Method for growing group 13 element nitride crystal layer, nitride semiconductor ingot, and sputtering target

Abstract

[Problem] To achieve a thick crystal layer by a growing a group 13 element nitride crystal layer at high growth speed. [Solution] The group 13 element nitride crystal layer is grown on a base substrate that contains at least a seed crystal layer. The base substrate is immersed in a melt containing flux, and a group 13 element nitride crystal layer is grown two-dimensionally with the flux method on a nitrogen polar surface of a seed crystal layer.

Description

[Technical field]

[0001] The present invention relates to a method for growing a Group 13 element nitride crystal layer, a nitride semiconductor ingot, and a sputtering target. [Background technology]

[0002] Nitride semiconductors have a wide direct transition band gap, a high dielectric breakdown field, and a high saturated electron velocity, and are therefore attracting attention as semiconductor materials for light-emitting devices such as LEDs and LDs, as well as for high-frequency / high-power electronic devices.

[0003] It is known that gallium nitride crystals can be grown in the -c-axis direction on the inner wall surface of a crucible by the so-called flux method (Patent Document 1: JP 2005-206415 A). In this method, elements such as Mn, Fe, Cr, Co, and Ni are added to the melt to promote the N-face growth of gallium nitride crystals on the inner wall surface of the crucible, but in the examples, only columnar crystals with a length of about 1.5 mm are grown.

[0004] Meanwhile, it has been proposed to produce an ingot by growing a gallium nitride crystal into a thick film. For example, Patent Document 2 (JP 2010-280562 A) discloses a method for producing an ingot by combining a flux method and a vapor phase method to grow a thick gallium nitride crystal and processing it so that the surface roughness Ra is 5 nm or less and the curvature radius of the warp is 2 m or more.

[0005] Also, a technique has been disclosed for producing a sputtering target by sintering gallium nitride crystal powder (Patent Document 3: WO2016 / 158651).

[0006] In addition, as a method of direct bonding by surface activation treatment, a method of bonding GaN to a support substrate at room temperature via an oxide layer has been disclosed (Patent Document 4: JP 2019-003090 A (0060) to (0061)).

[0007] Also disclosed is a method in which a GaN thin film is irradiated with a UV laser to decompose the GaN at the interface with the base substrate, thereby peeling the GaN thin film off from the substrate (Patent Document 5: JP 2000-101139 A). This method is hereinafter referred to as the laser lift-off method. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent Publication 2005-206415 [Patent Document 2] Patent Publication No. 2010-280562 [Patent Document 3] WO2016 / 158651 [Patent Document 4] Patent Publication No. 2019-003090 [Patent Document 5] Patent Publication 2000-101139 [Patent Document 6] Patent Publication No. 2005-263622 Summary of the Invention [Problem to be solved by the invention]

[0009] According to Patent Document 6 (JP 2005-263622 A), the upper limit of the growth rate of GaN crystal by the flux method is about 100 μm / h.

[0010] In addition, in Patent Document 3, when gallium nitride powder is sintered and processed into a sputtering target to form a gallium nitride thin film, the oxygen concentration of the gallium nitride thin film is 1×10 20 cm -3 It has been shown that the oxygen concentration is larger than that of powdered gallium nitride. Because powdered gallium nitride has a large surface area, its surface is easily oxidized in the atmosphere, and oxygen is released when the sputtering process begins. As the gallium nitride thin film is formed on the substrate, oxygen is easily mixed into the film. For this reason, it is thought to be difficult to form a homogeneous gallium nitride thin film with a low oxygen concentration.

[0011] If it were possible to form a GaN bulk material by growing GaN thickly on an oriented crystal using, for example, the HVPE or flux method, rather than a sintered body of GaN powder, it would be possible to create a sputtering target with a low impurity concentration, especially oxygen concentration, and form a gallium nitride thin film with a low oxygen concentration by sputtering. However, it would take a long time to grow the target to the thickness required for a sputtering target, and it would be prone to warping and cracking, so it is thought to be difficult to produce a sputtering target using existing manufacturing methods.

[0012] An object of the present invention is to grow a Group 13 element nitride crystal layer at a high growth rate, thereby making it possible to obtain a thick Group 13 element nitride crystal layer.

[0013] Another object of the present invention is to provide a homogeneous sputtering target having a low oxygen concentration. [Means for solving the problem]

[0014] The present invention relates to Offset angle is 0.3 to 2 degrees forming a seed crystal layer made of a group 13 element nitride on a substrate made of sapphire by metal organic chemical vapor deposition; bonding a group 13 element polar surface of the seed crystal layer to a support substrate; peeling the base body from the seed crystal layer to obtain a base substrate including the seed crystal layer; and A step of immersing the base substrate in a melt containing a sodium flux and two-dimensionally growing a group 13 element nitride crystal layer on the nitrogen polarity surface of the seed crystal layer by a sodium flux method. The present invention relates to a method for growing a Group 13 element nitride crystal layer, comprising the steps of:

[0015] By separating the Group 13 element nitride crystal layer from the base substrate, a nitride semiconductor ingot consisting of the Group 13 element nitride crystal layer can be obtained. Effect of the Invention

[0016] The present inventors, when growing a Group 13 element nitride crystal layer by the flux method, introduced a seed crystal into a melt and grew the Group 13 element nitride crystal layer two-dimensionally on the nitrogen polarity face of the seed crystal. They found that the Group 13 element nitride crystal layer could be grown at a higher growth rate than when growing the Group 13 element nitride crystal layer on a Group 13 element polarity face (e.g., a gallium polarity face).

[0017] As a result, it has become possible to grow a thick film, for example a Group 13 element nitride crystal layer having a thickness of 5 mm or more, at a practical speed, and it has become possible to provide a nitride semiconductor ingot. It has been found that such a nitride semiconductor ingot has excellent properties as a sputtering target, and in particular, it is possible to provide a homogeneous target with a low oxygen concentration.

[0018] Furthermore, it was found that a plurality of nitride semiconductor wafers can be produced by slicing the nitride semiconductor ingot thus obtained, which is an extremely excellent mass production method.

[0019] It was also found that the crystal lattice of the nitride semiconductor ingot obtained in this way is moderately curved internally, and that the orientation of the crystal lattice (especially the c-plane) changes moderately between the nitrogen polarity plane and the group 13 element polarity plane. As the crystal growth of such a nitride semiconductor ingot progresses, the growth surface side becomes closer to a single crystal, and the in-plane crystal distortion of the nitride semiconductor wafer obtained by slicing the nitride semiconductor ingot becomes smaller. This resulted in the production of a nitride semiconductor wafer with a small distribution of off-angles within the plane. [Brief description of the drawings]

[0020] [Figure 1] (a) shows a state in which a seed crystal layer 2 is formed on a base 1, (b) shows a state in which a surface 2a of the seed crystal layer 2 and a surface 3a of a support substrate 3 are irradiated with activation beams A and B, and (c) shows a state in which the seed crystal layer 2 and the support substrate 3 are directly bonded to each other. [Diagram 2]1A shows a state in which the substrate 1 has been peeled off from the seed crystal layer 2, FIG. 1B shows a state in which a Group 13 element nitride crystal layer 4 has been grown on the nitrogen-polarity face 2b of the seed crystal layer 2, FIG. 1C shows a state in which the support substrate 3 has been peeled off from the Group 13 element nitride crystal layer 4, and FIG. 1D shows an ingot 5 made of the Group 13 element nitride crystal layer. [Diagram 3] FIG. 2 is a plan view showing measurement points on a nitride semiconductor ingot 5 and a nitride semiconductor wafer obtained by slicing the nitride semiconductor ingot. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The present invention will now be described in detail with reference to the accompanying drawings. 1(a), a seed crystal layer 2 is formed on a surface 1a of a substrate 1. At this time, 2b is a nitrogen polarity surface, and the growth surface 2a is a group 13 element polarity surface.

[0022] Next, this seed crystal layer 2 is bonded to a separate support substrate. In a preferred embodiment, as shown in FIG. 1(b), the Group 13 element polar surface 2a of the seed crystal layer 2 is irradiated with an activation beam A for surface activation. In addition, the surface 3a of the support substrate 3 is irradiated with an activation beam as shown by an arrow B for surface activation. Next, as shown in FIG. 1(c), the Group 13 element polar surface 2a of the seed crystal layer 2 and the activated surface 3a of the support substrate 3 are brought into contact with each other and directly bonded to each other, thereby obtaining a bonded body.

[0023] Next, as shown in Fig. 2(a), the base 1 is separated from the seed crystal layer 2 to obtain a base substrate 6. At this point, the nitrogen polar surface 2b of the seed crystal layer 2 is exposed. Next, as shown in Fig. 2(b), a group 13 element nitride crystal layer 4 is grown on the nitrogen polar surface 2b of the seed crystal layer 2 by a flux method.

[0024] Next, by removing the support substrate 3 from the crystal layer 4, a laminate consisting of the crystal layer 4 and the seed crystal layer 2 can be obtained as shown in Fig. 2(c). Next, by removing the seed crystal layer 2, it is also possible to obtain a nitride semiconductor ingot 5 as shown in Fig. 2(d). Note that 4a and 5a are nitrogen polarity planes, and 4b and 5b are group 13 element polarity planes.

[0025] In the present invention, a group 13 element nitride crystal layer is grown on a base substrate including at least a seed crystal layer. The entire base substrate may be made of the seed crystal layer, but preferably the seed crystal layer is formed on a support substrate. At this time, a Group 13 element nitride crystal layer is grown two-dimensionally on the nitrogen polarity face of the seed crystal layer by a flux method.

[0026] Note that, two-dimensionally growing a Group 13 element nitride crystal layer means that the crystal grows so as to cover the nitrogen polarity face of the seed crystal layer to generate a crystal layer.

[0027] In the present invention, the Group 13 element nitride crystal layer is preferably grown on the nitrogen polarity surface of the seed crystal layer to a thickness of 5 mm or more, more preferably 10 mm or more. There is no particular upper limit to the thickness of the Group 13 element nitride crystal layer, but in practice, it is often 50 mm or less.

[0028] In addition, when growing a group 13 element nitride crystal layer by the flux method, if the group 13 element nitride crystal layer is epitaxially grown thickly directly on the nitrogen polarity surface of the base substrate, the crystal may crack together with the base substrate. However, in the above-mentioned preferred embodiment, after forming a seed crystal layer on a base, this seed crystal layer is bonded to a separate support substrate, and then the original base is removed to expose the nitrogen polarity surface of the seed crystal layer on the support substrate. When a group 13 element nitride crystal layer is grown thick on this nitrogen polarity surface by the flux method, the crystal peels off at the interface between the support substrate and the crystal before it cracks together with the support substrate, so that a thick crystal can be obtained while preventing the crystal from cracking. This makes it possible to obtain a sufficiently thick nitride semiconductor ingot.

[0029] It is preferable to provide a low-temperature buffer layer on the substrate and then provide a seed crystal layer on the substrate. The method for forming such a buffer layer is preferably a vapor phase growth method, such as a metal organic chemical vapor deposition (MOCVD) method, a hydride vapor phase epitaxy (HVPE) method, or an MBE method.

[0030] As a preferred example of a method for forming the seed crystal layer, a vapor phase growth method can be given, and examples thereof include a metal organic chemical vapor deposition (MOCVD) method, a hydride vapor phase epitaxy (HVPE) method, a pulsed photoexcited deposition (PXD) method, a molecular beam epitaxy (MBE) method, and a sublimation method. A metal organic chemical vapor deposition method is particularly preferred.

[0031] In addition, in the group 13 element nitride constituting the seed crystal layer, the group 13 element is an element in group 13 according to the periodic table established by IUPAC, specifically, boron, gallium, aluminum, indium, thallium, etc.

[0032] The thickness of the seed crystal layer is preferably 0.5 μm or more, more preferably 2 μm or more, from the viewpoint of preventing meltback or disappearance during crystal growth, and is preferably 15 μm or less from the viewpoint of productivity.

[0033] The material of the substrate is Offset angle is 0.3 to 2 degrees It's sapphire.

[0034] The material of the support substrate is not particularly limited, but examples thereof include sapphire, crystal-oriented alumina, and single crystal nitride of an element of Group 13. From the viewpoint of handling, the thickness of the support substrate is preferably 500 μm or more, and more preferably 1000 μm or more.

[0035] Examples of a method for bonding the seed crystal layer on the base body to the support substrate include direct bonding and bonding with an adhesive.

[0036] The fact that the growth surface of the group 13 element nitride crystal layer is a nitrogen polarity surface can be confirmed, for example, by the CBED (Convergent-Beam Electron Diffraction) method. Specifically, a focused electron beam is incident on the sample, a circular diffraction spot is obtained from the sample, and it can be confirmed as a nitrogen polarity surface by comparing it with a diffraction image (CBED pattern) calculated by simulation.

[0037] When growing a group 13 element nitride crystal layer on the nitrogen polarity surface of the seed crystal layer, the group 13 element nitride crystal layer is grown by a flux method. In this group 13 element nitride crystal layer, the group 13 element is an element in group 13 according to the periodic table established by IUPAC. Specifically, the group 13 element nitride is preferably GaN, AlN, InN, AlGaN, or a mixed crystal thereof.

[0038] The group 13 element nitride crystal layer is preferably a single crystal. The definition of a single crystal is explained below. It includes a textbook single crystal in which atoms are regularly arranged throughout the crystal, but is not limited to this, and means a single crystal that is generally distributed in industry. In other words, the crystal may contain some defects, have inherent distortion, or have impurities incorporated therein, and this is the same as calling these single crystals to distinguish them from polycrystals (ceramics).

[0039] When the Group 13 element nitride crystal layer is grown by a flux method, the type of flux that is particularly preferred is a flux that contains sodium metal.

[0040] The flux is used by mixing a metal source material. The metal source material may be a single metal, an alloy, or a metal compound, but a single metal is preferable from the viewpoint of handling. The growth temperature and holding time for the Group 13 element nitride crystal layer in the flux method are not particularly limited and are changed appropriately depending on the composition of the flux. When growing gallium nitride crystal using a sodium-containing flux, the growth temperature is preferably 800 to 950°C, and more preferably 850 to 900°C.

[0041] In the flux method, a group 13 element nitride crystal layer is grown in an atmosphere containing a gas containing nitrogen atoms. This gas is preferably nitrogen gas, but may be ammonia. The pressure of the atmosphere is not particularly limited, but from the viewpoint of preventing evaporation of the flux, it is preferably 10 atmospheres or more, more preferably 30 atmospheres or more. However, since a large-scale apparatus is required when the pressure is high, the total pressure of the atmosphere is preferably 2000 atmospheres or less, more preferably 500 atmospheres or less. Gases other than the gas containing nitrogen atoms in the atmosphere are not limited, but an inert gas is preferable, and argon, helium, and neon are particularly preferable.

[0042] In order to grow a group 13 element nitride crystal layer two-dimensionally on the nitrogen polarity surface of the seed crystal layer by the flux method, it is preferable to arrange the base substrate horizontally in the crucible, and it is preferable to promote the supply of nitrogen over the entire surface of the seed crystal layer of the base substrate. Furthermore, it is preferable to sufficiently increase the nitrogen concentration in the flux liquid. To increase the nitrogen concentration, it is necessary to dissolve nitrogen until the nitrogen concentration in the entire liquid becomes supersaturated by, for example, increasing the temperature of the flux liquid and stirring the flux liquid sufficiently.

[0043] The method for separating the base body from the seed crystal layer and the method for separating the support substrate from the Group 13 element nitride crystal layer are not particularly limited, and examples thereof include grinding, laser ablation, and chemical mechanical polishing, with the laser lift-off method being particularly preferred. In the case of the laser lift-off method, examples of the laser light source include the third harmonic, fourth harmonic, and fifth harmonic of the Nd:YAG laser, F2 excimer laser, ArF excimer laser, KrF excimer laser, XeCl excimer laser, XeF excimer laser, the third harmonic and fourth harmonic of the YVO4 laser, and the third harmonic and fourth harmonic of the YLF laser. Particularly preferred laser light sources include the third harmonic of the Nd:YAG laser, the fourth harmonic of the Nd:YAG laser, the third harmonic and fourth harmonic of the YVO4 laser, and the KrF excimer laser.

[0044] The shape of the laser irradiation may be circular, elliptical, rectangular, or linear. The laser profile may be shaped through a beam profiler. The laser profile may be Gaussian, Gaussian-like, doughnut, or top hat. Gaussian and top hat are preferred. In order to adjust the irradiation size and energy density of the laser, the laser may be irradiated onto the substrate after passing through a lens, a slit, or an aperture.

[0045] In a preferred embodiment, it is preferable to adjust the formation of the ridges by using a pulsed laser. There is no particular limitation on the pulse width of the laser, but a laser of 100 fs to 200 ns can be used. The pulse width of the laser is preferably 200 ns or less, and more preferably 1 ns or less. The supporting substrate may be irradiated with the laser while being heated. Heating reduces warping, allowing uniform processing within the substrate surface.

[0046] By slicing the nitride semiconductor ingot, multiple nitride semiconductor wafers having nitrogen polarity faces and group 13 element polarity faces can be produced. This significantly improves productivity compared to manufacturing wafers on a sheet-by-sheet basis. The material of the nitride semiconductor wafer is the same as that of the nitride semiconductor ingot, and examples of the material include GaN wafers, AlN wafers, and AlGaN wafers.

[0047] (Nitride semiconductor ingot) According to the present invention, it is possible to provide a nitride semiconductor ingot made of a Group 13 element nitride, having a diameter of 75 mm or more and 200 mm or less and a thickness of 5 mm or more. Such nitride semiconductor ingots are difficult to manufacture and have not previously been available.

[0048] (As a sputtering target) The nitride semiconductor ingot of the present invention has a low concentration of oxygen as an impurity, and the unevenness of the oxygen concentration in the thickness direction and within the surface is small. 17 cm -3 That's it, 2 x 10 17 cm -3 The oxygen concentration on the nitrogen polarity surface of the nitride semiconductor ingot is 0.5×10 17 cm -3 That's it, 1.5 x 10 17 cm -3 It can be as follows: Conventional nitride semiconductor ingots made from sintered bodies only had high concentrations of impurities such as oxygen. However, the present invention makes it possible to use a highly pure Group 13 element nitride crystal layer, and in particular to provide a sputtering target with a sufficiently low oxygen concentration.

[0049] A functional device structure can be formed on the thus obtained group 13 element nitride crystal layer. Alternatively, this functional device structure can be obtained by forming a film by sputtering using the obtained sputtering target. This functional device structure can be used for high-brightness, high-color-rendering white LEDs, blue-violet laser disks for high-speed, high-density optical memory, power devices for inverters in hybrid vehicles, and so on. EXAMPLES

[0050] Example 1 (Deposition of seed crystal layer) According to the manufacturing method shown in FIG. 1 and FIG. 2, a Group 13 element nitride crystal layer and a nitride semiconductor ingot of the present invention were produced. Specifically, a 3-inch sapphire substrate (substrate 1) with an off-angle of 0.5 degrees was placed on a susceptor in an MOCVD furnace (metal organic chemical vapor deposition furnace), and the substrate temperature was raised to 1200°C in a hydrogen atmosphere to perform a cleaning process. Next, the temperature was lowered to 520°C, and a gallium nitride layer (buffer layer) was formed to a thickness of 20 nm using hydrogen as a carrier gas and TMG (trimethylgallium) and ammonia as raw materials. Thereafter, the substrate temperature was raised to 1100°C using nitrogen and hydrogen as carrier gas, and a GaN seed crystal layer 2 was grown to a thickness of 3 μm using TMG (trimethylgallium) and ammonia as raw materials. Thereafter, the substrate on which the GaN crystal layer was grown was lowered to room temperature in a nitrogen atmosphere and then removed from the MOCVD furnace (see FIG. 1(a)).

[0051] (direct bonding) The substrate 1 on which the GaN seed crystal layer 2 was formed was taken out, and the surface of the GaN seed crystal layer 2 was bonded to a support substrate 3 made of polycrystalline alumina by room temperature direct bonding (surface activation method). The surface of the support substrate 3 made of polycrystalline alumina was polished to a surface roughness RMS of 1 nm. Argon beams A and B were irradiated, and the polished surfaces were brought into contact with each other in a vacuum and a load was applied to perform direct bonding.

[0052] (Peeling of substrate 1) The directly bonded assembly (Figure 1(c)) was subjected to pulsed irradiation of a short-wavelength laser from the substrate 1 side to separate the GaN seed crystal layer 2 and the substrate 1, thereby producing a base substrate 6 (Figure 2(a)) in which the GaN seed crystal layer 2 was directly bonded to the support substrate 3. The third harmonic of a Nd:YAG laser (wavelength 355 nm) was used as the laser light source, and it was a pulsed laser. The repetition rate was 10 Hz, the pulse width was 10 ns, the light was focused by a lens with a focal length of 700 mm, the distance between the lens and the substrate surface was 400 mm, and the light energy density during laser lift-off was 500 mJ / cm. 2 The entire substrate was scanned so that the irradiated dots by the pulsed laser overlapped each other.

[0053] (Thick film growth of nitride semiconductor ingots by flux method) Using a 3-inch polycrystalline alumina support substrate 3 to which a GaN seed crystal layer 2 was bonded, a GaN crystal layer 4 was grown thick by a flux method (FIG. 2(b)). Specifically, an alumina crucible was prepared, and the 3-inch polycrystalline alumina support substrate 3 with the GaN seed crystal layer 2 bonded thereto was placed in the alumina crucible. Then, 400 g of metallic Ga and 800 g of metallic Na were filled in the alumina crucible, so that the 3-inch polycrystalline alumina support substrate 3 with the GaN seed crystal layer 2 bonded thereto was immersed in a melt containing a flux. The alumina crucible was then placed in a growth vessel made of a heat-resistant metal and sealed. The temperature inside the furnace was set to 850° C., and nitrogen gas was introduced to set the pressure inside the furnace to 4 MPa. In a heat-resistant and pressure-resistant crystal growth furnace, the growth vessel was held for 35 hours while being rotated horizontally, so that a GaN crystal layer was grown on the polycrystalline alumina support substrate 3 with the GaN seed crystal layer 2 bonded thereto. After cooling to room temperature, the substrate on which the GaN crystal layer had grown was removed from the alumina crucible. The GaN seed crystal layer 2 and the support substrate 3 were naturally peeled off, and a thick GaN crystal layer 4 with a diameter of 3 inches and a thickness of approximately 5.5 mm was obtained.

[0054] The front and back surfaces (peeled surfaces) of the removed thick GaN crystal layer 4 were polished with diamond abrasive grains to be flattened to a thickness of 5 mm, thereby obtaining a nitride semiconductor ingot 5 having a diameter of 3 inches (FIG. 2(d)).

[0055] Example 2 The off-angle of the 3-inch sapphire substrate used in Example 1 was changed to 0.0 degrees, 0.3 degrees, 1 degree, 2 degrees, and 3 degrees to prepare five types, and an attempt was made to produce a nitride semiconductor ingot in the same manner as in Example 1. When the off-angles were 0.0 degrees and 3 degrees, the growth of the thick GaN crystal layer 4 was not confirmed, but for the three types of off-angles of 0.3 degrees, 1 degree, and 2 degrees, a 3-inch diameter 5 mm thick nitride semiconductor ingot was obtained in the same manner as in Example 1. These three types of nitride ingots were classified in order of the smallest off-angle as #A (0.3 degrees), #B (1 degree), and #C (2 degrees), and SIMS analysis was performed at nine points within the plane of each of the gallium polarity plane and the nitrogen polarity plane. The nine points within the plane are, as shown in FIG. 3, a virtual circle C1 with a radius of 30 mm and a virtual circle C2 with a radius of 60 mm are set around the center O of the surface 5a of the nitride ingot 5. In addition, virtual lines P and H that pass through the center O and are perpendicular to each other are set. The measurement points were the center O, the intersections A1, A2, A3, and A4 between the imaginary circle C1 and the imaginary lines P and H, and the intersections B1, B2, B3, and B4 between the imaginary circle C2 and the imaginary lines P and H. The oxygen concentration at depths of 5 μm to 25 μm was averaged at each of the nine points on this surface, and the maximum and minimum values ​​were determined, as shown in Table 1.

[0056] [Table 1]

[0057] (Example 3: Sputtering target) The nitride semiconductor ingot of Example 2 was used, and a copper plate (backing plate) was heated and bonded to the nitride semiconductor ingot using metallic indium to prepare a sputtering target. This sputtering target was used, and Ar 20sccm, N 2GaN films were formed by sputtering at 100 sccm, pressure 1 Pa, RF power 400 W, using a 2-inch sapphire substrate as the base material, and the substrate temperature was set to 250°C. After the sputtering process, the sapphire substrate was removed, and a uniform GaN film with a thickness of 1 μm was found to have been formed. This sputtering process was repeated to produce 20 GaN films on sapphire substrates, which were then analyzed by SIMS, and the oxygen concentration was found to be 1×10 17 (cm -3 ) was. As described above, when a film was formed using the sputtering target of the present invention, a GaN film of the same quality could be stably formed even if the sputtering target was consumed.

[0058] Example 4 In the same manner as in Example 1, a GaN crystal layer was grown as a thick film by a flux method using a 3-inch polycrystalline alumina support substrate to which a GaN seed crystal layer was bonded. In the flux method, 2000 g of metallic Ga and 4000 g of metallic Na are filled into an alumina crucible. The alumina crucible is then placed in a heat-resistant metal growth vessel and sealed. The temperature inside the furnace is set to 850°C, and nitrogen gas is introduced to set the pressure inside the furnace to 4 MPa. In a heat-resistant and pressure-resistant crystal growth furnace, the growth vessel is held for 300 hours while rotating horizontally, thereby growing a GaN crystal layer on a 3-inch polycrystalline alumina support substrate bonded with a GaN seed crystal layer. After cooling to room temperature, the substrate on which the GaN crystal layer is grown is taken out of the alumina crucible. The GaN crystal layer and the polycrystalline alumina support substrate are naturally peeled off, and a thick GaN crystal layer measuring 3 inches and about 52 mm thick is obtained.

[0059] The top and bottom surfaces of the removed thick GaN crystal layer were polished with diamond abrasives to flatten it, yielding a 50 mm thick nitride semiconductor ingot. This nitride semiconductor ingot was sliced ​​to obtain 50 3-inch GaN wafers (nitride semiconductor wafers) with a thickness of 0.5 mm. Three GaN wafers were taken out of the obtained wafers, and the off-angle, its distribution, and the warpage of the GaN wafers were measured. The wafer closest to the gallium polarity plane in the ingot before slicing was designated #D, the wafer closest to the nitrogen polarity plane was designated #F, and the wafer between #D and #F was designated #E. The off-angle was measured at nine points on the gallium polarity plane of the GaN wafer. The measurement positions of the nine points on the plane were O, A1, A2, A3, A4, B1, B2, B3, and B4 shown in Figure 3. The off-angle was measured using a Bruker AXS D2 Cryso, and the difference between the maximum and minimum off-angles measured at the nine points on the plane was taken as the off-angle width. The warpage was measured using a NIDEK FT-17 flatness tester. The results are shown in Table 2. As shown in Table 2, the substrates obtained had smaller off-angle widths as they were closer to the nitrogen polarity plane.

[0060] [Table 2]

[0061] Example 5 A GaN film that was thin-film grown on a substrate by sputtering was used as a seed crystal to produce a larger diameter GaN wafer. Specifically, when a sputtering process was carried out using the sputtering target obtained in Example 3 on a sapphire substrate having a diameter of 200 mm as a base material, a GaN film having a uniform thickness of 1 μm was formed. When the polarity was determined by the CBED method, the surface of the GaN film was found to be a gallium polar surface.

[0062] Using this GaN film, a GaN crystal layer was grown thick by the flux method. 2000 g of metallic Ga and 4000 g of metallic Na were filled into an alumina crucible. Furthermore, this alumina crucible was placed in a heat-resistant metal growth vessel and sealed. The temperature inside the furnace was set to 850°C, and nitrogen gas was introduced to set the furnace pressure to 4 MPa. In a heat-resistant and pressure-resistant crystal growth furnace, the growth vessel was held for 200 hours while rotating horizontally, thereby growing a GaN crystal layer on the sapphire substrate on which the GaN film was formed. After cooling to room temperature, the substrate on which the GaN crystal had grown was taken out of the alumina crucible, and the GaN crystal layer and the support substrate made of polycrystalline alumina were naturally peeled off, and a thick GaN crystal layer with a diameter of 200 mm and a thickness of about 6 mm was obtained.

[0063] The front and back surfaces of the removed thick GaN crystal layer were polished and flattened with diamond abrasive grains to obtain a nitride semiconductor ingot with a diameter of 200 mm and a thickness of 5 mm. This nitride semiconductor ingot was sliced, and the front and back surfaces were polished and flattened with diamond abrasive grains to obtain three GaN wafers with a diameter of 200 mm and a thickness of 1 mm.

Claims

1. A step of forming a seed crystal layer made of a group 13 element nitride on a substrate made of sapphire with an off-angle of 0.3 degrees to 2 degrees by metal organic chemical vapor deposition; bonding a group 13 element polar surface of the seed crystal layer to a support substrate; A step of peeling the base body from the seed crystal layer to obtain a base substrate including the seed crystal layer; and A step of immersing the base substrate in a melt containing a sodium flux and two-dimensionally growing a group 13 element nitride crystal layer on the nitrogen polarity surface of the seed crystal layer by a sodium flux method.

1. A method for growing a group 13 element nitride crystal layer, comprising:

2. 2. The method according to claim 1, wherein the group 13 element nitride crystal layer is grown to a thickness of 5 mm or more.

3. 3. The method according to claim 1, wherein the growth surface of the group 13 element nitride crystal layer is a nitrogen polarity surface.

4. The method according to any one of claims 1 to 3, wherein the group 13 element nitride crystal layer is separated from the base substrate to obtain a nitride semiconductor ingot made of the group 13 element nitride crystal layer.

5. 5. The method according to claim 4, wherein the nitride semiconductor ingot has a diameter of 75 mm to 200 mm, and a thickness of 5 mm to 50 mm.

6. The method according to claim 4 or 5, characterized in that a sputtering target made of the nitride semiconductor ingot is obtained.

7. The oxygen concentration on the Group 13 element polar surface of the nitride semiconductor ingot is 0.8×10 １７ cm －３ That's it, 2 x 10 １７ cm －３ The oxygen concentration on the nitrogen polarity face of the nitride semiconductor ingot is 0.5×10 or less. １７ cm －３ That's it, 1.5 x 10 １７ cm －３ 7. The method of claim 6, wherein:

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