such growth conditions, in which roughly convex isotherms are realized, would grow roughly parallel to the isotherms, thereby ensuring the polytype stability described above.

[0059] However, when increasing the diameter of the grown crystal to 150 mm (6 inches) or more, if the temperature at the center of the grown crystal is optimized to be equivalent to that of conventional 100 mm (4-inch) diameter single crystal growth in terms of growth rate, etc., and the temperature gradient during growth is controlled so that the growth surface shape of the grown crystal is roughly convex in the growth direction, the temperature at the periphery of the seed crystal inevitably becomes higher compared to the case of small-diameter crystal growth. As a result, there was a problem that the SiC single crystal of the seed crystal itself was prone to thermal decomposition at its outer peripheral. Patent Document 1 addresses this problem by primarily using a seed crystal made of silicon carbide single crystal with a thickness of 2.0 mm or more.

[0060] In this invention, when producing an 8-inch diameter SiC single crystal ingot, we have succeeded in producing an 8-inch diameter SiC single crystal ingot with properties comparable to a 6-inch diameter SiC single crystal ingot by using a method that does not involve the typical method for producing a 6-inch diameter SiC single crystal ingot as shown in Patent Document 1. This is achieved by using an insulating material that can move along the extension direction of the guide member on the outside of the guide member that guides crystal growth, and by controlling not only the radial temperature gradient but also the vertical (crystal growth direction) temperature gradient. The SiC single crystal manufacturing apparatus and the SiC single crystal ingot manufacturing process will be described below.

[0061] Figure 7 is a schematic cross-sectional view of an example of a SiC single crystal manufacturing apparatus for carrying out the process of producing SiC single crystal ingots.

[0062] The SiC single crystal manufacturing apparatus 100 shown in Figure 7 comprises a crucible 10, a seed crystal placement section 11, a guide member 20, and a heat insulating material 30. In Figure 7, for ease of understanding, the raw material G, the seed crystal S, and the single crystal C grown on the seed crystal S are shown simultaneously. In the following diagrams, the direction in which the seed crystal placement section 11 and the raw material G face each other is defined as the vertical direction, and the direction perpendicular to the vertical direction is defined as the left-right direction.

[0063] Crucible 10 surrounds the film deposition space K where the single crystal C is grown. Any known crucible for producing single crystal C by sublimation can be used for crucible 10. For example, graphite, tantalum carbide, etc., can be used. Crucible 10 becomes hot during growth. Therefore, it needs to be made of a material that can withstand high temperatures. For example, graphite has an extremely high sublimation temperature of 3550°C and can withstand the high temperatures during growth.

[0064] The seed crystal placement section 11 is positioned opposite the raw material G within the crucible 10. By positioning the seed crystal placement section 11 opposite the raw material G, the raw material gas can be efficiently supplied to the seed crystal S and the single crystal C.

[0065] The guide member 20 extends from around the seed crystal placement section 11 toward the raw material G. That is, the guide member 20 is positioned along the crystal growth direction of the single crystal C. Therefore, the guide member 20 functions as a guide when the single crystal C grows from the seed crystal S.

[0066] The lower end of the guide member 20 is supported by the support 21. The support 21 seals the space between the lower end of the guide member 20 and the crucible 10, preventing the raw material gas from entering the area outside the guide member 20. If the raw material gas enters this area, polycrystalline material will grow between the guide member 20 and the thermal insulation material 30, hindering the free movement of the thermal insulation material 30.

[0067] The connection between the guide member 20 and the support 21 is preferably a crimped structure. A crimped structure is a structure designed so that when a physical force is applied to the guide member 20, the connection between the guide member 20 and the support 21 tightens. For example, a screw structure in which the connection part is threaded is an example of a crimped structure. The guide member 20 may come into physical contact with the single crystal C that is growing, and in that case, the guide member 20 can be prevented from falling off.

[0068] In Figure 7, the guide member 20 extends vertically in the vertical direction. The shape of the guide member 20 is not limited to this shape. Figure 9 is a schematic cross-sectional view of another example of the SiC single crystal manufacturing apparatus 101 according to this embodiment. In Figure 9, the guide member 25 expands in diameter from the seed crystal placement section 11 toward the raw material G. By expanding the diameter of the guide member 25, the diameter of the single crystal C can be increased.

[0069] Furthermore, although the upper end of the guide member 20 in Figure 7 is open, the upper end of the guide member 20 may be connected to the inner surface of the crucible 10 to create a closed space where the insulation material 30 exists.

[0070] The surface of the guide member 20 is preferably coated with tantalum carbide. The guide member 20 is constantly exposed to the raw material gas in order to control the flow of the raw material gas. If the guide member 20 is used with exposed graphite, the graphite may react with the raw material gas and deteriorate or become damaged. When deterioration or damage occurs, holes may form in the guide member 20. In addition, carbon powder that peels off due to deterioration can be incorporated into the single crystal C, which can lead to a deterioration in the quality of the single crystal C. In contrast, tantalum carbide can withstand high temperatures and does not cause unwanted reactions with the raw material gas. Therefore, stable growth of high-quality SiC single crystals can be achieved.

[0071] The thermal insulation material 30 moves along the extension direction of the guide member 20, on the outside of the guide member 20. By moving the thermal insulation material 30, the positional relationship between the end face of the thermal insulation material 30 on the raw material G side (hereinafter referred to as the bottom surface 30a) and the surface Ca of the single crystal C can be controlled. Therefore, the temperature distribution near the surface Ca of the single crystal C can be freely controlled, and the surface shape of the single crystal C from which crystal growth occurs can be freely controlled. During the crystal growth process, the positional relationship between the raw material-side end face 30a of the insulating material 30 and the surface Ca of the single crystal C can be controlled. Furthermore, during the crystal growth process, the raw material-side end face 30a of the insulating material 30 can be positioned within 20 mm of the surface Ca of the single crystal C. Furthermore, during the crystal growth process, the end face 30a of the insulating material 30 on the raw material side can be positioned closer to the seed crystal installation section 11 than the surface Ca of the single crystal C. Furthermore, the thickness of the insulation material 30 can be reduced to less than half the growth amount of the SiC single crystal ingot manufactured with a thickness of 0.2 mm or more.

[0072] Figure 10 is a schematic cross-sectional view of a drive mechanism for moving the thermal insulation material 30 up and down. The drive mechanism is not particularly limited as long as it can move the thermal insulation material 30 in the vertical direction. For example, as shown in Figure 10(a), a drive member 31 extending from the top of the thermal insulation material 30 to the outside of the crucible 10 may be provided, and the thermal insulation material 30 may be moved by pushing and pulling the drive member up and down. Alternatively, as shown in Figure 10(b), a lifting drive member 32 may be provided to support the thermal insulation material 30 from the bottom. Furthermore, as shown in Figure 10(c), a notch may be provided on a part of the side surface of the crucible 10, and a drive member 33 extending to the outside of the crucible 10 through this notch may be provided, and the thermal insulation material 30 may be moved by raising and lowering the drive member.

[0073] The thermal insulation material 30 is preferably composed of a material having a thermal conductivity of 40 W / mk or less at high temperatures of 2000°C or higher. Examples of materials having a thermal conductivity of 40 W / mk or less at high temperatures of 2000°C or higher include graphite members with a thermal conductivity of 120 W / mk or less at room temperature. Furthermore, it is more preferable that the thermal insulation material 30 is composed of a material having a thermal conductivity of 5 W / mk or less at high temperatures of 2000°C or higher. Examples of materials having a thermal conductivity of 5 W / mk or less at high temperatures of 2000°C or higher include graphite and felt materials mainly composed of carbon.

[0074] The shape of the insulation material 30 is appropriately designed to match the shape of the area sandwiched between the guide member 20 and the inner surface of the crucible 10. As shown in Figure 8, when the distance between the guide member 20 and the inner surface of the crucible 10 is constant, the insulation material 30 is positioned to fill the gap between them. Also, as shown in Figure 8, when the distance between the guide member 25 and the inner surface of the crucible 10 changes, the shape of the insulation material 35 is designed to match the position where the gap between them is narrowest. By designing in this way, it is possible to avoid the insulation material 35 becoming stuck between the guide member 25 and the inner surface of the crucible 10 and becoming immobile.

[0075] The thickness of the insulating material 30 is preferably 0.2 mm or more, more preferably 5 mm or more, and even more preferably 20 mm or more. If the thickness of the insulating material 30 is too thin, it may not be able to provide sufficient insulation. Furthermore, the thickness of the insulating material 30 is preferably half or less of the length of the single crystal that is finally produced. Here, the single crystal length refers to the length in the vertical direction of the single crystal C after crystal growth (the amount of growth of the single crystal C). If the amount of growth of the single crystal is 100 mm, the thickness of the insulating material 30 is preferably 50 mm or less, and if the amount of growth of the single crystal is within 50 mm, the thickness of the insulating material 30 is preferably 25 mm or less. If the thickness of the insulating material 30 is too thick, the movement of the insulating material 30 will be hindered. Furthermore, if the thickness of the insulating material 30 is within the specified range, a temperature difference can be formed in the vertical direction within the single crystal C through the insulating material 30. Therefore, it is possible to prevent the raw material gas from recrystallizing in parts other than the surface Ca of the single crystal C.

[0076] As described above, the SiC single crystal manufacturing apparatus allows for relative control of the position of the insulating material with respect to the single crystal being grown. By controlling the position of the insulating material, the temperature distribution near the surface of the single crystal C during crystal growth can be freely controlled. Since the single crystal C grows along an isothermal surface, controlling the temperature distribution near the surface of the single crystal C leads to controlling the shape of the single crystal C.

[0077] The SiC single crystal manufacturing apparatus described above can be used to produce SiC single crystal ingots. The following explanation will use the SiC single crystal manufacturing apparatus 100 shown in Figure 8 as an example.

[0078] In the process of manufacturing SiC single crystal ingots, a single crystal C is grown from a seed crystal S placed in a seed crystal placement section 11. The single crystal C grows when the raw material gas, sublimated from the raw material G, recrystallizes on the surface of the seed crystal S. The raw material G is sublimated by heating the crucible 10 with an external heating means. The sublimated raw material gas is supplied towards the seed crystal S along the guide member 20.

[0079] In the process of producing a SiC single crystal ingot, the positional relationship between the lower surface 30a of the insulating material 30 and the surface Ca of the single crystal C is controlled during the crystal growth process from the seed crystal S. By controlling these positional relationships, the shape of the surface Ca of the single crystal C can be freely controlled.

[0080] Figure 11 shows the positional relationship between the lower surface 30a of the insulating material 30 and the surface Ca of the single crystal C, and the relationship with the isothermal surface near the single crystal C. Figure 11(a) is an example where the surface Ca (crystal growth surface) of the single crystal C is flat, Figure 11(b) is an example where the surface Ca (crystal growth surface) of the single crystal C is concave, and Figure 11(c) is an example where the surface Ca (crystal growth surface) of the single crystal C is convex.

[0081] As shown in Figures 11(a) to (c), the shape of the surface Ca of the single crystal C changes depending on the position of the insulating material 30 relative to the surface Ca of the single crystal C. As shown in Figure 11(a), when the position of the surface Ca of the single crystal C and the lower surface 30a of the insulating material 30 are approximately the same, the surface Ca of the single crystal C becomes flat. In contrast, as shown in Figure 11(b), when the lower surface 30a of the insulating material 30 is on the raw material G side of the surface Ca of the single crystal C, the surface Ca of the single crystal C becomes concave, and as shown in Figure 11(c), when the surface Ca of the single crystal C is on the raw material G side of the lower surface 30a of the insulating material 30, the surface Ca of the single crystal C becomes convex.

[0082] The shape of the surface Ca of the single crystal C changes depending on the position of the insulating material 30 relative to the surface Ca of the single crystal C because the shape of the isothermal surface T in the film deposition space K changes. Figure 12 schematically shows the shape of the isothermal surface T near the single crystal C during crystal growth. Figure 12(a) shows the case without the insulating material 30, and Figure 12(b) shows the case with the insulating material 30.

[0083] The single crystal carbon (C) of SiC has a low thermal conductivity and therefore possesses an insulating effect on its own. On the other hand, the thermal conductivity of the guide member 20 is higher than that of the single crystal carbon. Therefore, as shown in Figure 12(a), when there is no insulating material 30, the isothermal surface T is formed to extend from the single crystal carbon. The crystal growth plane of the single crystal carbon grows along the isothermal surface T. Therefore, when there is no insulating material 30, the shape of the surface Ca (crystal growth plane) of the single crystal carbon is fixed as a concave shape.

[0084] In contrast, as shown in Figure 12(b), when the insulating material 30 is provided, the shape of the isothermal surface T changes. The shape of the isothermal surface T can be freely designed by controlling the position of the insulating material 30 relative to the single crystal C. The design of the shape of the isothermal surface T can be accurately performed by confirming it in advance through simulations, etc. In this way, by controlling the position of the insulating material 30 relative to the single crystal C, the shape of the surface Ca of the single crystal C can be freely designed.

[0085] Furthermore, controlling the position of the insulating material 30 relative to the single crystal C has the effect of suppressing the adhesion of polycrystals to the guide member 20, and also reduces the temperature difference in the in-plane direction within the single crystal C.

[0086] Polycrystalline material forms in the lower temperature region near the crystal growth surface of the single crystal C. For example, as shown in Figure 12(a), if the temperature difference between the single crystal C and the guide member 20 is large, polycrystalline material will grow on the guide member 20. When the polycrystalline material grown on the guide member 20 comes into contact with the single crystal C, it disrupts the crystallinity of the single crystal C and causes defects. In contrast, as shown in Figure 12(b), if there is an insulating material 30 near the surface Ca of the single crystal C, the temperature difference between the single crystal C and the guide member 20 can be reduced, and the growth of polycrystalline material can be suppressed.

[0087] Furthermore, if there is a large temperature difference in the in-plane direction within a single crystal C, stress will be generated during the growth process of the single crystal C. Stresses within a single crystal of carbon (C) can cause distortion and displacement of crystal planes. This distortion and displacement can lead to the formation of killer defects such as basal plane dislocations (BPDs).

[0088] Up to this point, we have explained how the shape of the surface Ca of single crystal carbon can be controlled. The shape of the surface Ca of single crystal carbon is preferably flat or convex toward the raw material G. If the shape of the surface Ca of single crystal carbon is concave toward the raw material G, the quality will be inferior. In order to make the shape of the surface Ca of single crystal carbon flat or convex, the position of the surface Ca of single crystal carbon and the lower surface 30a of the heat insulating material 30 should be made approximately the same, or the surface Ca of single crystal carbon should be placed on the raw material G side of the lower surface 30a of the heat insulating material 30.

[0089] Here, "approximately identical" does not mean that the surface Ca of the single crystal C and the lower surface 30a of the insulating material 30 are at exactly the same height, but rather that a positional displacement within a range that does not significantly affect the isothermal surface T is permitted. Specifically, if the lower surface 30a of the insulating material 30 is located within 30 mm of the surface Ca of the single crystal C, then it can be said that the surface Ca of the single crystal C and the lower surface 30a of the insulating material 30 are in approximately the same positional relationship. On the other hand, in order to make the shape of the surface Ca of the single crystal C flat, it is preferable that the positional relationship between the surface Ca of the single crystal C and the lower surface 30a of the insulating material 30 be as close to perfectly identical as possible, and it is preferable that the lower surface 30a of the insulating material 30 is located within 20 mm of the surface Ca of the single crystal C, and more preferably within 10 mm.

[0090] Furthermore, it is preferable that the surface Ca of the single crystal C is on the raw material G side of the lower surface 30a of the insulating material 30. That is, it is preferable that the lower surface 30a of the insulating material 30 is on the seed crystal installation section 11 side of the surface Ca of the single crystal C. Even if external factors such as temperature fluctuations occur in the film deposition space K, it is possible to suppress the surface Ca of the single crystal C from becoming concave.

[0091] Furthermore, it is preferable to control the position of the thermal insulation material 30 from the start of crystal growth. That is, it is preferable to control the positional relationship between the lower surface 30a of the thermal insulation material 30 and the surface of the seed crystal S at the start of crystal growth.

[0092] Immediately after the start of crystal growth, the seed crystal placement section 11 is located around the seed crystal S, and the distance between the seed crystal S and the crucible 10 is short. Therefore, the isothermal surface T in the film deposition space K is also affected by the temperature (thermal conductivity) of these materials. In other words, the effect of using the insulating material 30 is most pronounced in the region where the single crystal C has grown 30 mm or more from the seed crystal S. On the other hand, this does not mean that the insulating material 30 has no effect immediately after the start of crystal growth.

[0093] For example, if the shape of the crystal growth surface of the single crystal C immediately after crystal growth is concave without the provision of the insulating material 30, it becomes necessary to return the shape of the crystal growth surface of the single crystal C to a convex shape during the subsequent growth process. When the shape of the crystal growth surface changes from concave to convex during the growth process, stress accumulates within the single crystal C, making it easier for defects to occur. Therefore, it is preferable to control the position of the insulating material 30 from the start of crystal growth. The positional relationship of the insulating material 30 with respect to the seed crystal S can be designed in the same way as the positional relationship between the insulating material 30 and the single crystal C during the crystal growth process.

[0094] The process for producing a SiC single crystal ingot is similar to that of a normal SiC single crystal ingot in that it includes a preparation step of placing SiC raw material powder and a seed crystal in a crystal growth furnace, a heating step of raising the temperature to the crystal growth temperature at which the SiC raw material powder sublimes, a single crystal growth step of growing a SiC single crystal on the seed crystal, and a cooling step of lowering the temperature inside the crystal growth furnace once the SiC single crystal has grown to a predetermined length. However, in order to adjust the amount and distribution of non-MP defects in the SiC single crystal ingot, (i) in the cooling step, the SiC single crystal ingot is cooled under predetermined conditions after growth, or (ii) the SiC single crystal ingot is annealed under predetermined conditions between the single crystal growth step and the cooling step.

[0095] (i) Cooling process under specified conditions (cooling process) In order to adjust the generation amount and distribution of non-MP defects in the SiC single crystal ingot, in the cooling process from a growth temperature exceeding 2000 °C to room temperature (about 25 °C), after growth, the cooling rate from 1500 °C is set within the range of 100 to 320 °C / h, and the cooling rate from 1500 °C to room temperature is controlled to be within the range of 50 to 300 °C / h.

[0096] (ii) A step of annealing the grown SiC single crystal ingot under predetermined conditions between the single crystal growth step and the temperature reduction step (annealing step) Annealing is performed on the grown SiC single crystal ingot in an inert atmosphere. Put the SiC single crystal ingot and a Si source for suppressing the carbonization of the ingot surface into a graphite container. Typical Si sources include Si, SiC, and Si3N4, but are not limited thereto. From the perspective of cost, it is desirable to perform the process under an argon atmosphere. The container may be filled with graphite powder to facilitate controlling the temperature gradient. Also, the heating means and the heat insulating material 30 etc. are adjusted so that the radial temperature gradient of the SiC single crystal ingot is 20 °C / cm or less and the temperature gradient in the growth direction is within the range of 0 to 50 °C / cm, and annealing is performed at 1800 to 2000 °C for 10 to 20 hours.

[0097] <Process for manufacturing a SiC single crystal substrate> In the process of fabricating a SiC single crystal substrate from the obtained SiC single crystal ingot (hereinafter sometimes referred to as the substrate fabrication process), a SiC single crystal substrate can be obtained by performing normal substrate processing (cylindrical processing, slicing, and polishing). For example, this may include a planarization process including lapping and a process alteration layer removal process. As described above, in order to adjust the amount and distribution of non-MP defects in the SiC single crystal ingot, in the SiC single crystal ingot fabrication process, a process of cooling the SiC single crystal ingot under predetermined conditions after growth ((i)), or an annealing process of annealing the SiC single crystal ingot under predetermined conditions after growth ((ii)), or both (i) and (ii) may be performed. Alternatively, or in addition to these, in this substrate fabrication process, in order to adjust the amount and distribution of non-MP defects in the SiC single crystal ingot, (iii) a substrate annealing process of annealing the SiC single crystal ingot under predetermined conditions after slicing may be performed. The following describes this substrate annealing process and lapping processing using a characteristic slurry. For other processing steps, such as obtaining a SiC single crystal substrate from a SiC single crystal ingot, known methods can be used.

[0098] The substrate annealing process involves slicing the SiC single crystal ingot and then performing an annealing treatment. This process may be performed after each step in the substrate formation process. If the adjustment of the non-MP defect etch pit density was imperfect in the SiC single crystal ingot manufacturing process, that is, if the adjustment of the non-MP defect etch pit density was imperfect in (i) the cooling process (cooling process) under predetermined conditions, and / or (ii) the annealing process between the single crystal growth process and the cooling process, then this (iii) substrate annealing process may be performed as an additional annealing treatment. Annealing increases the surface roughness of the substrate, so performing annealing after the final polishing is not desirable from a cost standpoint, but it can be reprocessed. It is preferable to perform annealing when the substrate surface roughness is high, before polishing.

[0099] Figure 6 is a schematic cross-sectional view of an annealing crucible, illustrating an example of a substrate annealing process using an annealing crucible.

[0100] The substrate annealing process will be explained using the annealing crucible 200 shown in Figure 6. The substrate annealing process includes the steps of preparing a sliced ​​substrate 201, placing a Si source in a graphite container 200, placing the target substrate 201 in the container, placing these in a heating device, and performing the annealing process. The step of placing the Si source may be performed together with the step of placing the target substrate in the container 200. To form a desired temperature distribution, graphite powder 203 may be filled into the container 200, or graphite components may be placed inside. The annealing conditions are similar to those for annealing a SiC single crystal ingot, for example, processing is performed in an inert atmosphere such as argon at a temperature in the range of 1800°C to 2000°C for about 10 to 20 hours.

[0101] As shown in Figure 6, the SiC single crystal substrate 201 to be subjected to the substrate annealing process may be placed, for example, in the center of the annealing crucible 20, and the substrate annealing process may be carried out with the SiC single crystal substrate 201 sandwiched between dummy wafers 204 to prevent surface carbonization of the SiC single crystal substrate 201.

[0102] For example, the annealing conditions in the substrate annealing process include holding the substrate at 1950°C for 20 hours under an argon (Ar) atmosphere (e.g., 700 Torr).

[0103] When performing molten KOH etching to measure the non-MP defect density, the surface is ground with the same amount of material removal, regardless of whether or not the substrate annealing process is performed, and then molten KOH etching is carried out.

[0104] In Figure 7, the XRT image (g(1-100)) of a SiC single crystal substrate is shown on the right. No variations in density corresponding to defects are visible in this XRT image. The lower left and upper left images of Figure 7 show the presence or absence of non-MP etch pits in each divided region in optical microscope images after molten KOH etching. The lower left image shows the case where the substrate annealing process was not performed, and the upper left image shows the case where the substrate annealing process was performed. No etch pits are seen in the lower left image where the substrate annealing process was not performed, but as indicated by the arrows, many non-MP etch pits are present in the upper left image where the substrate annealing process was performed. Thus, the number of non-MP etch pits can be increased by annealing the substrate. In other words, the density of non-MP etch pits can be adjusted by annealing the substrate. Furthermore, the upper left diagram in Figure 7 shows that the increase in non-MP etch pits is greater in the outer region than in the central region. Thus, the ratio of non-MP etch pit density between the central and outer regions can be adjusted by the annealing conditions in the substrate annealing process.

[0105] Next, we will detail the types of slurries available for lapping. In the free abrasive processing method, a slurry containing, for example, water, boron carbide abrasive grains, and an additive to disperse the boron carbide abrasive grains is poured between the upper and lower platen, and pressure is applied to the SiC substrate 1 by the upper and lower platen to flatten the surface of the SiC substrate 1. The slurry used in the processing process is, for example, a slurry mainly composed of water. When a slurry mainly composed of water is used, the dispersibility of the boron carbide abrasive grains is improved, and secondary aggregation is less likely to occur during the processing process. Also, when a slurry mainly composed of water is used, the surface of the SiC substrate on the upper platen side, where the slurry supply holes are provided, is cleaned by the direct supply of water, while the surface on the lower platen side, where the slurry supply holes are not provided, is cleaned by water supplied through the gap between the SiC substrate and the carrier plate. The slurry used in the lapping process is collected in a tank and supplied again from the tank.

[0106] The modified Mohs hardness (14) of boron carbide abrasive grains is slightly greater than the modified Mohs hardness (13) of the SiC substrate as the non-abrasive target, and less than the modified Mohs hardness (15) of diamond. Therefore, by using such a slurry, it is possible to suppress the occurrence of cracks in the SiC substrate, which has a modified Mohs hardness (13), while relatively increasing the processing speed and suppressing the reduction in the particle size of the boron carbide abrasive grains.

[0107] The proportion of boron carbide abrasive grains in the slurry is, for example, 15% by mass or more and 45% by mass or less, preferably 20% by mass or more and 40% by mass or less, and more preferably 25% by mass or more and 35% by mass or less. By having a proportion of boron carbide abrasive grains of 15% by mass or more in the slurry, the content of boron carbide abrasive grains in the slurry can be increased, and the processing speed of the lapping process can be increased. Furthermore, by having a proportion of boron carbide abrasive grains of 45% by mass or less in the slurry, the frequency and area of ​​contact between boron carbide abrasive grains can be suppressed, making it easier to suppress the reduction in particle size and wear of the boron carbide abrasive grains.

[0108] The boron carbide abrasive grains in the slurry used in the processing step preferably have an average particle size of 15 μm to 40 μm, and more preferably 25 μm to 35 μm. Using boron carbide abrasive grains with an average particle size of 15 μm or more makes it easier to increase the processing speed for lapping the surface of the SiC substrate 1, and also allows sufficient adhesion of the additives described later to the surface, leading to improved dispersibility and suppression of particle size reduction. Furthermore, by setting the average particle size to 40 μm or less, it is easier to suppress the generation of cracks in the SiC substrate and the cracking of the SiC substrate, and it is also possible to suppress excessive adhesion of the additives described later to the surface, thereby suppressing a decrease in processing speed due to a reduction in the contact area with the SiC substrate as the workpiece. In addition, using such boron carbide abrasive grains makes it easier to suppress changes in particle size before and after lapping. Here, the average particle size of the boron carbide abrasive grains is the average particle size of the boron carbide abrasive grains before processing, and the average particle size of the boron carbide abrasive grains after processing is, for example, 14 μm to 48 μm, and preferably 23 μm to 42 μm, since the ratio of the average particle sizes of the boron carbide abrasive grains before and after processing is 0.91 or more and 1.2 or less.

[0109] Here, the average particle size of the boron carbide abrasive grains is measured based on the particle size distribution measured by laser scattered light measurement using a particle size distribution analyzer, either the Mastersizer Hydro 2000MU (Spectris Inc.) or the MT3000II (Microtrac-Bell Inc.).

[0110] As additives, polyhydric alcohols, esters and their salts, homopolymers and their salts, copolymers, etc., can be used. Specific examples include one or more selected from the group consisting of glycerin, 1-vinylimidazole, sodium methyl taurate, sodium lauric acid amide ether sulfate, sodium myristate acid amide ether sulfate, polyacrylic acid, and acrylic acid-maleic acid copolymers.

[0111] These additives are thought to improve the dispersibility of boron carbide abrasive particles in the slurry.

[0112] The additive adheres to the surface of the boron carbide abrasive grains, preventing direct contact between the grains. In this way, the additive enhances the dispersibility of the boron carbide abrasive grains in the slurry and suppresses the reduction in grain size during the machining process.

[0113] The proportion of additives in the slurry is, for example, 3% to 20% by volume, preferably 5% to 15% by volume, and preferably 10% to 15% by volume. Here, the proportion of additives in the slurry refers to the ratio obtained by dividing the volume of additives (additive components) such as glycerin by the volume of the slurry. When the proportion of additives in the slurry is within the above range, they adhere sufficiently to the surface of the boron carbide in the slurry, a desirable degree of dispersion of boron carbide abrasive grains in the slurry is obtained, and it is easier to suppress the reduction in particle size of boron carbide abrasive grains during the processing step.

[0114] In this lapping process, the processing speed for processing the surface of the SiC substrate is preferably, for example, 14 μm / h to 45 μm / h, preferably 16 μm / h to 40 μm / h, and more preferably 18 μm / h to 25 μm / h. The processing speed depends on the processing pressure and the average particle size of the boron carbide abrasive grains as described above. By setting the processing speed to 45 μm / h or less, it is easier to obtain the effect of suppressing the reduction in the particle size of the boron carbide abrasive grains and the wear of the boron carbide abrasive grains. By setting the processing speed to 14 μm / h or more, throughput can be increased. When lapping is performed in multiple stages, it is sufficient that the processing speed obtained by dividing the total change in the thickness of the SiC substrate by the total processing time is within the above range, and it is preferable that the processing speed at each stage is within the above range. In other words, when lapping is performed in multiple stages, it is preferable that the processing speed calculated for each stage is within the above range.

[0115] Here, the processing speed is calculated from the difference in thickness of the SiC substrate 1 before and after lapping and the processing time. Specifically, the processing speed is calculated using the following method. The measurement positions for the thickness of the SiC substrate 1 are: position 1c, which corresponds to the center of the SiC substrate before the orientation flat OF is formed on the SiC substrate 1; position 1a, which is 5 to 10 mm away from the midpoint of the orientation flat OF toward position 1c; position 1b, which is on the same straight line c as positions 1a and 1c and is 5 to 10 mm away from the outer edge of the SiC substrate 1 in the direction of position 1a; and positions 1d and 1e, which are on a straight line perpendicular to the straight line c and are 5 to 10 mm away from the outer edge of the SiC substrate 1 in the direction of position 1a. The thickness of the SiC substrate 1 at these five positions 1a to 1e is measured using an indicator (ID-C150XB, manufactured by Mitutoyo), and the obtained thickness is treated as the thickness of the SiC substrate 1. The processing speed is calculated by dividing the difference in thickness (μm) of the SiC substrate 1 before and after processing, obtained in this way, by the processing time (h).

[0116] By attaching additives to the surface of boron carbide abrasive grains in the slurry used in the processing step, the dispersibility of the boron carbide abrasive grains is improved, and contact between the boron carbide abrasive grains is suppressed, thereby preventing a reduction in the particle size of the boron carbide abrasive grains. Specifically, the change in the particle size of boron carbide abrasive grains can be suppressed to such an extent that the ratio of the average particle size of boron carbide abrasive grains after processing to the average particle size of boron carbide abrasive grains before processing is between 0.91 and 1.2. The reason why this ratio includes values ​​greater than 1 is that during the processing process, the boron carbide abrasive grains undergo secondary aggregation, and the particle size of some of the boron carbide abrasive grains may become larger than that before processing.

[0117] In conventional lapping processes, the particle size of boron carbide abrasive grains in the slurry decreases significantly during the lapping process. Therefore, if lapping is performed again, it is necessary to add abrasive grains to the slurry each time, and it is also necessary to perform complicated management to determine the particle size distribution of the abrasive grains in the slurry, which depends on the number of times lapping has been performed. Thus, this lapping process makes it easy to control the particle size of boron carbide abrasive grains, reduces costs, lowers environmental impact, and suppresses crack formation.

[0118] Furthermore, in this lapping process, the particle size of the boron carbide abrasive grains does not change significantly, which suppresses changes in the processing speed during the lapping process and allows the lapping process to be continued under the same conditions. This lapping process is particularly effective when using boron carbide as the abrasive grain, as it has a slightly higher modified Mohs hardness than silicon carbide, which is the non-abrasive material. Because this lapping process uses such abrasive grains and substrate, it is also possible to suppress cracks that frequently occur when using diamond as the abrasive grain and a SiC substrate as the material to be polished.

[0119] Furthermore, this lapping process suppresses the reduction and wear of boron carbide abrasive grain size, resulting in less variation in the particle size of boron carbide abrasive grains in the slurry during lapping. The processing speed of lapping depends on the particle size of the abrasive grains used, but this lapping process suppresses the variation in particle size of the abrasive grains, so the entire surface of the SiC substrate is processed with abrasive grains of roughly uniform size, resulting in less in-plane variation of the SiC substrate after processing. [Examples]

[0120] The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments.

[0121] (Example 1) First, a SiC single crystal ingot was fabricated using the SiC single crystal manufacturing apparatus shown in Figure 8. First, a 4H-SiC single crystal with a diameter of 200 mm and a thickness of 5 mm, with the (0001) plane as the main plane and an off-angle of 4°, was used as the seed crystal S. In accordance with the crystal growth, the insulating material 30 was moved in stages so that the raw material side end face (bottom surface) of the insulating material 30 was on the lid side of the single crystal surface and the distance in the growth direction between the raw material side end face of the insulating material 30 and the single crystal surface was within 10 mm. The single crystal growth process was terminated when the SiC single crystal ingot reached a length of approximately 20 mm. As a cooling process, in order to adjust the amount and distribution of non-MP defects in the SiC single crystal ingot, the cooling from a growth temperature of over 2000°C to room temperature (approximately 25°C) was controlled so that the cooling rate up to 1500°C was 300°C / h and the cooling rate from 1500°C to room temperature was 300°C / h. The resulting SiC single crystal ingot had a diameter of 208 mm and a height of 20.2 mm.

[0122] Next, twelve 8-inch SiC substrates, each 1.0 mm thick and having a (0001) plane with an off-angle of 4°, were obtained from a SiC single crystal ingot using a known processing method.

[0123] The thickness of this SiC substrate was measured. Next, the SiC substrate, whose thickness had been measured, was placed on the carrier plate of the polishing apparatus and lapped. The lapping slurry was obtained by adding a predetermined amount of boron carbide abrasive grains and AD8 (10% by volume) as an additive to water and dispersing them. As the boron carbide abrasive grains, a particle size of F320 (JIS R6001) was used. Here, the proportion of glycerin (manufactured by I-Chem Techno Co., Ltd.) as an additive in the slurry was 6% by volume. Lapping was performed using a free abrasive method while supplying lapping slurry at a rate of 16 L / min. The lapping slurry was reused in a circulating manner.

[0124] The driving conditions for the polishing machine in lapping are a processing pressure of 160 g / cm². 2The lower platen rotation speed was set to 16 rpm, the upper platen rotation speed to 5.5 rpm, the center gear rotation speed to 2.8 rpm, the internal gear rotation speed to 6.0 rpm, and the machining time to 40 minutes. After lapping, the particle size distribution of boron carbide abrasive grains in the slurry was measured using the same method as before processing, and the plate thickness was measured using the same method as before processing. The processing speed was also calculated. In this lapping process, the average processing speed for 15 SiC substrates was 18 μm / h. After the measurement, the slurry used in the previous lapping process was supplied, and a second lapping process and measurement were performed while circulating the slurry. In Example 1, this process was repeated, resulting in a total of eight lapping and measurement cycles.

[0125] Next, an etching process was performed to remove the processed altered layer, and a CMP process was performed for mirror polishing to obtain the SiC single crystal substrate of Example 1.

[0126] (Example 2) A SiC single crystal substrate was obtained under the same conditions as in Example 1, except that the cooling rate up to 1500°C was changed to 200°C / h during the cooling process.

[0127] (Example 3) A SiC single crystal substrate was obtained under the same conditions as in Example 1, except that the cooling rate up to 1500°C was changed to 100°C / h during the cooling process.

[0128] (Example 4) A SiC single crystal substrate was obtained under the same conditions as in Example 1, except that the cooling rate to 1500°C was changed to 100°C / h and the cooling rate to room temperature was changed to 200°C / h during the cooling process.

[0129] (Example 5) A SiC single crystal substrate was obtained under the same conditions as in Example 2, except that a seed crystal S with a diameter of 150 mm was used.

[0130] (Comparative Example 1) A SiC single crystal substrate was obtained under the same conditions as in Example 1, except that the cooling rate up to 1500°C was changed to 330°C / h during the cooling process.

[0131] (Comparative Example 2) A SiC single crystal substrate was obtained under the same conditions as in Example 1, except that the cooling rate up to 1500°C was changed to 40°C / h during the cooling process.

[0132] (Comparative Example 3) A SiC single crystal substrate was obtained under the same conditions as in Example 1, except that the cooling conditions in the temperature reduction process were changed to a cooling rate of 40°C / h up to 1500°C and a cooling rate of 50°C / h down to room temperature.

[0133] (evaluation) The non-MP defect pit density and SORI were measured for the SiC single-crystal substrates of Examples 1-5 and Comparative Examples 1-3. Then, nitrogen ions were implanted into the surface using an ion implanter, and annealing, a process typically performed in conjunction with ion implantation during device fabrication, was carried out in a vacuum at 1600°C for 30 minutes. The SORI of the SiC single-crystal substrates was then measured. The non-MP defect pit density was measured by etch pits appearing after KOH etching at 550°C for 10 minutes. The results are shown in Table 1. The rate of change in SORI before and after ion implantation was calculated using the formula {(SORI before implantation - SORI after implantation) / (SORI before implantation)} × 100.

[0134] [Table 1]

[0135] (Examples 6-10, Comparative Examples 4-7) A SiC single crystal substrate was obtained in the same manner as in Example 1, and the density distribution of non-MP etch pits in the central region and the surrounding outer region of the SiC single crystal substrate was adjusted by annealing to obtain SiC single crystal substrates for evaluation in Examples 6-9 and Comparative Examples 4-7. For Example 10, the SiC single crystal substrate for evaluation was obtained in the same manner as in Examples 6-9 and Comparative Examples 4-7, except that the SiC single crystal substrate was obtained in the same manner as in Example 5. The density of non-MP defect pits and SORI were measured in the central and outer regions of the obtained SiC single crystal substrates. The results are shown in Table 2.

[0136] [Table 2]

[0137] From the results of Examples 1 to 4 shown in Table 1, it was found that the non-MP defect density can be adjusted by the cooling rate during the cooling process after crystal growth. Within the range of cooling rates in the examples, it was found that the non-MP defect density increased as the cooling rate decreased. Furthermore, the non-MP defect density is 0.01 to 50.2 [defects / cm³]. 2 In the case of (Examples 1-4), the rate of change of SORI before and after ion implantation was 500% or less. In contrast, when the non-MP defect density was 0 [defects / cm³], 2 In the case of (Comparative Example 1), the rate of change of SORI before and after ion implantation exceeded 1500%. Also, the non-MP defect density was 50 [defects / cm³]. 2 When the value exceeded [ ] (Comparative Examples 2 and 3), the rate of change of SORI before and after ion implantation significantly exceeded 500%. Furthermore, the non-MP defect density is 1.5 to 9.8 [defects / cm³]. 2 When the ion implantation rate was 1.5 [defects / cm³], the change rate of SORI before and after ion implantation was 400% or less. 2 The smallest change in SORI before and after ion implantation was observed at 324% during this period. Furthermore, in Example 5, which uses a 6-inch SiC single crystal substrate, the presence of non-MP defects was confirmed, similar to Examples 1-4, which use an 8-inch SiC single crystal substrate.

[0138] From the results of Examples 6-9 and Comparative Examples 4-5 shown in Table 2, it was found that the ratio NP of the density of non-MP defect pits in the central and outer regions can be adjusted by performing a substrate annealing process after obtaining a SiC single crystal substrate. Furthermore, when the NP was between 0.051 and 0.469 (Examples 6-9), the rate of change of SORI before and after ion implantation was 750% or less. In contrast, when the NP was 0.005 (Comparative Example 4), the rate of change of SORI before and after ion implantation exceeded 1600%, and when the NP exceeded 0.5 (Comparative Examples 5-7), the rate of change of SORI before and after ion implantation became close to 1000%, and when the NP was 0.694, the rate of change of SORI before and after ion implantation exceeded 3000%. Furthermore, when the NP was between 0.137 and 0.213 (Examples 7 and 8), the rate of change of SORI before and after ion implantation was approximately 300% or less. When the NP was 0.213 (Example 8), the rate of change of SORI before and after ion implantation was the smallest, at 210%. Furthermore, it was found that, similar to Examples 6-inch SiC single crystal substrates (Example 10), the ratio NP of non-MP defect pit densities in the central and outer regions could be adjusted. [Explanation of Symbols]

[0139] 1 SiC single crystal substrate 1A Central area 1B Outer area

Claims

1. The main surface has an off-angle with respect to the (0001) surface in the range of 0° to 6° in the <11-20> direction and in the range of 0° to 0.5° in the <1-100> direction. When etching the Si surface with molten KOH at 500°C for 15 minutes, the etch pits that appear are hexagonal in shape and have no core, and furthermore, the observed etch pit area is 10% or more larger than the etch pit area of ​​TSD etch pits and 110% or less of the etch pit area of ​​micropipe (MP) etch pits, and includes non-MP defects that can be distinguished from the transmitted X-ray topography image of the micropipe (MP) in the transmitted X-ray topography image. In the aforementioned etch pits, there are 0.1 non-MP defect pits / cm² that are identified as non-MP defects. ２ ~50 pieces / cm ２ It appears within the range, When the substrate is divided into a central region within a range of r / 2 from the center and an outer region located outside the central region, The density of non-MP defect pits in the central region is NA [number of pits / cm²]. ２ ] and the density of non-MP defect pits in the outer region NB [pieces / cm³] ２ ] and, 0.01 < NP < 0.5 (where NP = {NA / (NA + NB)}) Satisfying the relationship, A SiC single crystal substrate with a diameter ranging from 145 mm to 155 mm.

2. The main surface has an off-angle with respect to the (0001) surface in the range of 0° to 6° in the <11-20> direction and in the range of 0° to 0.5° in the <1-100> direction. When etching the Si surface with molten KOH at 500°C for 15 minutes, the etch pits that appear are hexagonal in shape and have no core, and furthermore, the observed etch pit area is 10% or more larger than the etch pit area of ​​TSD etch pits and 110% or less of the etch pit area of ​​micropipe (MP) etch pits, and includes non-MP defects that can be distinguished from the transmitted X-ray topography image of the micropipe (MP) in the transmitted X-ray topography image. In the aforementioned etch pits, there are 0.1 non-MP defect pits / cm² that are identified as non-MP defects. ２ ~50 pieces / cm ２ It appears within the range, When the substrate is divided into a central region within a range of r / 2 from the center and an outer region located outside the central region, The density of non-MP defect pits in the central region is NA [number of pits / cm²]. ２ ] and the density of non-MP defect pits in the outer region NB [pieces / cm³] ２ ] and, 0.01 < NP < 0.5 (where NP = {NA / (NA + NB)}) Satisfying the relationship, SiC single crystal substrates with a diameter ranging from 190 mm to 205 mm.

3. In the etch pit, the non-MP defect pits, which are pits identified as the non-MP defects, are present in a range of 0.1 pits / cm ２ to 20 pits / cm ２ The SiC single crystal substrate according to any one of claims 1 or 2, which appears within the range.

4. In the aforementioned etch pits, there are 0.1 non-MP defect pits / cm² that are identified as non-MP defects. ２ ~10 pieces / cm ２ A SiC single crystal substrate according to claim 1 or 2, which appears within the range.

5. In the etch pits, there is one non-MP defect pit per cm², which is identified as a non-MP defect. ２ ~50 pieces / cm ２ A SiC single crystal substrate according to claim 1 or 2, which appears within the range.

6. In the etch pits, there is one non-MP defect pit per cm², which is identified as a non-MP defect. ２ ~20 pieces / cm ２ A SiC single crystal substrate according to claim 1 or 2, which appears within the range.

7. In the etch pits, there is one non-MP defect pit per cm², which is identified as a non-MP defect. ２ ~10 pieces / cm ２ A SiC single crystal substrate according to claim 1 or 2, which appears within the range.

8. In the aforementioned etch pits, there are 1.5 non-MP defect pits per cm², which are identified as non-MP defects. ２ ~50 pieces / cm ２ A SiC single crystal substrate according to claim 1 or 2, which appears within the range.

9. In the aforementioned etch pits, there are 1.5 non-MP defect pits per cm², which are identified as non-MP defects. ２ ~20 pieces / cm ２ A SiC single crystal substrate according to claim 1 or 2, which appears within the range.

10. In the aforementioned etch pits, there are 1.5 non-MP defect pits per cm², which are identified as non-MP defects. ２ ~9.8 pieces / cm ２ A SiC single crystal substrate according to claim 1 or 2, which appears within the range.

11. The SiC single crystal substrate according to claim 1 or 2, wherein the NP is 0.051 to 0.

469.

12. The SiC single crystal substrate according to claim 1 or 2, wherein the NP is 0.137 to 0.213.

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