WO2024252544A1 - 坩堝、それを用いたベータ型三酸化二ガリウム単結晶基板の製造方法、およびベータ型三酸化二ガリウム単結晶基板 - Google Patents
坩堝、それを用いたベータ型三酸化二ガリウム単結晶基板の製造方法、およびベータ型三酸化二ガリウム単結晶基板 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
Definitions
- This disclosure relates to a crucible, a method for producing a beta-type digallium trioxide single crystal substrate using the crucible, and a beta-type digallium trioxide single crystal substrate.
- Patent Document 1 JP 2016-079080 A
- Patent Document 2 JP 2017-193466 A
- Patent Document 3 JP 2021-031367 A
- Patent Document 4 JP 2021-031379 A
- Patent Document 5 JP 2020-059633 A
- Hoshikawa et al. Journal of the Japanese Society for Crystal Growth, Vol. 44, No.
- Non-Patent Document 1 discloses a method for growing beta-type gallium trioxide single crystals (hereinafter also referred to as "beta-type Ga 2 O 3 single crystals") by a vertical boat method using a crucible made of a platinum-rhodium alloy (hereinafter also referred to as "Pt-Rh alloy”) or a crucible or die made of a platinum-iridium alloy (hereinafter also referred to as " Pt-Ir alloy "), or an EFG (Edge-defined Film-fed Growth) method, etc.
- JP 2000-129465 A discloses a method for depositing platinum or a platinum-based alloy by thermal spraying on the surface of a refractory substrate such as ceramics.
- JP 2016-079080 A JP 2017-193466 A JP 2021-031367 A JP 2021-031379 A JP 2020-059633 A JP 2000-129465 A
- the crucible according to the present disclosure is a crucible for growing beta-type gallium trioxide single crystals.
- the crucible has a thickness of 1 mm or more and 10 mm or less.
- the maximum inner diameter of the crucible is 100 mm or more.
- the composition of the crucible is stabilized zirconia containing both or either of yttrium oxide and calcium oxide.
- the surface on the inner peripheral side of the crucible is covered with a thermal spray film containing both or either of rhodium and platinum.
- the thickness of the thermal spray film is 100 ⁇ m or more and 500 ⁇ m or less.
- the stabilized zirconia contains at least 12.0 mass% or more and 15.5 mass% or less of the yttrium oxide, or 10.2 mass% or more and 11.4 mass% or less of the calcium oxide.
- FIG. 1 is a schematic diagram illustrating a single crystal growth apparatus used in the manufacturing method of a beta type Ga 2 O 3 single crystal substrate according to this embodiment, and a main part of a crucible of a first embodiment used in the single crystal growth apparatus.
- FIG. 2 is an enlarged cross-sectional view of a main part of a crucible according to a second embodiment used in the single crystal growth apparatus of FIG.
- FIG. 3 is an enlarged cross-sectional view of a main portion of a crucible according to a third embodiment used in the single crystal growth apparatus of FIG.
- FIG. 4 is an enlarged cross-sectional view of a main portion of a crucible according to a fourth embodiment used in the single crystal growth apparatus of FIG.
- FIG. 1 is a schematic diagram illustrating a single crystal growth apparatus used in the manufacturing method of a beta type Ga 2 O 3 single crystal substrate according to this embodiment, and a main part of a crucible of a first embodiment used in the single crystal growth apparatus.
- FIG. 2
- FIG. 5 is an enlarged cross-sectional view of a main part of a crucible according to a fifth embodiment used in the single crystal growth apparatus of FIG.
- FIG. 6 is a flow chart showing an example of a method for manufacturing a beta type Ga 2 O 3 single crystal substrate according to this embodiment.
- FIG. 7 is a schematic diagram illustrating a beta type Ga 2 O 3 single crystal substrate according to this embodiment.
- FIG. 8 is an explanatory diagram for explaining a Hall measurement sample prepared using the central portion of a beta type Ga 2 O 3 single crystal substrate according to this embodiment in order to measure the carrier concentration in the substrate.
- Patent Documents 1 to 5 and Non-Patent Document 1 it is known that beta-type Ga 2 O 3 single crystals are grown and obtained using a crucible made of Pt-Rh alloy or Pt-Ir alloy. These crucibles made of Pt-Rh alloy, Pt-Ir alloy, etc. are expensive, and it is considered to reduce the thickness in order to reduce costs. However, the crucibles made of the above-mentioned Pt-Rh alloy, Pt-Ir alloy, etc.
- a crucible using a thin film of a Pt-Rh alloy, Pt-Ir alloy, etc. that can at least suppress the occurrence of cracking and chipping during crystal growth and thereby produce beta-type Ga2O3 single crystals with a high yield has not yet been obtained, and its development is eagerly awaited.
- the present disclosure aims to provide a crucible that can suppress the occurrence of cracks, chips, etc. during crystal growth, a method for manufacturing a beta-type digallium trioxide single crystal substrate using the crucible, and a beta-type digallium trioxide single crystal substrate.
- the present inventors have made extensive studies to solve the above problems and have completed the present disclosure.
- the present inventors have focused on zirconia, which is a material with low thermal conductivity, stable against temperature changes, and difficult to deform, as a material for a crucible to which the vertical boat method is applied.
- the inner peripheral surface of the crucible made of zirconia is covered with a thin film containing both or either of rhodium and platinum, for example, a thin film made of a Pt- Rh alloy containing Rh, which can handle the temperature (around 1800°C) required during crystal growth of a beta-type Ga 2 O 3 single crystal.
- a crucible according to one embodiment of the present disclosure is a crucible for growing beta-type digallium trioxide single crystals.
- the crucible has a thickness of 1 mm or more and 10 mm or less.
- the maximum inner diameter of the crucible is 100 mm or more.
- the composition of the crucible is stabilized zirconia containing both or either of yttrium oxide and calcium oxide.
- the surface on the inner peripheral surface side of the crucible is covered with a sprayed film containing both or either of rhodium and platinum.
- the thickness of the sprayed film is 100 ⁇ m or more and 500 ⁇ m or less.
- the stabilized zirconia contains at least 12.0 mass% or more and 15.5 mass% or less of the yttrium oxide, or 10.2 mass% or more and 11.4 mass% or less of the calcium oxide.
- a crucible having such characteristics can suppress the occurrence of cracks, chips, etc. during crystal growth.
- the sprayed film is preferably made of a platinum-rhodium alloy containing 10% by mass or more and 30% by mass or less of rhodium. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- the sprayed film preferably has pores.
- the porosity which is the volume ratio of the pores in the sprayed film, is preferably 30 volume % or more and 50 volume % or less. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- the surface roughness Rz of the surface is preferably 300 ⁇ m or more and 500 ⁇ m or less.
- the sprayed film preferably has pores.
- the porosity which is the volume ratio of the pores in the sprayed film, is preferably 10 vol.% or more and less than 30 vol.%. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- the surface roughness Rz of the surface is 300 ⁇ m or more and 500 ⁇ m or less. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- the sprayed film preferably comprises a first film and a second film.
- the first film preferably covers the surface.
- the first film preferably comprises rhodium or a platinum-rhodium alloy mainly composed of rhodium.
- the second film preferably covers the first film.
- the second film preferably comprises platinum or a platinum-rhodium alloy mainly composed of platinum.
- the thickness of the sprayed film, including the first film and the second film is preferably 100 ⁇ m or more and 500 ⁇ m or less. This makes it possible to suppress the incorporation of rhodium into the beta-type gallium trioxide single crystal.
- both the first film and the second film have pores. It is preferable that the first film porosity, which is the volume ratio of the pores in the first film, and the second film porosity, which is the volume ratio of the pores in the second film, are both 30 volume % or more and 50 volume % or less. This can further suppress the occurrence of cracks, chips, etc. during crystal growth.
- the surface roughness Rz of the surface is preferably 300 ⁇ m or more and 500 ⁇ m or less.
- the first film and the second film both preferably have pores.
- the first film porosity, which is the volume ratio of the pores in the first film, and the second film porosity, which is the volume ratio of the pores in the second film, are both preferably 10 vol.% or more and less than 30 vol.%. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- the surface roughness Rz of the surface is 300 ⁇ m or more and 500 ⁇ m or less. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- a method for producing a beta-type digallium trioxide single crystal substrate is a method for producing a beta-type digallium trioxide single crystal substrate using the crucible described in any one of [1] to [9] above.
- the method includes the steps of preparing the crucible, obtaining a beta-type digallium trioxide single crystal by a vertical boat method using the crucible, and processing the beta-type digallium trioxide single crystal to obtain a beta-type digallium trioxide single crystal substrate having a circular main surface.
- a method having such characteristics can produce a beta-type digallium trioxide single crystal substrate with good yield and product yield.
- a beta-type digallium trioxide single crystal substrate is a beta-type digallium trioxide single crystal substrate having a circular main surface.
- the diameter of the beta-type digallium trioxide single crystal substrate is 100 mm or more.
- the main surface is the (001) plane of the beta-type digallium trioxide single crystal.
- the main surface is a plane having an off angle of more than 0° and not more than 10° from the (001) plane of the beta-type digallium trioxide single crystal, and an off direction in the [010] direction of the beta-type digallium trioxide single crystal or a direction perpendicular to the [010] direction.
- the beta-type digallium trioxide single crystal substrate contains both or either one of rhodium and iridium.
- the rhodium concentration and the iridium concentration are both less than 3 ppm by mass in glow discharge mass spectrometry.
- a beta-type digallium trioxide single crystal substrate having such characteristics can be excellent in both electrical and optical properties.
- the transmittance for light having a wavelength of 400 nm or more and 430 nm or less is preferably 70% or more.
- the carrier concentration measured at 25° C. in the Hall measurement by the Van der Pauw method is preferably 1 ⁇ 10 17 cm ⁇ 3 or more and 1.0 ⁇ 10 19 cm ⁇ 3 or less. This makes it possible to achieve better electrical and optical properties.
- A-B refers to the upper and lower limits of a range (i.e., greater than or equal to A and less than or equal to B). If no unit is stated for A, and only a unit is stated for B, the units of A and B are the same. Furthermore, when compounds are expressed in chemical formulas in this specification, if the atomic ratio is not specifically limited, this includes all conventionally known atomic ratios, and should not necessarily be limited to only those within the stoichiometric range.
- yield means the ratio of the amount of beta-type gallium trioxide single crystal that can be grown to the desired thickness in the crucible without cracking or chipping in the crucible.
- product yield means the ratio of the mass of the ingot of beta-type gallium trioxide single crystal grown in the crucible, which is evaluated as a good product for the substrate by the evaluation method described below, after first excluding the area where the crucible cracks or chips or the crystal cracks or chips during cooling, which would prevent the desired diameter from being obtained when processed into a beta-type gallium trioxide single crystal substrate. The larger the value of the "product yield" of the single crystal, the less likely it is that cracks, chips, etc. occurred in the crucible in which the single crystal was grown.
- main component means a component whose content exceeds 95 mass% in a composition such as an alloy.
- the "maximum inner diameter" of a crucible refers to the inner diameter of the crucible at the position where the inner diameter of the ring that appears in a cross section perpendicular to the axial direction of the cylindrical crucible is maximum when compared along the axial direction of the crucible.
- the crucible preferably has a structure that includes a cylindrical seed crystal storage section, an increased diameter section connected to the seed crystal storage section, and a straight body section connected to the increased diameter section, as described below.
- the “maximum inner diameter” refers to the inner diameter of the straight body section.
- the "main surface" of a beta-type gallium trioxide single crystal substrate means both of the two circular faces of the beta-type gallium trioxide single crystal substrate. In the beta-type gallium trioxide single crystal substrate, if at least one of the two faces satisfies the scope of the claims of this disclosure, it falls within the technical scope of this disclosure. Furthermore, in this specification, the "face” used in the term “in-plane” means the “main surface.” Furthermore, when the diameter of a beta-type gallium trioxide single crystal substrate is described as "100 mm,” this means that the diameter is approximately 100 mm (approximately 95 to 105 mm), or 4 inches. When the diameter is described as "150 mm,” this means that the diameter is approximately 150 mm (approximately 145 to 155 mm), or 6 inches. The diameter can be measured using a conventionally known outer diameter measuring device such as a caliper.
- the crucible according to this embodiment is a crucible for growing beta-type digallium trioxide single crystals (beta-type Ga2O3 single crystals).
- the crucible has a thickness of 1 mm or more and 10 mm or less.
- the maximum inner diameter of the crucible is 100 mm or more.
- the composition of the crucible is stabilized zirconia containing both or either of yttrium oxide and calcium oxide.
- the surface on the inner peripheral surface side of the crucible is covered with a sprayed film containing both or either of rhodium (Rh) and platinum (Pt).
- the sprayed film is preferably made of a platinum-rhodium alloy (Pt-Rh alloy) containing 10 mass % or more and 30 mass % or less of Rh.
- the thickness of the sprayed film is 100 ⁇ m or more and 500 ⁇ m or less.
- the stabilized zirconia contains at least the yttrium oxide in an amount of 12.0% by mass to 15.5% by mass, or the calcium oxide in an amount of 10.2% by mass to 11.4% by mass.
- a crucible having such characteristics can suppress the occurrence of cracks, chips, and the like during crystal growth.
- the crucible is a crucible for growing beta - type Ga2O3 single crystal as described above.
- the crucible is applied to a single crystal growth apparatus, for example, as shown in FIG. 1, for the purpose of growing and obtaining a beta-type Ga2O3 single crystal.
- the crucible according to this embodiment will be described in detail below by explaining the single crystal growth apparatus shown in FIG. 1.
- FIG. 1 is a schematic diagram illustrating the main parts of the single crystal growth apparatus used in the manufacturing method of the beta-type Ga2O3 single crystal substrate according to this embodiment, and the crucible of the first embodiment used in the single crystal growth apparatus.
- the single crystal growth apparatus 100 includes the crucible 5 described above, a crucible holder 6 that holds the crucible 5, and a heating device 7 that heats the crucible 5.
- the single crystal growth apparatus 100 may further include a sealed container 9 in which it is housed. There are no particular limitations on the dimensions and material of the sealed container 9, so long as it can house the single crystal growth apparatus 100 and the like and has the function of preventing impurities from entering from the outside.
- the crucible 5 includes a cylindrical seed crystal accommodation portion 51, an increased diameter portion 52 connected to the seed crystal accommodation portion 51, and a straight body portion 53 connected to the increased diameter portion 52.
- the seed crystal accommodation portion 51 is cylindrical, has a hollow portion that opens to the side connected to the increased diameter portion 52 and has a bottom wall formed on the side opposite to the increased diameter portion 52.
- the seed crystal accommodation portion 51 can accommodate and hold the seed crystal 8a in the hollow portion.
- the increased diameter portion 52 has a truncated cone shape that expands upward in the axial direction of the crucible 5, and is connected to the seed crystal accommodation portion 51 on the small diameter side of the increased diameter portion 52.
- the straight body portion 53 has a hollow cylindrical shape and is connected to the large diameter side of the increased diameter portion 52.
- the diameter increasing portion 52 and the straight body portion 53 have a function of holding a block of gallium trioxide bulk material (specifically, polycrystalline Ga2O3 . Hereinafter, also referred to as " Ga2O3 bulk material") therein.
- the diameter increasing portion 52 and the straight body portion 53 have a function of growing a beta-type Ga2O3 single crystal as a crystal by solidifying the gallium trioxide melt as described later.
- the crucible 5 has a thickness of 1 mm or more and 10 mm or less. More specifically, the side wall 5a of the seed crystal accommodation portion 51, the diameter increasing portion 52, and the straight body portion 53 of the crucible 5 all have a thickness of 1 mm or more and 10 mm or less. It is preferable that the side wall 5a of the seed crystal accommodation portion 51, the diameter increasing portion 52, and the straight body portion 53 of the crucible 5 all have a thickness of 5 mm or more and 10 mm or less. Furthermore, the maximum inner diameter of the crucible 5 is 100 mm or more. More specifically, it is preferable that the inner diameter of the straight body portion 53 of the crucible 5 is 100 mm or more. It is also preferable that the inner diameter of the straight body portion 53 of the crucible 5 is 150 mm or more. The upper limit of the maximum inner diameter of the crucible 5 is not particularly limited, but is, for example, 165 mm.
- the thickness of the crucible 5 is less than 1 mm, there is a possibility that cracking and chipping of the crucible 5 during crystal growth may not be sufficiently suppressed. There is also a possibility that the crucible 5 may be deformed during crystal growth. When the thickness of the crucible 5 exceeds 10 mm, there is a possibility that the adverse effect of the increase in the cost of the crucible 5 may outweigh the effect of cost reduction and the like obtained by suppressing cracking and chipping of the crucible 5 during crystal growth.
- the maximum inner diameter of the crucible 5 100 mm or more, it is possible to suppress cracking and chipping of the crucible 5 when manufacturing a large-diameter beta -type Ga2O3 single crystal substrate with a diameter of 4 inches or 6 inches.
- the composition of the crucible 5 is stabilized zirconia (hereinafter also referred to as "stabilized ZrO 2 ") containing both or either of yttrium oxide (yttria: Y 2 O 3 ) and calcium oxide (calcia: CaO).
- the composition of the crucible 5 is preferably stabilized ZrO 2 containing either Y 2 O 3 or CaO.
- the stabilized ZrO 2 contains at least 12.0 mass% to 15.5 mass% of Y 2 O 3 , or 10.2 mass% to 11.4 mass% of CaO.
- Stabilized ZrO2 refers to ZrO2 in which a high-temperature phase (typically a cubic or tetragonal solid solution) can exist stably up to room temperature by adding Y2O3 , CaO, magnesium oxide (MgO), aluminum oxide (alumina: Al2O3 ) , etc. to ZrO2 . Note that the oxides that are solid-solved in stabilized ZrO2 are not limited to Y2O3 , CaO, MgO , and Al2O3 .
- the surface on the inner circumferential surface side of the crucible is coated with a sprayed film containing both or either of Rh and Pt.
- the sprayed film is preferably made of a Pt-Rh alloy containing 10% by mass to 30% by mass of Rh.
- the crucible 5 of the first embodiment shown in FIG. 1 it is coated with a sprayed film 5b made of a platinum-rhodium alloy (Pt-Rh alloy) containing 10% by mass to 30% by mass of Rh.
- the thickness of the sprayed film 5b is 100 ⁇ m to 500 ⁇ m.
- the sprayed film 5b preferably coats the entire surface on the inner circumferential surface side of the crucible 5. However, even if a part of the surface is not coated with the sprayed film 5b or the composition of the sprayed film 5b is partially different, it does not deviate from the scope of the present disclosure.
- the above-mentioned thermal spraying can be performed by a conventionally known method, for example, plasma spraying.
- the above-mentioned thermal spraying can be performed by supplying the thermal spray material, which is made by heating the above-mentioned Pt-Rh alloy to molten particles or particles close to that (for example, particle diameter: 45 to 300 ⁇ m), toward the inner peripheral surface of the side wall portion 5a from a direction inclined at 30 to 45 degrees with respect to the axial direction of the crucible 5 using a thermal spray nozzle.
- the thickness of the thermal spray film 5b can be determined by controlling the supply speed of the thermal spray material.
- the supply speed of the thermal spray material may be 50 to 75 g/min.
- the porosity described later can be determined by controlling the angle of the thermal spray nozzle and the supply speed of the thermal spray material.
- the surface roughness Rz described later can be increased by increasing the particle diameter of the thermal spray material.
- the Rh content in the Pt-Rh alloy that constitutes the sprayed film 5b be 10 mass% or more, cracking and chipping of the crucible 5 during crystal growth can be more adequately suppressed.
- the Rh content in the Pt-Rh alloy that constitutes the sprayed film 5b be 30 mass% or less, cracking and chipping of the crucible 5 during crystal growth can be more adequately suppressed without increasing the cost of the crucible 5. It is more preferable that the sprayed film 5b be made of a Pt-Rh alloy containing 20 mass% or more and 30 mass% or less of Rh.
- the sprayed film 5b may peel off from the side wall portion 5a, and cracking and chipping of the crucible 5 during crystal growth may not be sufficiently suppressed. If the thickness of the sprayed film 5b exceeds 500 ⁇ m, the adverse effect of increased cost of the crucible 5 may outweigh the cost reduction and other benefits obtained by suppressing cracking and chipping of the crucible 5 during crystal growth.
- the thickness of the sprayed film 5b is preferably 200 ⁇ m or more and 500 ⁇ m or less.
- the thickness of the sprayed coating is measured in accordance with JIS H 8401:1999 (Testing method for thickness of sprayed products). Specifically, it can be measured by a direct method using a micrometer (for example, product name (product number): "U-shaped micrometer PMU100-25" manufactured by Mitutoyo Corporation, or product name (product number): "Laser digital micrometer LSM-501S” manufactured by Mitutoyo Corporation) to determine the difference between the crucible thickness before spraying and the crucible thickness after spraying.
- the concentration of Rh in the Pt-Rh alloy can be determined when preparing the sprayed material.
- the sprayed film preferably has pores.
- the porosity which is the volume ratio of the pores in the sprayed film, is preferably 30% by volume or more and 50% by volume or less. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- FIG. 2 is an enlarged cross-sectional view of a main part for explaining a main part of a crucible of a second embodiment used in the single crystal growth apparatus of FIG. 1.
- the sprayed film 5b present on the inner peripheral surface side of the side wall portion 5a has pores 5c.
- the porosity which is the volume ratio of the pores 5c in the sprayed film 5b, is preferably 30% by volume or more and 50% by volume or less.
- the porosity is measured in accordance with JIS K 7112:1999 Method A (underwater displacement method). Specifically, the density of the crucible is first measured before and after spraying to calculate the actual density of the sprayed film. The composition of the sprayed film is then determined using an energy dispersive X-ray device attached to a transmission electron microscope (SEM-EDX: Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy), and the ideal density is calculated from this composition. The porosity can be calculated by dividing the actual density by the ideal density x 100.
- the crucible of the second embodiment is made of the above-mentioned stabilized ZrO2, it is difficult to deform due to thermal contraction during crystal growth and cooling after crystal growth.
- the beta-type Ga2O3 single crystal present in the crucible presses the side wall portion 5a due to some thermal contraction of the crucible, especially during cooling after crystal growth, the pores 5c contained in the sprayed film 5b are crushed, thereby suppressing the occurrence of cracks, chipping, etc. of the crucible.
- the porosity is less than 30% by volume, the effect of suppressing cracks and chipping of the crucible by only crushing the pores 5c may not be sufficient.
- the porosity is more than 50% by volume, it may be difficult to spray such a sprayed film 5b on the side wall portion 5a.
- FIG. 3 is an enlarged cross-sectional view of a main part of a crucible of a third embodiment used in the single crystal growth apparatus of FIG. 1. In the crucible of the third embodiment shown in FIG.
- the surface roughness Rz of the surface on the inner peripheral surface side of the side wall portion 5a is 300 ⁇ m or more and 500 ⁇ m or less.
- the sprayed film 5b on the inner peripheral surface side of the side wall portion 5a has pores 5c.
- the porosity which is the volume ratio of pores 5c in the sprayed film 5b, is 10 vol.% or more and less than 30 vol.%.
- the surface roughness Rz of the inner peripheral surface of the side wall portion 5a is preferably 300 ⁇ m or more and 400 ⁇ m or less.
- the method for measuring the surface roughness Rz of the inner peripheral surface of the side wall portion 5a is as follows. That is, the surface roughness Rz can be measured by determining the maximum height (Rz) of the inner peripheral surface of the side wall portion 5a as defined in JIS B0601:2001.
- a surface roughness measuring instrument product name (product number): "Surface roughness measuring instrument SV-2100M4" manufactured by Mitutoyo Corporation, or product name (product number): "Surface roughness measuring instrument SURFCOM TOUCH 550" manufactured by Tokyo Seimitsu Co., Ltd.
- the surface roughness Rz can be measured by setting a measuring unit inside the crucible and performing roughness measurement using a display/control unit.
- the method for measuring the porosity can be the same as the method for measuring the porosity of the sprayed film of the crucible of the second embodiment.
- the crucible of the third embodiment is made of the above-mentioned stabilized ZrO2, so that it is difficult to deform due to thermal contraction during crystal growth and cooling after crystal growth.
- the beta-type Ga2O3 single crystal in the crucible presses the side wall portion 5a due to some thermal contraction of the crucible, especially during cooling after crystal growth, the convex portion existing on the surface of the inner peripheral surface side of the side wall portion 5a is crushed based on the surface roughness, so that the occurrence of cracks, chips, etc. of the crucible can be suppressed.
- the pores 5c contained in the sprayed film 5b are crushed, so that the occurrence of cracks, chips, etc. of the crucible can also be suppressed.
- the effect of suppressing cracks and chips of the crucible due to the convex portion being crushed may not be sufficient. If the surface roughness Rz exceeds 500 ⁇ m, the strength of the crucible itself is reduced, which may cause the convex parts to break during crystal growth, leading to cracks and chipping of the crucible. Furthermore, if the porosity is less than 10% by volume, the effect of suppressing cracks and chipping of the crucible due to crushing of the pores 5c may not be sufficient.
- the surface roughness Rz of the surface is 300 ⁇ m or more and 500 ⁇ m or less. This makes it possible to further suppress the occurrence of cracks, chipping, etc. during crystal growth based on the presence of the above-mentioned surface protrusions and voids 5c.
- the surface roughness Rz be 300 ⁇ m or more, the effect of suppressing cracking and chipping of the crucible due to the convex parts being crushed can be sufficiently obtained.
- the surface roughness Rz be 500 ⁇ m or less, the effect of suppressing cracking and chipping of the crucible during crystal growth, etc. can be sufficiently obtained without reducing the strength of the crucible itself.
- the aspect in which the surface roughness Rz of the surface is 300 ⁇ m or more and 500 ⁇ m or less can have the same configuration as the aspect in which the porosity is 30 volume % or more and 50 volume % or less in the crucible of the third embodiment.
- the sprayed film is preferably made of a first film and a second film.
- the first film preferably covers the surface.
- the first film is preferably made of Rh or a Pt-Rh alloy mainly composed of Rh.
- the second film preferably covers the first film.
- the second film is preferably made of Pt or a Pt-Rh alloy mainly composed of Pt.
- the thickness of the sprayed film is preferably 100 ⁇ m or more and 500 ⁇ m or less in total including the first film and the second film. This not only suppresses the occurrence of cracks, chips, etc. during crystal growth, but also suppresses the incorporation of Rh into the beta type Ga 2 O 3 single crystal.
- FIG. 4 is an enlarged cross-sectional view of a main part of a crucible of a fourth embodiment used in the single crystal growth apparatus of FIG. 1.
- the sprayed film is made of a first film 5b1 and a second film 5b2.
- the first film 5b1 covers the surface on the inner circumferential side of the side wall portion 5a.
- the first film 5b1 is made of Rh or a Pt-Rh alloy mainly composed of Rh, and is preferably made of Rh, for example.
- the second film 5b2 covers the first film 5b1.
- the second film 5b2 is made of Pt or a Pt-Rh alloy mainly composed of Pt, and is preferably made of Pt, for example.
- the thickness of the sprayed film is 100 ⁇ m or more and 500 ⁇ m or less, in total, for the first film 5b1 and the second film 5b2. It is more preferable that the thickness of the above-mentioned sprayed film is 100 ⁇ m or more and 300 ⁇ m or less in total of the first film 5b1 and the second film 5b2. If the total thickness of the first film 5b1 and the second film 5b2 is less than 100 ⁇ m, the first film 5b1 and the second film 5b2 may peel off from the side wall portion 5a, and the effect of suppressing cracking and chipping of the crucible 5 during crystal growth based on the sprayed film being composed of the first film 5b1 and the second film 5b2 may not be sufficient.
- the adverse effect of increasing the cost of the crucible 5 may outweigh the effect of reducing costs and the like obtained by suppressing cracking and chipping of the crucible 5 during crystal growth.
- the method for measuring the thickness of the first film and the second film can be the same as the method for measuring the thickness of the sprayed film of the crucible in the first embodiment.
- both the first film 5b1 and the second film 5b2 have pores 5c.
- the first film porosity which is the volume ratio of the pores 5c in the first film 5b1
- the second film porosity which is the volume ratio of the pores 5c in the second film 5b2
- the method for measuring the first film porosity and the second film porosity can be the same as the method for measuring the porosity of the sprayed film of the crucible in the second embodiment.
- the sprayed film is made of the first film 5b1 and the second film 5b2.
- the first film 5b1 is made of Rh or a Pt-Rh alloy mainly composed of Rh
- the second film 5b2 is made of Pt or a Pt-Rh alloy mainly composed of Pt.
- the first film 5b1 covers the inner peripheral surface of the side wall 5a
- the second film 5b2 covers the first film 5b1. Therefore, the Rh in the sprayed film does not directly contact the beta type Ga 2 O 3 single crystal in the crucible, or even if it does, the amount of contact is very small, so that it is possible to suppress the incorporation of Rh into the beta type Ga 2 O 3 single crystal during crystal growth, etc.
- the sprayed film is composed of the first film 5b1 and the second film 5b2. Therefore, by considering the first film 5b1 and the second film 5b2 together, the sprayed film can be composed of a Pt-Rh alloy containing 10% by mass or more and 30% by mass or less of Rh.
- the sprayed film can be composed of the first film 5b1 composed of Rh and the second film 5b2 composed of Pt, and the thickness of the first film 5b1 can be one-third that of the second film 5b2.
- the crucible of the fourth embodiment can include a sprayed film composed of a Pt-Rh alloy containing 10% by mass or more and 30% by mass or less of Rh.
- the thickness of the sprayed film is 100 ⁇ m or more and 500 ⁇ m or less, the total thickness of the first film 5b1 and the second film 5b2.
- the surface roughness Rz of the surface on the inner peripheral side is preferably 300 ⁇ m or more and 500 ⁇ m or less.
- both the first film and the second film have pores.
- the first film porosity, which is the volume ratio of the pores in the first film, and the second film porosity, which is the volume ratio of the pores in the second film are both preferably 10 volume% or more and less than 30 volume%. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth.
- Figure 5 is an enlarged cross-sectional view of the main part of a crucible of the fifth embodiment used in the single crystal growth apparatus of Figure 1.
- the surface roughness Rz of the surface on the inner peripheral side of the side wall portion 5a is 300 ⁇ m or more and 500 ⁇ m or less.
- the first film 5b1 and the second film 5b2 on the inner circumferential surface side of the side wall portion 5a each have pores 5c.
- the first film porosity and the second film porosity, which are the volume ratios of the pores 5c in the first film 5b1 and the second film 5b2, are 10 volume % or more and less than 30 volume %.
- the surface roughness Rz of the surface on the inner circumferential surface side of the side wall portion 5a is preferably 300 ⁇ m or more and 400 ⁇ m or less.
- the occurrence of cracks, chipping, etc. during crystal growth can be further suppressed based on the presence of the convex parts and holes 5c on the inner peripheral surface side.
- the Rh in the sprayed film does not directly contact the beta type Ga2O3 single crystal in the crucible, or even if it does, the contact is very slight, so that it is possible to suppress the incorporation of Rh into the beta type Ga2O3 single crystal during crystal growth, etc.
- the surface roughness Rz of the surface is 300 ⁇ m or more and 500 ⁇ m or less. This makes it possible to further suppress the occurrence of cracks, chips, etc. during crystal growth based on the presence of the above-mentioned surface protrusions and voids 5c.
- the embodiment in which the surface roughness Rz of the surface is 300 ⁇ m or more and 500 ⁇ m or less has the same configuration as the embodiment in which the first membrane porosity and the second membrane porosity are 30 volume % or more and 50 volume % or less, respectively, in the crucible of the fifth embodiment.
- the single crystal growth apparatus 100 includes a crucible holder 6 for holding a crucible 5.
- the crucible holder 6 is in contact with the bottom of the crucible 5 to hold the crucible 5.
- the crucible holder 6 may have a cylindrical appearance.
- the material of the crucible holder 6 is not particularly limited, but may be, for example, quartz, alumina, zirconia, silicon carbide, or the like.
- the outer diameter of the crucible holder 6 depends on the diameter of the crucible 5 to be supported, but is, for example, 75 mm or more and 200 mm or less.
- the heating device 7 is installed for the purpose of heating the crucible 5.
- the heating device 7 can be, for example, a conventionally known electric heater (hereinafter, also simply referred to as "heater”).
- the heater is, for example, two units, and the two units are arranged to surround the outer periphery of the crucible 5.
- the output of the heater may be controlled independently for each unit.
- the heater may be divided into a plurality of parts in a direction perpendicular to the axis of the crucible 5 for each unit, thereby forming a multi-stage structure. In this case, it is preferable that the output of the heater is controlled independently for each of the multi-stage parts.
- the heater output is controlled independently for each of the multi-stage parts to heat the diameter-increasing portion 52 and the straight body portion 53, thereby stabilizing the growth rates of the crystals growing in the diameter-increasing portion 52 and the straight body portion 53.
- the single crystal growth apparatus 100 can be equipped with a thermocouple capable of measuring the temperature of the crucible 5 heated by the heater.
- a plurality of thermocouples may be arranged on the outside of the crucible 5 along the axial direction.
- the thermocouple may be, for example, a known temperature monitor.
- the manufacturing method of the beta-type gallium trioxide single crystal substrate (beta-type Ga 2 O 3 single crystal substrate) according to this embodiment is preferably a beta-type Ga 2 O 3 single crystal substrate using the crucible described above. That is, the manufacturing method preferably includes a step of preparing the crucible, a step of obtaining a beta-type gallium trioxide single crystal (beta-type Ga 2 O 3 single crystal) by a vertical boat method using the crucible, and a step of obtaining a beta-type Ga 2 O 3 single crystal substrate having a circular main surface by processing the beta-type Ga 2 O 3 single crystal.
- the manufacturing method of the beta-type Ga 2 O 3 single crystal substrate having such characteristics reduces the cracking and chipping of the crucible during crystal growth, etc., so that the beta-type Ga 2 O 3 single crystal substrate can be obtained with a high yield.
- Fig. 6 is a flow chart showing an example of a method for manufacturing a beta type Ga2O3 single crystal substrate according to this embodiment.
- the method for manufacturing a beta type Ga2O3 single crystal substrate according to this embodiment preferably includes a beta type Ga2O3 single crystal manufacturing step S100 and a beta type Ga2O3 single crystal substrate manufacturing step S200 shown in the flow chart of Fig. 6. According to Fig.
- the method for manufacturing a beta type Ga2O3 single crystal substrate preferably includes, more specifically, as the beta type Ga2O3 single crystal manufacturing step S100, a step (first step: preparation step S110) of preparing a single crystal growth apparatus including at least a cylindrical crucible and a heating device arranged so as to surround the outer periphery of the crucible.
- a seed crystal and a block-shaped Ga2O3 bulk body are preferably also prepared.
- the beta type Ga2O3 single crystal manufacturing process S100 preferably includes a step (second step: raw material charging step S120) of accommodating the seed crystal at the bottom of the crucible and accommodating the Ga2O3 bulk body above the seed crystal in the crucible.
- the Ga2O3 bulk body is preferably accommodated above the seed crystal in the crucible.
- the beta type Ga2O3 single crystal manufacturing process S100 preferably includes a step (third step: raw material melting step S130) of heating the crucible with the heating device, melting a part of the Ga2O3 bulk body and the seed crystal to obtain a Ga2O3 melt, and contacting the Ga2O3 melt with the remaining part of the seed crystal.
- the beta-type Ga2O3 single crystal manufacturing process S100 preferably includes a process (fourth process: Ga2O3 single crystal growing process S140) of obtaining a beta-type Ga2O3 single crystal by growing a crystal from the Ga2O3 melt on the remaining part of the seed crystal.
- the manufacturing method of the beta type Ga2O3 single crystal substrate according to this embodiment can include a cutting step, a peripheral grinding step, and a polishing step as described below as a beta type Ga2O3 single crystal substrate manufacturing step S200.
- the above steps are performed in this order to obtain a beta type Ga2O3 single crystal substrate.
- a crucible 5 applied to the single crystal growth apparatus 100 shown in Fig. 1 is used to grow a beta type Ga2O3 single crystal by the vertical boat method.
- the vertical boat method is abbreviated as the VB method.
- the VB method includes the vertical Bridgman method and the vertical temperature gradient solidification method.
- ⁇ Beta type Ga2O3 single crystal manufacturing process S100> (Preparation step S110) As shown in Fig. 1 and Fig. 6, in the beta type Ga2O3 single crystal manufacturing process S100, a process (preparation process S110) of preparing a single crystal growth apparatus 100 including at least a cylindrical crucible 5 and a heating device 7 arranged so as to surround the outer periphery of the crucible 5 is first performed. In the preparation process S110, in addition to the above-mentioned single crystal growth apparatus 100 for manufacturing the beta type Ga2O3 single crystal 81 , it is preferable that a seed crystal 8a and a block-shaped Ga2O3 bulk body are also prepared.
- the seed crystal 8a is made of a beta type Ga2O3 single crystal.
- the Ga2O3 bulk body may be made of polycrystalline Ga2O3 .
- the seed crystal 8a and the block-shaped Ga2O3 bulk body may be prepared by a conventionally known method or by obtaining commercially available products.
- the crucible 5 is prepared as any one of the crucibles of the first to fifth aspects described above.
- the above-mentioned features can be provided by using a conventionally known method. That is, a crucible 5 having a side wall portion 5a with a thickness of 1 to 10 mm and an inner diameter of the straight body portion 53 of 100 mm or more can be manufactured by a conventionally known method.
- the composition of the crucible 5 can be, for example, stabilized ZrO 2 containing at least 12.0 mass % to 15.5 mass % Y 2 O 3 or 10.2 mass % to 11.4 mass % CaO.
- thermal spray material Pt-Rh alloy thermal spray material containing 10-30 mass% Rh Particle size: 45-300 ⁇ m Supply rate of thermal spray material: 50 to 75 g/min. Orientation of thermal spray nozzle: 30 to 45 degrees with respect to the axial direction of the crucible. Distance between the thermal spray nozzle and the inner peripheral surface of the side wall of the crucible: 20 to 120 mm.
- the thickness of the sprayed film 5b can be set to, for example, 100 to 500 ⁇ m.
- the porosity in the sprayed film 5b can be adjusted to 10 to 50 volume %.
- the surface roughness Rz of the surface on the inner circumferential side of the side wall portion 5a of the crucible 5 can be adjusted to 300 to 500 ⁇ m.
- a first spray material made of Rh or a Pt-Rh alloy mainly composed of Rh and having a particle size of 45 to 300 ⁇ m, and a second spray material made of a Pt-Rh alloy mainly composed of Pt and having a particle size of 45 to 300 ⁇ m can be used as the spray material.
- the surface on the inner circumferential side of the side wall portion 5a of the crucible 5 can be coated with a first film.
- the first film can be coated with a second film.
- the raw material charging step S120 is a step of placing the seed crystal at the bottom of the crucible and placing a block-shaped Ga 2 O 3 bulk body above the seed crystal in the crucible. In S120, it is preferable that solid B2O3 is also accommodated in the crucible 5 above the seed crystal 8a along with the massive Ga2O3 bulk body. In the raw material charging step S120, various raw materials for crystal growth are charged into the crucible using the growth apparatus 100. First, beta-type Ga 2 A seed crystal 8a consisting of an O3 single crystal is charged.
- a plurality of Ga2O3 bulk bodies made of polycrystalline Ga2O3 are charged into the diameter increasing portion 52 and the straight body portion 53 of the crucible 5 and stacked.
- the raw material charging step S120 When a plurality of Ga2O3 bulk bodies are charged into the crucible 5, it is preferable to add a predetermined amount of Sn or Si. This makes it possible to obtain a beta type Ga2O3 single crystal by the beta type Ga2O3 single crystal manufacturing process S100. From the Ga 2 O 3 single crystal 81, a beta type Ga 2 O 3 single crystal substrate containing the above Sn or Si as a dopant is obtained.
- the concentration of the dopant is, for example, 1.0 ⁇ 10 18 cm ⁇ 3 (5.0 ⁇ 10 17 cm ⁇ 3 or more and 4.0 ⁇ 10 It is preferable to adjust the amount of addition so that the density of the SiO 2 is 19 cm ⁇ 3 or less.
- the raw material melting step S130 is a step of heating the crucible with the heating device, melting the Ga2O3 bulk body and a part of the seed crystal to obtain a Ga2O3 melt, and bringing the Ga2O3 melt into contact with the remaining part of the seed crystal.
- the purpose of the raw material melting step S130 is to melt the Ga2O3 bulk body and a part of the seed crystal 8a to bring the remaining part of the seed crystal 8a into contact with the Ga2O3 melt 82 when growing a crystal using the single crystal growing apparatus 100. This allows a beta-type Ga2O3 single crystal 81 to be grown on the remaining part of the seed crystal 8a in the next step, the Ga2O3 single crystal growing step S140.
- the crucible 5 containing the seed crystal 8a and the Ga2O3 bulk body therein is supported by the crucible holder 6. Then, a current is supplied to the heating device 7 to heat the crucible 5. This melts the Ga2O3 bulk body to become a Ga2O3 melt 82. Next, a part of the seed crystal 8a also melts, and the remaining part of the seed crystal 8a and the Ga2O3 melt 82 come into contact with each other at the interface.
- the Ga2O3 single crystal growth step S140 is a step of growing a crystal from the Ga2O3 melt on the remaining part of the seed crystal to obtain a beta type Ga2O3 single crystal.
- the crucible 5 is gradually lowered downward (towards the seed crystal housing part 51) along its axis relative to the heating device 7, so that a temperature gradient is formed in the crucible 5 such that the temperature on the seed crystal 8a side is low and the temperature on the Ga2O3 melt 82 side is high.
- the Ga2O3 melt 82 in contact with the seed crystal 8a is solidified, and the beta type Ga2O3 single crystal 81 to be continuously grown from the Ga2O3 melt 82 on the remaining part of the seed crystal 8a.
- the temperature on the Ga2O3 melt 82 side is, for example, 1800 to 1820° C.
- the temperature gradient at the interface between the Ga2O3 melt 82 and the growing beta type Ga2O3 single crystal 81 is, for example, 3 to 8° C./cm.
- the speed at which the crucible 5 is pulled downward along its axis is not particularly limited, but can be, for example, 0.1 to 2 mm/hour.
- the crucible 5 is pulled downward along its axis relative to the heating device 7, so that the interface between the beta type Ga2O3 single crystal 81 and the Ga2O3 melt 82 rises to the liquid B2O3 side , and the Ga2O3 melt 82 is solidified as the beta type Ga2O3 single crystal 81.
- the crystal growth of the beta type Ga2O3 single crystal 81 continues until the solidification of the Ga2O3 melt 82 remaining in the straight body part 53 of the crucible 5 is completed. In this manner, an ingot of the beta type Ga2O3 single crystal 81 can be obtained.
- the manufacturing method of the beta type Ga2O3 single crystal substrate includes a step (beta type Ga2O3 single crystal substrate manufacturing step S200) of obtaining a beta type Ga2O3 single crystal substrate having a circular main surface by processing the beta type Ga2O3 single crystal obtained by the Ga2O3 single crystal growth step S140 as shown in Fig. 6.
- the beta type Ga2O3 single crystal substrate manufacturing step S200 includes the following cutting step, outer circumference grinding step, and polishing step, and the beta type Ga2O3 single crystal substrate can be obtained by performing these steps in this order.
- the cutting step is a step of slicing the ingot made of the beta type Ga 2 O 3 single crystal taken out of the crucible into a wafer having a predetermined thickness in order to obtain a beta type Ga 2 O 3 single crystal substrate from the ingot.
- the outer periphery grinding step is a step of obtaining a beta type Ga 2 O 3 single crystal substrate having a main surface having a circular shape by grinding the outer periphery of the wafer.
- the outer periphery grinding step may include, for example, a step of performing chamfering.
- the cutting step and the outer periphery grinding step may use a conventionally known cutting method and outer periphery grinding method.
- the polishing step is a step of mirror-finishing the center part of the main surface.
- the polishing step may use a conventionally known polishing method.
- the center part may have a surface roughness Ra of 10 nm or less as specified in, for example, JIS B 0681-2:2018.
- the beta type Ga2O3 single crystal substrate according to this embodiment is manufactured.
- the beta type Ga2O3 single crystal is manufactured using any one of the crucibles of the first to fifth aspects described above, so that the crucible is less likely to break or chip during crystal growth. Therefore, the beta type Ga2O3 single crystal substrate can be obtained with a high yield.
- the beta-type gallium trioxide single crystal substrate (beta-type Ga2O3 single crystal substrate) according to this embodiment is a beta-type Ga2O3 single crystal substrate having a circular main surface.
- the diameter of the beta-type Ga2O3 single crystal substrate is 100 mm or more.
- the main surface is the (001) plane of the beta-type Ga2O3 single crystal.
- the main surface is a plane having an off angle of more than 0° and not more than 10° from the (001) plane of the beta-type Ga2O3 single crystal, and an off direction in the [010] direction of the beta -type Ga2O3 single crystal or a direction perpendicular to the [010] direction.
- the beta-type Ga2O3 single crystal substrate contains both or either one of rhodium (Rh) and iridium (Ir).
- Rh rhodium
- Ir iridium
- the Rh concentration and the Ir concentration are each less than 3 ppm by mass as measured by glow discharge mass spectrometry (GDMS).
- GDMS glow discharge mass spectrometry
- the beta type Ga2O3 single crystal substrate having such characteristics contains very small amounts of the Rh and Ir, and therefore has excellent electrical and optical properties.
- the present inventors have focused on making the concentration of rhodium and iridium, which may be contained in the beta type Ga2O3 single crystal substrate and may inhibit the good electrical and optical properties of the substrate because they are not of the same group as gallium ( Ga ), extremely small in the substrate.
- Rh and Ir are prevented from directly contacting the beta type Ga2O3 single crystal and the Ga2O3 melt that is the raw material for the beta type Ga2O3 single crystal.
- a beta type Ga2O3 single crystal is produced using the crucible of the fifth embodiment described above, and a beta type Ga2O3 single crystal substrate is obtained from the beta type Ga2O3 single crystal.
- the inventors have devised a beta type Ga 2 O 3 single crystal substrate in which the Rh concentration and the Ir concentration are both less than 3 mass ppm, and have completed the present disclosure.
- ⁇ Diameter> 7 is a schematic diagram for explaining the beta type Ga2O3 single crystal substrate according to this embodiment.
- the diameter is 100 mm or more.
- the diameter of the beta type Ga2O3 single crystal substrate 1 is preferably 100 mm or more and 155 mm or less.
- the beta type Ga2O3 single crystal substrate 1 having a diameter of 100 mm or more and 155 mm or less is preferably 101.6 mm or 152.4 mm, in other words, preferably 4 inches or 6 inches.
- the large-diameter beta type Ga2O3 single crystal substrate having a diameter of 100 mm or more and 155 mm or less can be excellent in both electrical properties and optical properties.
- the diameter of the beta-type Ga2O3 single crystal substrate is determined based on the circular shape before the formation of the orientation flat (hereinafter also referred to as "OF"), index flat (hereinafter also referred to as “IF”), etc., even if the main surface does not have a geometrically circular shape due to the influence of the orientation flat (hereinafter also referred to as "OF"), index flat (hereinafter also referred to as "IF”), etc.
- the diameter of the beta-type Ga2O3 single crystal substrate can be measured by using a conventionally known outer diameter measuring device such as a caliper. The definition of "circular shape” representing the shape of the main surface in this specification will be described later.
- the beta-type Ga2O3 single crystal substrate 1 has a circular main surface 10 as described above.
- the term "circular shape" representing the shape of the main surface includes a geometrical circular shape, as well as a shape in which the main surface does not form a geometrical circular shape due to at least one of a notch, OF, or IF being formed on the periphery of the main surface 10.
- shape in which the main surface does not form a geometrical circular shape refers to a shape in which, among the line segments extending from any point on the periphery of the main surface 10 to the center of the main surface 10, the line segments extending from any point on the notch, OF, and IF to the center of the main surface are shorter in length.
- shape in which the main surface does not form a geometrical circular shape also includes a shape in which the lengths of all the line segments extending from any point on the periphery of the main surface 10 to the center of the main surface 10 are not necessarily the same due to the shape of the beta-type Ga2O3 single crystal that is the raw material of the beta -type Ga2O3 single crystal substrate 1.
- the center of the main surface 10 refers to the position of the center of gravity
- the diameter of the beta-type Ga2O3 single crystal substrate 1 refers to the length of the longest line segment that extends from any point on the outer periphery of the beta-type Ga2O3 single crystal substrate 1, passing through the center of the main surface 10, to another point on the outer periphery.
- the main surface 10 is the (001) plane of the beta type Ga2O3 single crystal.
- the main surface 10 is a plane having an off angle of more than 0° and not more than 10° from the (001) plane of the beta type Ga2O3 single crystal, and an off direction in the [010] direction of the beta type Ga2O3 single crystal or a direction perpendicular to the [010] direction.
- the crystal plane of the main surface 10 has a precision error of ⁇ 0.5°.
- the main surface 10 when the main surface 10 is the "(001) plane" of a beta-type Ga2O3 single crystal, it means that the main surface 10 may be a (001) just plane, or the main surface 10 may be a plane having an off angle of -0.5 to +0.5° from the (001) plane.
- the off angle and off direction from the (001) plane on the main surface 10 of the beta-type Ga2O3 single crystal substrate 1 can be measured by using a conventionally known crystal orientation measuring device (for example, product name (product number): "FSASIII", manufactured by Rigaku Corporation).
- the beta type Ga2O3 single crystal substrate contains both or either of rhodium (Rh) and iridium (Ir).
- the concentration of Rh and the concentration of Ir are both less than 3 mass ppm in GDMS.
- the concentration of Rh and the concentration of Ir are both preferably 1 mass ppm or less in GDMS, more preferably 0.1 mass ppm or less, and even more preferably 0.01 mass ppm or less.
- the lower limit of the concentration of Rh and the concentration of Ir is that they are not detected in GDMS.
- the beta type Ga2O3 single crystal substrate can be excellent in both electrical properties and optical properties by having the Rh and Ir be less than 3 mass ppm.
- the Rh and Ir are known elements that may be contained in the beta type Ga2O3 single crystal substrate.
- the concentration of Rh and the concentration of Ir can be easily made less than 3 mass ppm in GDMS based on the material of the crucible and the structure of the sprayed film consisting of the first film and the second film. Therefore, the beta type Ga2O3 single crystal substrate excellent in both electrical properties and optical properties can be obtained with good yield.
- GDMS Glow Discharge Mass Spectroscopy
- GDMS Glow Discharge Mass Spectroscopy
- a method for measuring the concentrations of Rh and Ir in the beta-type Ga2O3 single crystal substrate using glow discharge mass spectrometry (GDMS) will be described.
- GDMS refers to a technique in which a glow discharge plasma is generated using an analytical sample as a cathode in a high-purity argon atmosphere, and the surface of the analytical sample is sputtered in the plasma, and the ionized constituent elements in the analytical sample are measured with a mass spectrometer. This makes it possible to qualitatively and quantitatively determine impurity elements, including Rh and Ir, other than Ga and O contained in the beta -type Ga2O3 single crystal substrate.
- the ion source for the GDMS either a flat cell or a pin-shaped cell is applied.
- the pin-shaped cell can be applied to an analytical sample that can be formed into a strip shape of approximately 2 mm square and 20 mm long. Specifically, it is used when analyzing Si single crystals, gallium arsenide (GaAs) single crystals, indium phosphide (InP) single crystals, etc., which can be prepared by cleavage.
- the flat cell can be applied to an analytical sample that can be formed into a disk shape with a diameter of about 10 mm, for example, when analyzing a polycrystalline body.
- the beta-type Ga2O3 single crystal substrate can be used to prepare a pin-shaped analytical sample with the cleavage in the longitudinal direction, it is preferable to prepare an analytical sample in the shape of a pin-shaped cell from the beta-type Ga2O3 single crystal substrate and use this as the ion source of the GDMS.
- the GDMS can be carried out, for example, as follows. First, a beta type Ga2O3 single crystal substrate is obtained by the manufacturing method described later. The beta type Ga2O3 single crystal substrate is then cleaved in the longitudinal direction to obtain a rectangular Ga2O3 analysis sample having a size of 2 mm square and a length of 20 mm, which is then placed on the sample placement section of the apparatus described below. Here, it is preferable to clean the sample placement section in accordance with a conventional method to prevent contamination and to remove foreign matter, and to perform pre-sputtering for 60 minutes. The analysis value during pre-sputtering is the background.
- GDMS can be performed on the Ga2O3 analysis sample placed on the sample placement surface under the following conditions.
- Rh and Ir which are elements other than Ga and O among the constituent elements of the Ga2O3 analysis sample
- semi - quantitative values can be calculated by correcting the ion intensity ratio between Ga and Rh or the ion intensity ratio between Ga and Ir with a relative sensitivity factor (RSF).
- RSF relative sensitivity factor
- values built into the software attached to the following device can be used.
- Glow discharge mass spectrometer product name (product number): VG-9000, manufactured by VG Elemental
- Ion source Pin cell (cooled with liquid nitrogen during analysis)
- Discharge area diameter 10mm
- Discharge gas High purity argon (6N grade)
- Discharge conditions 2 mA, 1 kV (constant current mode)
- Detector Faraday cup and multiplier.
- Mass resolution 4000 or more m/ ⁇ m (high resolution mode).
- the detection limit of the GDMS is preferably 0.01 mass ppm.
- the transmittance for light having a wavelength of 400 nm or more and 430 nm or less is preferably 70% or more.
- the carrier concentration measured at 25°C in the Hall measurement by the Van der Pauw method is preferably 1 x 1017 cm -3 or more and 1.0 x 1019 cm -3 or less. This makes it possible to achieve better electrical and optical properties.
- the transmittance for light having a wavelength of 400 nm or more and 430 nm or less is preferably 70% or more.
- the transmittance is more preferably 75% or more, and even more preferably 80% or more.
- the upper limit of the transmittance is 100%, which is an ideal value.
- the transmittance can be obtained by measuring the transmittance of light for the beta type Ga2O3 single crystal substrate measured using an ultraviolet-visible-infrared spectrophotometer or the like. Hereinafter, the procedure for specifically obtaining the transmittance will be described with reference to FIG. 7.
- one beta type Ga2O3 single crystal substrate 1 is obtained based on the above-mentioned manufacturing method. From this one beta type Ga2O3 single crystal substrate 1, a rectangular slice 10a (for example, 600 ⁇ m thick) with a size of 20 mm length x 20 mm width centered on its center O (for example, the center O of the main surface 10) is prepared, thereby obtaining a sample for transmittance measurement.
- a rectangular slice 10a for example, 600 ⁇ m thick
- its center O for example, the center O of the main surface 10
- the carrier concentration measured at 25°C in the Hall measurement by the Van der Pauw method is preferably 1x1017cm -3 or more and 1.0x1019cm -3 or less.
- the carrier concentration measured at 25°C in the Hall measurement by the Van der Pauw method using the center of the beta type Ga2O3 single crystal substrate as the measurement target is preferably 1x1017cm -3 or more and 1.0x1019cm-3 or less. If the carrier concentration is less than 1.0x1017cm-3 , when a semiconductor device is created, no current flows, and the device may not operate.
- the carrier concentration exceeds 1.0x1019cm -3 , it suggests that the crystal contains 1.0x1019cm -3 or more of inactive impurities, which may adversely affect the operation of the device.
- the carrier concentration is more preferably 5.0 ⁇ 10 17 cm -3 or more and 3.8 ⁇ 10 18 cm -3 or less. This allows the n-type beta type Ga 2 O 3 single crystal substrate to have good electrical characteristics that can be used for various electronic devices and optical devices.
- the carrier concentration can be determined by the following measurement method.
- FIG. 8 is an explanatory diagram for explaining a Hall measurement sample prepared using the center of a beta type Ga2O3 single crystal substrate according to this embodiment in order to measure the carrier concentration in the substrate.
- a single beta type Ga2O3 single crystal substrate 1 is obtained based on the above-mentioned manufacturing method, for example.
- a rectangular slice 10a (for example, 600 ⁇ m thick) having a length of 4 mm and a width of 4 mm is prepared with its center O (for example, the center O of the main surface 10) as the center.
- electrodes 21 made of an alloy containing gold and titanium are formed at the four corners of the rectangular slice 10a (surface to be measured), thereby obtaining a Hall measurement sample.
- the shape of the electrode 21 is not limited to the rectangular shape shown in the figure, and may be a sector shape or a circle.
- the carrier concentration can be obtained by applying Hall measurement by the Van der Pauw method to the rectangular piece 10a equipped with such electrodes 21 in an atmosphere of 25° C.
- the carrier concentration obtained by using the rectangular piece as the measurement object is defined as the carrier concentration of the beta-type Ga2O3 single crystal substrate measured at 25° C. in Hall measurement by the Van der Pauw method.
- the beta type Ga2O3 single crystal substrate according to this embodiment has excellent electrical and optical properties, and can be used as a substrate for forming optical devices and electronic devices.
- the beta type Ga2O3 single crystal substrate is preferably used as a substrate for forming electronic devices based on its excellent electrical properties .
- a single crystal manufacturing apparatus as shown in FIG. 1 and a crucible having the essential parts as shown in FIGS. 2 to 5 were used to manufacture a beta-type Ga 2 O 3 single crystal substrate according to the flow chart shown in FIG. 6.
- Samples 101 to 115, Samples 201 to 213, and Samples 301 to 313 are examples.
- Samples 10A to 10C, and Samples 20A to 20C are comparative examples.
- the "crystal outer diameter" of the beta type Ga2O3 single crystal in each of the following samples refers to the crystal outer diameter obtained by the following method: the outer diameter of the beta type Ga2O3 single crystal ingot taken out of the crucible is obtained at three points, namely, the position corresponding to the boundary between the diameter-increasing part and the straight body part (hereinafter also referred to as "measurement point 1"), the position 10 mm below the crystal growth end side of the ingot (hereinafter also referred to as "measurement point 2”), and the intermediate position between the measurement points 1 and 2 (hereinafter also referred to as "measurement point 3"), and the average value thereof is defined as the "crystal outer diameter".
- ⁇ Sample 10B> A beta type Ga2O3 single crystal was manufactured with the growth direction set to the [001] direction in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 10A. In this test example, no cracks were observed in the crucible. The crystal outer diameter of the beta type Ga2O3 single crystal was 120 mm . Furthermore, the above-mentioned cutting process, outer circumference grinding process, and polishing process were performed on the beta type Ga2O3 single crystal in this order. As a result, a beta type Ga2O3 single crystal substrate of sample 10B was obtained. The diameter of the beta type Ga2O3 single crystal substrate of sample 10B was 101.6 mm, and the thickness was 650 ⁇ m. The Rh concentration in the beta type Ga 2 O 3 single crystal substrate of sample 10B was 25 mass ppm in the above-mentioned GDMS, and the Ir concentration was 0.02 mass ppm in the above-mentioned GDMS.
- ⁇ Sample 10C> A beta type Ga2O3 single crystal was produced with the growth direction set to the [001] direction in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 10A, except that the thickness of the side wall of the crucible was set to 1.0 mm . In this test example, no cracks were observed in the crucible. The crystal outer diameter of the beta type Ga2O3 single crystal was 108 mm. Furthermore, the above-mentioned cutting process, outer circumference grinding process, and polishing process were performed on the beta type Ga2O3 single crystal in this order. As a result, a beta type Ga2O3 single crystal substrate of sample 10C was obtained.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 10C was 101.6 mm , and the thickness was 650 ⁇ m .
- the Rh concentration in the beta type Ga 2 O 3 single crystal substrate of sample 10C was 45 mass ppm in the above-mentioned GDMS, and the Ir concentration was 0.02 mass ppm in the above-mentioned GDMS.
- a single crystal growth apparatus 100 a seed crystal 8a consisting of a beta type Ga2O3 single crystal, and a block-shaped Ga2O3 polycrystal were prepared by a conventionally known method or by obtaining commercially available products.
- a crucible 5 constituting the single crystal growth apparatus 100 a crucible was used which was made of stabilized ZrO2 with a purity of 89.2 mass% containing 10.8 mass% CaO , had a side wall portion 5a with a thickness of 3 mm, and a sprayed film 5b with a thickness of 500 ⁇ m. More specifically, the inner diameter of the straight body portion of the crucible 5 was 105 mm.
- the surface roughness Rz of the surface on the inner peripheral surface side of the side wall portion 5a was 20 ⁇ m.
- the composition of the sprayed film 5b was a Pt-Rh alloy containing 30 mass% Rh, and the porosity of the sprayed film 5b was 10%.
- a seed crystal 8a was accommodated in the seed crystal accommodation portion 51 of the crucible 5, and a chunk of Ga2O3 polycrystal was accommodated above the seed crystal 8a. Specifically, a plurality of chunks of Ga2O3 polycrystal were accommodated in the diameter increasing portion 52 and the straight body portion 53, and stacked. Next, the crucible 5, which accommodated the seed crystal 8a and the chunk of Ga2O3 polycrystal inside, was supported by the crucible holder 6.
- the temperature gradient at the interface was 5°C/cm.
- the speed at which the crucible 5 was pulled downward along its axis was 1 mm/hour. In this manner, an ingot of a beta type Ga 2 O 3 single crystal was obtained.
- the outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- Regarding the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- the beta-type Ga2O3 single crystal ingot obtained in the Ga2O3 single crystal growth step S140 was processed in each step of a cutting step, a peripheral grinding step, and a polishing step to obtain a beta-type Ga2O3 single crystal substrate.
- the cutting step the ingot was sliced into a wafer having a thickness of 700 ⁇ m using a conventionally known method.
- the peripheral grinding step the wafer was ground so as to be chamfered on the outer periphery using a conventionally known method to obtain a wafer having a main surface consisting of a central portion and an outer periphery surrounding the outer periphery of the central portion.
- the polishing step the central portion was polished using a conventionally known polishing method, and the surface roughness Ra of the central portion, for example, as specified in JIS B 0681-2:2018, was set to 8 nm.
- a beta type Ga2O3 single crystal substrate of sample 101 was manufactured.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 101 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 101 was 15 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- a crucible was prepared in which the porosity of the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 20%, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 101.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm .
- the beta type Ga2O3 single crystal substrate of sample 102 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 102 was 101.6 mm and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 102 was 20 mass ppm in the above-mentioned GDMS, and the concentration of Ir was 0.01 mass ppm in the above-mentioned GDMS.
- the concentration of Ir was 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible was prepared in which the porosity of the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 30%, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 101.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm .
- the beta type Ga2O3 single crystal substrate of sample 103 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 103 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga 2 O 3 single crystal substrate of sample 103 was 18 ppm by mass in the above-mentioned GDMS, and the Ir concentration was 0.01 ppm by mass in the above-mentioned GDMS.
- a crucible was prepared in which the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 200 ⁇ m thick, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 101.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 104 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 104 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 104 was 17 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible was prepared in which the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 200 ⁇ m thick, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 102.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 105 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 105 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 105 was 25 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible was prepared in which the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 200 ⁇ m thick, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 103.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 106 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 106 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga 2 O 3 single crystal substrate of sample 106 was 40 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a crucible having a surface roughness Rz of 100 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method of obtaining the beta type Ga2O3 single crystal substrate of sample 104.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 107 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 107 was 101.6 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 107 was 28 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was less than 0.01 ppm by mass in the above-mentioned GDMS.
- crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible having a surface roughness Rz of 100 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 105.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- the beta type Ga2O3 single crystal substrate of sample 108 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 108 was 101.6 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 108 was 15 mass ppm in the above-mentioned GDMS, and the concentration of Ir was less than 0.01 mass ppm in the above-mentioned GDMS.
- crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible having a surface roughness Rz of 300 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 104.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- the beta type Ga2O3 single crystal substrate of sample 109 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 109 was 101.6 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 109 was 22 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a crucible having a surface roughness Rz of 300 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 105.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- the beta type Ga2O3 single crystal substrate of sample 110 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 110 was 101.6 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 110 was 25 mass ppm in the above-mentioned GDMS, and the concentration of Ir was 0.02 mass ppm in the above-mentioned GDMS.
- a crucible having a surface roughness Rz of 300 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method of obtaining the beta type Ga2O3 single crystal substrate of sample 106.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- the beta type Ga2O3 single crystal substrate of sample 111 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 111 was 101.6 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 111 was 27 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 111.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 112 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 112 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 112 was 20 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a crucible was prepared in which the inner peripheral surface side of the side wall portion 5a was covered with a sprayed film consisting of the following first film 5b1 and second film 5b2, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 109. That is, in the preparation step of this test example, a first spray material was sprayed on the surface on the inner peripheral surface side of the side wall portion 5a of the crucible 5, thereby covering the surface with a first film 5b1 made of Rh, having a first film porosity of 30%, and having a thickness of 50 ⁇ m. Furthermore, a second spray material was sprayed on the first film 5b1, thereby covering the first film 5b1 with a second film 5b2 made of Pt, having a second film porosity of 30%, and having a thickness of 150 ⁇ m.
- the outer crystal diameter of the beta type Ga2O3 single crystal obtained in this way was 105.8 mm. Furthermore, a beta type Ga2O3 single crystal substrate of sample 113 was obtained from the beta type Ga2O3 single crystal. The diameter of the beta type Ga2O3 single crystal substrate of sample 113 was 101.6 mm, and the thickness was 650 ⁇ m. The Rh concentration in the beta type Ga2O3 single crystal substrate of sample 113 was less than 0.01 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 113.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 114 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 114 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 114 was 0.08 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 113.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 115 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 115 was 101.6 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 115 was 2.9 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was 0.01 ppm by mass in the above-mentioned GDMS.
- Example 20A and Sample 20B> Except for the inner diameter of the straight body of the crucible used for obtaining the Ga2O3 single crystal being 156 mm, the beta type Ga2O3 single crystal substrates of samples 20A and 20B were attempted to be manufactured in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrates of samples 10A and 10B. However, the crucible broke during crystal growth, and the beta type Ga2O3 single crystal substrates of samples 20A and 20B could not be obtained.
- ⁇ Sample 20C> A beta type Ga2O3 single crystal was produced with the growth direction set to the [001] direction in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 20A and sample 20B, except that the thickness of the side wall of the crucible was set to 1.0 mm . In this test example, no cracks were observed in the crucible. The crystal outer diameter of the beta type Ga2O3 single crystal was 165 mm. Furthermore, the above-mentioned cutting process, outer circumference grinding process, and polishing process were performed on the beta type Ga2O3 single crystal in this order. As a result, a beta type Ga2O3 single crystal substrate of sample 20C was obtained.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 20C was 152.4 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga 2 O 3 single crystal substrate of sample 20C was 38 ppm by mass in the above-mentioned GDMS, and the Ir concentration was 0.01 ppm by mass in the above-mentioned GDMS.
- a beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 101, except that a crucible with an inner diameter of the straight body part of 156 mm was prepared.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- the beta type Ga2O3 single crystal substrate of sample 201 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 201 was 152.4 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 201 was 15 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was 0.01 ppm by mass in the above-mentioned GDMS.
- crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible was prepared in which the porosity of the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 20%, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 201.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm .
- the beta type Ga2O3 single crystal substrate of sample 202 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 202 was 152.4 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 202 was 20 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth by heating, but cracks were observed during cooling after the crystal growth.
- a crucible was prepared in which the porosity of the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 30%, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 201.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm .
- the beta type Ga2O3 single crystal substrate of sample 203 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 203 was 152.4 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga 2 O 3 single crystal substrate of sample 203 was 23 mass ppm in the above-mentioned GDMS, and the Ir concentration was 0.01 mass ppm in the above-mentioned GDMS.
- a crucible was prepared in which the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 200 ⁇ m thick, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 201.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- a beta type Ga2O3 single crystal substrate of sample 204 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 204 was 152.4 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 204 was 27 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible was prepared in which the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 200 ⁇ m thick, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 202.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- a beta type Ga2O3 single crystal substrate of sample 205 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 205 was 152.4 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 205 was 15 mass ppm in the above-mentioned GDMS, and the Ir concentration was 0.02 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible was prepared in which the sprayed film 5b covering the inner peripheral surface side of the sidewall portion 5a was 200 ⁇ m thick, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 203.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- a beta type Ga2O3 single crystal substrate of sample 206 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 206 was 152.4 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga 2 O 3 single crystal substrate of sample 206 was 35 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a crucible having a surface roughness Rz of 100 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method of obtaining the beta type Ga2O3 single crystal substrate of sample 204.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- a beta type Ga2O3 single crystal substrate of sample 207 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 207 was 152.4 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 207 was 18 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was 0.01 ppm by mass in the above-mentioned GDMS.
- crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible having a surface roughness Rz of 100 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 205.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- the beta type Ga2O3 single crystal substrate of sample 208 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 208 was 152.4 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 208 was 25 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was less than 0.01 ppm by mass in the above-mentioned GDMS.
- crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- a crucible having a surface roughness Rz of 300 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 204.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- the beta type Ga2O3 single crystal substrate of sample 209 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 209 was 152.4 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of sample 209 was 32 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a crucible having a surface roughness Rz of 300 ⁇ m on the inner peripheral surface side of the sidewall portion 5a was prepared, and the beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of the sample 205.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- the beta type Ga2O3 single crystal substrate of the sample 210 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of the sample 210 was 152.4 mm, and the thickness was 650 ⁇ m.
- the concentration of Rh in the beta type Ga2O3 single crystal substrate of the sample 210 was 26 ppm by mass in the above-mentioned GDMS, and the concentration of Ir was 0.02 ppm by mass in the above-mentioned GDMS.
- a crucible was prepared in which the inner peripheral surface side of the side wall portion 5a was covered with a sprayed film consisting of the following first film 5b1 and second film 5b2, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 209. That is, in the preparation step of this test example, a first spray material was sprayed on the surface on the inner peripheral surface side of the side wall portion 5a of the crucible 5, thereby covering the surface with a first film 5b1 made of Rh, having a first film porosity of 30%, and having a thickness of 50 ⁇ m. Furthermore, a second spray material was sprayed on the first film 5b1, thereby covering the first film 5b1 with a second film 5b2 made of Pt, having a second film porosity of 30%, and having a thickness of 150 ⁇ m.
- the outer crystal diameter of the beta type Ga2O3 single crystal obtained in this way was 157.1 mm. Furthermore, a beta type Ga2O3 single crystal substrate of sample 211 was obtained from the beta type Ga2O3 single crystal. The diameter of the beta type Ga2O3 single crystal substrate of sample 211 was 152.4 mm, and the thickness was 650 ⁇ m. The Rh concentration in the beta type Ga2O3 single crystal substrate of sample 211 was 0.02 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 211.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- a beta type Ga2O3 single crystal substrate of sample 212 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 212 was 152.4 mm, and the thickness was 650 ⁇ m.
- Rh concentration in the beta type Ga2O3 single crystal substrate of sample 212 was less than 0.01 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 211.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 157.1 mm.
- a beta type Ga2O3 single crystal substrate of sample 213 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 213 was 152.4 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 213 was 2.8 ppm by mass in the above-mentioned GDMS, and the Ir concentration was 0.01 ppm by mass in the above-mentioned GDMS.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 11 mass% Rh, but otherwise an ingot of a beta type Ga 2 O 3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of the sample 101.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of the sample 301 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 301 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 301 was 14 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 11 mass% Rh, but otherwise a beta type Ga 2 O 3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 102.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 302 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 302 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 302 was 21 mass ppm in the above-mentioned GDMS, and the Ir concentration was 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , the side wall portion 5a having a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall portion 5a of the crucible 5 was a Pt-Rh alloy containing 11 mass% Rh, and an ingot of a beta type Ga 2 O 3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of the sample 103.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of the sample 303 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 303 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 303 was 19 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 11 mass% Rh, but otherwise a beta type Ga 2 O 3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 104.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 304 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 304 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 304 was 18 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 11 mass% Rh, but otherwise a beta type Ga 2 O 3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 105.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 305 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 305 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 305 was 24 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 10 mass% Rh, but otherwise a beta type Ga 2 O 3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 106.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 306 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 306 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 306 was 22 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and the side wall portion 5a having a thickness of 9 mm and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall portion 5a of the crucible 5 were Pt-Rh alloy containing 10 mass% Rh, and an ingot of a beta type Ga 2 O 3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 107.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 307 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 307 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 307 was 25 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 10 mass% Rh, but otherwise a beta type Ga 2 O 3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 108.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 308 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 308 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 308 was 17 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 no cracks were observed during the crystal growth, but cracks were observed during cooling after the crystal growth.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 10 mass% Rh, but otherwise a beta type Ga 2 O 3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 109.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 309 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 309 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 309 was 21 mass ppm in the above-mentioned GDMS, and the Ir concentration was less than 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , the side wall portion 5a having a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall portion 5a of the crucible 5 was a Pt-Rh alloy containing 10 mass% Rh, except that an ingot of a beta type Ga 2 O 3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of the sample 110.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of the sample 310 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of the sample 310 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of the sample 310 was 26 mass ppm in the above-mentioned GDMS, and the Ir concentration was 0.01 mass ppm in the above-mentioned GDMS.
- the crucible 5 constituting the single crystal growth apparatus 100 was made of stabilized ZrO 2 with a purity of 86.2 mass% containing 13.8 mass% Y 2 O 3 , and had a side wall 5a with a thickness of 9 mm, and the composition of the sprayed film 5b covering the inner peripheral surface side of the side wall 5a of the crucible 5 was a Pt-Rh alloy containing 10 mass% Rh, but otherwise a beta type Ga 2 O 3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga 2 O 3 single crystal substrate of sample 111.
- the crystal outer diameter of the beta type Ga 2 O 3 single crystal was 105.8 mm.
- a beta type Ga 2 O 3 single crystal substrate of sample 311 was obtained from the beta type Ga 2 O 3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 311 was 101.6 mm and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 311 was 14 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a beta type Ga2O3 single crystal ingot was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 311.
- the crystal outer diameter of the beta type Ga2O3 single crystal was 105.8 mm.
- a beta type Ga2O3 single crystal substrate of sample 312 was obtained from the beta type Ga2O3 single crystal.
- the diameter of the beta type Ga2O3 single crystal substrate of sample 312 was 101.6 mm, and the thickness was 650 ⁇ m.
- the Rh concentration in the beta type Ga2O3 single crystal substrate of sample 312 was 13 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- a crucible was prepared in which the inner peripheral surface side of the side wall portion 5a was covered with a sprayed film consisting of the following first film 5b1 and second film 5b2, and an ingot of a beta type Ga2O3 single crystal was obtained in the same manner as the method for obtaining the beta type Ga2O3 single crystal substrate of sample 309. That is, in the preparation step of this test example, a first spray material was sprayed on the surface on the inner peripheral surface side of the side wall portion 5a of the crucible 5, thereby covering the surface with a first film 5b1 made of Rh, having a first film porosity of 30%, and having a thickness of 50 ⁇ m. Furthermore, a second spray material was sprayed on the first film 5b1, thereby covering the first film 5b1 with a second film 5b2 made of Pt, having a second film porosity of 30%, and having a thickness of 150 ⁇ m.
- the outer crystal diameter of the beta type Ga2O3 single crystal obtained in this way was 105.8 mm. Furthermore, a beta type Ga2O3 single crystal substrate of sample 313 was obtained from the beta type Ga2O3 single crystal. The diameter of the beta type Ga2O3 single crystal substrate of sample 313 was 101.6 mm, and the thickness was 650 ⁇ m. The Rh concentration in the beta type Ga2O3 single crystal substrate of sample 313 was less than 0.01 ppm by mass in the above-mentioned GDMS, and the Ir concentration was less than 0.01 ppm by mass in the above-mentioned GDMS.
- Tables 1, 2 , and 3 show the configurations of the crucibles (inner diameter, composition, surface roughness Rz of the straight body, thickness of the side wall, composition, porosity, thickness, etc. of the sprayed film) used to manufacture the beta-type Ga2O3 single crystal substrates of Samples 10A to 10C, Samples 101 to 115, Samples 20A to 20C, Samples 201 to 213, and Samples 301 to 313.
- Tables 1 to 3 when the sprayed film is a single layer, its composition, porosity, and thickness are shown in the column "sprayed film (innermost layer; second film)".
- the product yield was obtained by the following method for the beta type Ga2O3 single crystals for obtaining the beta type Ga2O3 single crystal substrates of Samples 10B to 10C, Samples 101 to 115, Sample 20C, Samples 201 to 213, and Samples 301 to 313.
- the "product yield” means the ratio of the mass of the ingot of the beta type Ga2O3 single crystal grown in the crucible, excluding the region where the crucible breaks or chips or the crystal breaks or chips during cooling, and where the desired diameter cannot be obtained when processed into a beta type gallium trioxide single crystal substrate, and which is evaluated as being a good product as the substrate by the evaluation method described later. The better the product yield of the single crystal, the less likely it is that cracks, chips, etc. occurred in the crucible in which the single crystal was grown.
- a disk-shaped measurement sample (thickness: 1 mm) having a main surface of the (001) plane was cut out and prepared at the measurement points 1 and 2, which are the positions for measuring the crystal outer diameter described above. Furthermore, the main surface of the measurement sample was polished and etched with molten potassium hydroxide as known in the art.
- the entire surface of the measurement sample was observed with a differential interference microscope (product name (model number): "LV-150", manufactured by Nikon Corporation), and the number of crystal defects that appeared in one visual field of the differential interference microscope was counted for each visual field, and it was determined whether or not the sample was polycrystallized.
- the observation with the differential interference microscope was performed at a magnification of 10 times.
- one visual field of the differential interference microscope was 10 mm x 10 mm in size, and the number of crystal defects per visual field was calculated as the density (cm -2 ).
- the crystal defects refer to "etch pits" that appear as corrosion holes on the main surface due to the etching.
- etch pits are not academically synonymous with dislocations, they can be regarded as equivalent to dislocations in this technical field.
- dislocations refer to "threading dislocations” that exist inside a beta-type Ga 2 O 3 single crystal, and the threading dislocations are known as one type of crystal defect.
- the measurement sample was evaluated as good.
- the measurement sample was evaluated as defective.
- a new measurement sample was cut at a position 10 mm toward the measurement point 3 from the measurement point 1 or measurement point 2 from which the measurement sample was cut, and the above-mentioned observation was performed on the new measurement sample using the differential interference microscope. This operation was repeated until the measurement sample was judged to be good.
- the volume of the ingot was calculated from the length (height) of the ingot sandwiched between the cut-out positions of the measurement samples judged to be good and the diameter of the beta-type Ga2O3 single crystal substrate of each sample (i.e., 101.6 mm or 152.4 mm), and the mass of the ingot that could become a product (hereinafter also referred to as "good mass”) was calculated from the volume.
- good mass the mass of the ingot that could become a product
- the carrier concentration in each sample was obtained by carrying out the above-mentioned measurement method on the beta type Ga2O3 single crystal substrate of Samples 10B to 10C, Samples 101 to 115, Sample 20C, Samples 201 to 213, and Samples 301 to 313 , which were prepared using the center part of the substrate.
- the impurity concentration of Sn or Si in the beta type Ga2O3 single crystal substrate was obtained by using glow discharge mass spectrometry (GDMS).
- the activation rate in each sample was calculated by dividing the carrier concentration in each sample by the impurity concentration obtained by GDMS. The results are shown in Tables 4, 5, and 6.
- the transmittance of light having a wavelength of 427 nm in each sample was obtained by carrying out the above-mentioned measurement method on the transmittance measurement samples prepared using the central parts of the beta type Ga 2 O 3 single crystal substrates of Samples 10B to 10C, Samples 101 to 115, Sample 20C, Samples 201 to 213, and Samples 301 to 313. The results are shown in Tables 4, 5, and 6.
- the product yield of the beta type Ga 2 O 3 single crystal substrates of Samples 101 to 115 was better than that of the beta type Ga 2 O 3 single crystal substrates of Samples 10B to 10C. Therefore, it can be evaluated that the crucible for manufacturing the beta type Ga 2 O 3 single crystal substrates of Samples 101 to 115 can suppress the occurrence of cracks and chips during crystal growth compared to that for manufacturing the beta type Ga 2 O 3 single crystal substrates of Samples 10B to 10C.
- the product yield of the beta type Ga 2 O 3 single crystal substrates of Samples 201 to 213 was better than that of the beta type Ga 2 O 3 single crystal substrate of Sample 20C.
- the crucible for manufacturing the beta type Ga2O3 single crystal substrate of Samples 201 to 213 can suppress the occurrence of cracks and chips during crystal growth, compared with that for manufacturing the beta type Ga2O3 single crystal substrate of Sample 10C.
- the product yield of the beta type Ga2O3 single crystal substrate of Samples 301 to 313 was good, similar to that of the beta type Ga2O3 single crystal substrate of Samples 101 to 115. Therefore, it can be evaluated that the crucible for manufacturing the beta type Ga2O3 single crystal substrate of Samples 301 to 313 can suppress the occurrence of cracks and chips during crystal growth.
- the beta type Ga2O3 single crystal substrates of Samples 113 to 115, Samples 211 to 213, and Sample 313 were superior in activation rate and transmittance compared to the other samples. Therefore, it is evaluated that the beta type Ga2O3 single crystal substrates of Samples 113 to 115, Samples 211 to 213 , and Sample 313 can be provided as compound semiconductor substrates excellent in both electrical and optical properties.
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Abstract
Description
特許文献1~5および非特許文献1等に開示されるように、Pt-Rh合金またはPt-Ir合金からなる坩堝等を用い、ベータ型Ga2O3単結晶を成長させて得ることが公知である。これらのPt-Rh合金、Pt-Ir合金等からなる坩堝は、高価であって、コストダウンを図る目的で肉厚を薄くすることが考えられる。しかしながら、上記Pt-Rh合金、Pt-Ir合金等からなる坩堝は、熱収縮等によって変形しやすいことから、結晶成長時および結晶成長後の冷却時に、坩堝内に存するベータ型Ga2O3単結晶によって割れたり欠けたりするため、所望のベータ型Ga2O3単結晶を歩留良く得ることができないという問題が指摘されている。とりわけ結晶成長時における坩堝の割れは、ベータ型Ga2O3単結晶を得るのに致命的となる。特許文献6に開示された白金または白金系合金を溶射により被着させる方法は、坩堝等の割れ、欠けを抑制することを目的としておらず、もって結晶成長時における坩堝の割れを防ぐといった作用または効果に関する示唆は一切されていない。したがって、少なくとも結晶成長時の割れ、欠け等の発生を抑制することにより、ベータ型Ga2O3単結晶を歩留良く得ることができる、Pt-Rh合金、Pt-Ir合金等の薄膜を用いた坩堝は未だ得られておらず、その開発が切望されている。
本開示によれば、結晶成長時の割れ、欠け等の発生を抑制することができる坩堝、それを用いたベータ型三酸化二ガリウム単結晶基板の製造方法、およびベータ型三酸化二ガリウム単結晶基板を提供することができる。
以下、本開示の実施形態の概要について説明する。本発明者らは、上記課題を解決するために鋭意検討を重ね、本開示を完成させた。まず本発明者らは、縦型ボート法を適用する坩堝の材料として、熱伝導率が低く、かつ温度変化に対し安定で変形しにくい材料であるジルコニアに注目した。とりわけ上記ジルコニアからなる坩堝の内周側の表面を、ベータ型Ga2O3単結晶の結晶成長時に求められる温度(1800℃前後)に対応できるロジウムおよび白金の両方またはいずれか一方を含む薄膜、たとえば、Rhを含むPt-Rh合金等からなる薄膜で被覆した。これにより、少なくとも結晶成長時の割れ、欠け等の発生を抑制することができる坩堝を想到した。加えて、上記単結晶を歩留まり良く得るために適切となる上記坩堝の厚み、および上記薄膜の厚みについてもそれぞれ知見し、本開示に到達した。
[1]本開示の一態様に係る坩堝は、ベータ型三酸化二ガリウム単結晶成長用の坩堝である。上記坩堝は、1mm以上10mm以下の厚みを有する。上記坩堝の最大内径は、100mm以上である。上記坩堝の組成は、酸化イットリウムおよび酸化カルシウムの両方またはいずれか一方を含む安定化ジルコニアである。上記坩堝の内周面側の表面は、ロジウムおよび白金の両方またはいずれか一方を含む溶射膜により被覆される。上記溶射膜の厚みは、100μm以上500μm以下である。上記安定化ジルコニアは、少なくとも上記酸化イットリウムを12.0質量%以上15.5質量%以下含み、または上記酸化カルシウムを10.2質量%以上11.4質量%以下含む。このような特徴を有する坩堝は、結晶成長時の割れ、欠け等の発生を抑制することができる。
以下、本開示に係る一実施形態(以下、「本実施形態」とも記す)についてさらに詳細に説明するが、本開示はこれらに限定されるものではない。以下では図面を参照しながら説明する場合があるが、本明細書および図面において同一または対応する要素に同一の符号を付すものとし、それらについて同じ説明は繰り返さない。さらに図面においては、各構成要素を理解しやすくするために縮尺を適宜調整して示しており、図面に示される各構成要素の縮尺と実際の構成要素の縮尺とは必ずしも一致しない。
本実施形態に係る坩堝は、ベータ型三酸化二ガリウム単結晶(ベータ型Ga2O3単結晶)成長用の坩堝である。上記坩堝は、1mm以上10mm以下の厚みを有する。上記坩堝の最大内径は、100mm以上である。上記坩堝の組成は、酸化イットリウムおよび酸化カルシウムの両方またはいずれか一方を含む安定化ジルコニアである。上記坩堝の内周面側の表面は、ロジウム(Rh)および白金(Pt)の両方またはいずれか一方を含む溶射膜により被覆される。たとえば上記溶射膜は、Rhを10質量%以上30質量%以下含む白金-ロジウム合金(Pt-Rh合金)からなることが好ましい。上記溶射膜の厚みは、100μm以上500μm以下である。上記安定化ジルコニアは、少なくとも上記酸化イットリウムを12.0質量%以上15.5質量%以下含み、または上記酸化カルシウムを10.2質量%以上11.4質量%以下含む。このような特徴を有する坩堝は、結晶成長時の割れ、欠け等の発生を抑制することができる。
坩堝5は、1mm以上10mm以下の厚みを有する。より具体的には、坩堝5の種結晶収容部51、増径部52、および直胴部53において、その側壁部5aがいずれも1mm以上10mm以下の厚みを有する。坩堝5の種結晶収容部51、増径部52、直胴部53の側壁部5aは、いずれも5mm以上10mm以下の厚みを有していることが好ましい。さらに坩堝5の最大内径は、100mm以上である。より具体的には、坩堝5の直胴部53の内径が100mm以上であることが好ましい。坩堝5の直胴部53の内径は、150mm以上であることも好ましい。坩堝5の最大内径の上限は、特に制限されないが、たとえば165mmである。
坩堝5の組成は、酸化イットリウム(イットリア:Y2O3)および酸化カルシウム(カルシア:CaO)の両方またはいずれか一方を含む安定化ジルコニア(以下、「安定化ZrO2」とも記す)である。坩堝5の組成は、Y2O3またはCaOのいずれか一方を含む安定化ZrO2であることが好ましい。具体的には、上記安定化ZrO2は、少なくともY2O3を12.0質量%以上15.5質量%以下含み、またはCaOを10.2質量%以上11.4質量%以下含む。坩堝5の組成を、上述したような熱伝導率が低い安定化ZrO2とすることにより、結晶成長時に発生する結晶欠陥を結晶の外周側に排斥され易くし、もって結晶成長中のベータ型Ga2O3単結晶の多結晶化を防ぐことができる。「安定化ZrO2」とは、ZrO2にY2O3、CaO、酸化マグネシウム(MgO)、酸化アルミニウム(アルミナ:Al2O3)等を添加することにより、高温相(典型的には、立方晶または正方晶の固溶体)が、室温まで安定に存在し得るようになったZrO2をいう。なお安定化ZrO2に固溶する酸化物は、Y2O3、CaO、MgOおよびAl2O3のみに限られるものではない。
(組成)
坩堝の内周面側の表面は、RhおよびPtの両方またはいずれか一方を含む溶射膜により被覆される。たとえば上記溶射膜は、Rhを10質量%以上30質量%以下含むPt-Rh合金からなることが好ましい。たとえば図1に示す第1態様の坩堝5においては、Rhを10質量%以上30質量%以下含む白金-ロジウム合金(Pt-Rh合金)からなる溶射膜5bにより被覆される。溶射膜5bの厚みは、100μm以上500μm以下である。溶射膜5bは、坩堝5の内周面側の表面全面を被覆することが好ましい。しかしながら、上記表面の一部が溶射膜5bで被覆されていなかったり、溶射膜5bの組成が部分的に異なっていたりしていたとしても本開示の範囲を逸脱するものではない。
ここで溶射膜は、空孔を有することが好ましい。溶射膜に占める空孔の体積比率である空孔率は、30体積%以上50体積%以下であることが好ましい。これにより、結晶成長時の割れ、欠け等の発生をより抑制することができる。図2は、図1の単結晶成長装置に用いられる第2態様の坩堝の要部を説明する要部拡大断面図である。図2に示す第2態様の坩堝において、側壁部5aの内周面側に存する溶射膜5bは、空孔5cを有している。この溶射膜5bに占める空孔5cの体積比率である空孔率は、30体積%以上50体積%以下であることが好ましい。
坩堝の内周面側の表面の表面粗さRzは、300μm以上500μm以下であることが好ましい。この場合においても溶射膜は、空孔を有することが好ましい。溶射膜に占める空孔の体積比率である空孔率は、10体積%以上30体積%未満であることが好ましい。これにより、結晶成長時の割れ、欠け等の発生をより抑制することができる。図3は、図1の単結晶成長装置に用いられる第3態様の坩堝の要部を説明する要部拡大断面図である。図3に示す第3態様の坩堝において、側壁部5aの内周面側の表面の表面粗さRzは、300μm以上500μm以下である。側壁部5aの内周面側に存する溶射膜5bは、空孔5cを有している。この溶射膜5bに占める空孔5cの体積比率である空孔率は、10体積%以上30体積%未満である。側壁部5aの内周面側の表面の表面粗さRzは、300μm以上400μm以下であることが好ましい。
上記溶射膜は、第1膜および第2膜からなることが好ましい。第1膜は、上記表面を被覆することが好ましい。上記第1膜は、Rh、またはRhを主成分とするPt-Rh合金からなることが好ましい。上記第2膜は、上記第1膜を被覆することが好ましい。上記第2膜は、Pt、またはPtを主成分とするPt-Rh合金からなることが好ましい。上記溶射膜の厚みは、上記第1膜と上記第2膜との合計で100μm以上500μm以下であることが好ましい。これにより結晶成長時の割れ、欠け等の発生を抑制する効果に加え、上記ベータ型Ga2O3単結晶中へのRhの混入を抑制することができる。
図1に示すように、単結晶成長装置100は、坩堝5を保持する坩堝保持台6を備える。坩堝保持台6は、坩堝5の底部に接して坩堝5を保持する。坩堝保持台6は、円筒形の外観を有する場合がある。坩堝保持台6の材料としては、特に限定されないが、たとえば石英、アルミナ、ジルコニアまたは炭化ケイ素などを採用することができる。坩堝保持台6の外径は、支持する坩堝5の直径にも依るが、たとえば75mm以上200mm以下である。
加熱装置7は、坩堝5を加熱する目的で設置される。加熱装置7は、たとえば従来公知の電気式ヒータ(以下、単に「ヒータ」とも記す)を採用することができる。上記ヒータは、たとえば2体とされ、この2体が坩堝5の外周を囲むように配置される。ヒータの出力は、1体毎に独立して制御される場合がある。とりわけヒータは、1体毎に坩堝5の軸に対し垂直方向に複数の部分に分割されることにより、多段に構成される場合がある。この場合、多段に構成した部分毎にヒータの出力が独立して制御されることが好ましい。これにより坩堝5内の内容物の温度を、坩堝5の軸方向に沿って詳細に調整することができる。たとえば多段に構成した部分毎にヒータの出力を独立して制御して増径部52および直胴部53を加熱することにより、増径部52および直胴部53にて成長する結晶の成長速度をそれぞれ安定させることができる。
本実施形態に係るベータ型三酸化二ガリウム単結晶基板(ベータ型Ga2O3単結晶基板)の製造方法は、たとえば上述した坩堝を用いたベータ型Ga2O3単結晶基板であることが好ましい。すなわち上記製造方法は、上記坩堝を準備する工程と、上記坩堝を用いた縦型ボート(Vertical Boat)法によってベータ型三酸化二ガリウム単結晶(ベータ型Ga2O3単結晶)を得る工程と、上記ベータ型Ga2O3単結晶を加工することにより、円形状の主表面を有するベータ型Ga2O3単結晶基板を得る工程とを含むことが好ましい。このような特徴を備えるベータ型Ga2O3単結晶基板の製造方法により、結晶成長時等に坩堝が割れること、欠けることが低減されるため、歩留まり良くベータ型Ga2O3単結晶基板を得ることができる。
(準備工程S110)
図1および図6に示すように、まずベータ型Ga2O3単結晶製造工程S100においては、円筒状の坩堝5と、坩堝5の外周を包囲するように配置される加熱装置7とを少なくとも備える単結晶成長装置100を準備する工程(準備工程S110)が実行される。準備工程S110においては、ベータ型Ga2O3単結晶81を製造するための上述した単結晶成長装置100のほかに、種結晶8aおよび塊状のGa2O3バルク体もそれぞれ準備されることが好ましい。種結晶8aは、ベータ型Ga2O3単結晶からなる。Ga2O3バルク体は、多結晶Ga2O3からなる場合がある。種結晶8aおよび塊状のGa2O3バルク体は従来公知の方法により準備されてもよく、市販のものを入手することにより準備されてもよい。
溶射材:Rhを10~30質量%含むPt-Rh合金
溶射材の粒子径:45~300μm
溶射材の供給速度:50~75g/分
溶射ノズルの向き:坩堝の軸方向に対して30~45度
溶射ノズルと坩堝の側壁部の内周面側の表面との距離:20~120mm。
原材料装入工程S120は、上記坩堝の底部に上記種結晶を収容し、かつ上記坩堝内の上記種結晶よりも上部に塊状のGa2O3バルク体を収容する工程である。原材料装入工程S120においては、坩堝5内の種結晶8aよりも上部に塊状のGa2O3バルク体とともに、固体のB2O3も収容されることが好ましい。原材料装入工程S120の目的は、単結晶成長装置100を用いて結晶成長を行うための各種の原材料を坩堝内に封入することである。原材料装入工程S120においては、まず坩堝5の種結晶収容部51の中空部にベータ型Ga2O3単結晶からなる種結晶8aが装入される。次に坩堝5の増径部52および直胴部53に、多結晶Ga2O3からなる塊状のGa2O3バルク体が複数個装入され、積み重ねられる。原材料装入工程S120においては、坩堝5に塊状のGa2O3バルク体を複数個装入する際に、SnまたはSiを所定量添加することが好ましい。これによりベータ型Ga2O3単結晶製造工程S100により得られるベータ型Ga2O3単結晶81から、上記SnまたはSiをドーパントとして含むベータ型Ga2O3単結晶基板が得られる。上記SnまたはSiの添加に際しては、上記ドーパントの濃度がベータ型Ga2O3単結晶基板においてたとえば1.0×1018cm-3(5.0×1017cm-3以上4.0×1019cm-3以下)となるように添加量を調整することが好ましい。
原材料溶融工程S130は、上記加熱装置で上記坩堝を加熱し、上記Ga2O3バルク体および上記種結晶の一部を溶融することによってGa2O3融液を得るとともに、上記Ga2O3融液と上記種結晶の残部とを接触させる工程である。原材料溶融工程S130の目的は、単結晶成長装置100を用いて結晶を成長させるのに際し、Ga2O3バルク体および種結晶8aの一部を溶融することによって、種結晶8aの残部とGa2O3融液82とを接触させることである。これにより次工程であるGa2O3単結晶成長工程S140において、種結晶8aの残部上にベータ型Ga2O3単結晶81を成長させることができる。原材料溶融工程S130においては、具体的には、種結晶8aおよびGa2O3バルク体が内部に収容された坩堝5が、坩堝保持台6に支持される。その後、加熱装置7に電流が供給され、坩堝5が加熱される。これにより上記Ga2O3バルク体が溶融してGa2O3融液82となる。次いで種結晶8aの一部も溶融し、その界面にて種結晶8aの残部とGa2O3融液82とが接触する。
Ga2O3単結晶成長工程S140は、上記Ga2O3融液から上記種結晶の上記残部の上に結晶を成長させることによりベータ型Ga2O3単結晶を得る工程である。Ga2O3単結晶成長工程S140は、たとえば加熱装置7に対し坩堝5を、その軸に沿って下向き(種結晶収容部51側)に徐々に引き下げていくことにより、坩堝5において種結晶8a側の温度が低く、Ga2O3融液82側の温度が高くなるような温度勾配を形成することができる。これにより種結晶8aに接触するGa2O3融液82を凝固させ、種結晶8aの残部上でGa2O3融液82からベータ型Ga2O3単結晶81を連続的に成長させることができる。このとき、たとえばGa2O3融液82側の温度は、1800~1820℃である。Ga2O3融液82と成長中のベータ型Ga2O3単結晶81との界面における温度勾配は、たとえば3~8℃/cmである。坩堝5をその軸に沿って下向きに引下げるスピードは、特に制限されないが、たとえば0.1~2mm/時とすることができる。
上記ベータ型Ga2O3単結晶基板の製造方法は、図6に示すように、Ga2O3単結晶成長工程S140により得られたベータ型Ga2O3単結晶を加工することにより、円形状の主表面を有するベータ型Ga2O3単結晶基板を得る工程(ベータ型Ga2O3単結晶基板製造工程S200)を含む。ベータ型Ga2O3単結晶基板製造工程S200においては、次の切断工程、外周研削工程、および研磨工程が含まれ、これらの工程がこの順で実行されることによりベータ型Ga2O3単結晶基板を得ることができる。
上記の各工程が実行されることにより、本実施形態に係るベータ型Ga2O3単結晶基板が製造される。上記ベータ型Ga2O3単結晶基板の製造方法においては、上述した第1態様から第5態様のいずれか1つの坩堝を用いてベータ型Ga2O3単結晶が製造されるため、結晶成長時等に坩堝が割れること、欠けることが低減される。このため、歩留まり良くベータ型Ga2O3単結晶基板を得ることができる。
本実施形態に係るベータ型三酸化二ガリウム単結晶基板(ベータ型Ga2O3単結晶基板)は、円形状の主表面を有するベータ型Ga2O3単結晶基板である。上記ベータ型Ga2O3単結晶基板の直径は、100mm以上である。上記主表面は、ベータ型Ga2O3単結晶の(001)面である。または上記主表面は、上記ベータ型Ga2O3単結晶の(001)面から0°より大きく10°以下のオフ角、および上記ベータ型Ga2O3単結晶の[010]方向もしくは上記[010]方向に直交する方向のオフ方向を有する面である。上記ベータ型Ga2O3単結晶基板は、ロジウム(Rh)およびイリジウム(Ir)の両方またはいずれか一方を含む。上記Rhの濃度および上記Irの濃度は、グロー放電質量分析(Glow Discharge Mass Spectrometry:GDMS)においていずれも3質量ppm未満である。このような特徴を有するベータ型Ga2O3単結晶基板は、これに含まれる上記Rhおよび上記Irが極めて僅かであることにより、電気的特性および光学的特性の両者において優れることができる。
図7は、本実施形態に係るベータ型Ga2O3単結晶基板を説明する模式図である。図7に示すベータ型Ga2O3単結晶基板1において、その直径は、100mm以上である。とりわけベータ型Ga2O3単結晶基板1の直径は、100mm以上155mm以下であることが好ましい。直径が100mm以上155mm以下であるベータ型Ga2O3単結晶基板1は、具体的には、直径が101.6mmまたは152.4mmであることが好ましく、換言すれば直径が4インチまたは6インチであることが好ましい。これにより直径が100mm以上155mm以下の大口径のベータ型Ga2O3単結晶基板において、電気的特性および光学的特性の両者において優れることができる。ここでベータ型Ga2O3単結晶基板の直径については、上記主表面がオリエンテーションフラット(以下、「OF」とも記す)、インデックスフラット(以下、「IF」とも記す)等の影響によって幾何学的な円形状とはならない場合の形状であっても、上記OF、IF等が形成される前の円形状に基づいて求めるものとする。また、上記のとおりベータ型Ga2O3単結晶基板の直径は、ノギス等の従来公知の外径測定器を用いることにより測定することができる。なお、本明細書において主表面の形状を表す「円形状」の定義については後述する。
(円形状)
ベータ型Ga2O3単結晶基板1は、上述のように円形状の主表面10を有する。本明細書において当該主表面の形状を表す「円形状」には、幾何学的な円形状が含まれるほか、主表面10の外周にノッチ、OF、またはIFの少なくともいずれかが形成されることにより、主表面が幾何学的な円形状を形成しない場合の形状が含まれる。ここで「主表面が幾何学的な円形状を形成しない場合の形状」とは、主表面10の外周上の任意の点から主表面10の中心まで延びる線分のうち、上記ノッチ、OF、およびIF上の任意の点から主表面の中心まで延びる線分において長さが短くなる場合の形状を意味する。さらに「主表面が幾何学的な円形状を形成しない場合の形状」には、主表面10の外周上の任意の点から主表面10の中心まで延びる線分すべての長さが、ベータ型Ga2O3単結晶基板1の原料となるベータ型Ga2O3単結晶の形状に起因して、同一になるとは限らない場合の形状も含まれる。この場合、主表面10の中心については、重心の位置をいい、ベータ型Ga2O3単結晶基板1の直径については、ベータ型Ga2O3単結晶基板1の外周上の任意の点から主表面10の中心を通過し上記外周上の他の点まで延びる線分のうち、最長となる線分の長さをいうものとする。
主表面10は、ベータ型Ga2O3単結晶の(001)面である。または主表面10は、上記ベータ型Ga2O3単結晶の(001)面から0°より大きく10°以下のオフ角、および上記ベータ型Ga2O3単結晶の[010]方向もしくは上記[010]方向に直交する方向のオフ方向を有する面である。これにより、光学デバイス、電子デバイス等を形成するために汎用されるベータ型Ga2O3単結晶の(001)面等を主表面10としたベータ型Ga2O3単結晶基板1を提供することが可能となる。
上記ベータ型Ga2O3単結晶基板は、ロジウム(Rh)およびイリジウム(Ir)の両方またはいずれか一方を含む。上記Rhの濃度および上記Irの濃度は、いずれもGDMSにおいて3質量ppm未満である。上記Rhの濃度および上記Irの濃度は、いずれもGDMSにおいて1質量ppm以下であることが好ましく、0.1質量ppm以下であることがより好ましく、0.01質量ppm以下であることがよりさらに好ましい。上記Rhの濃度および上記Irの濃度の下限は、いずれもGDMSにおいて検出されないことである。上記ベータ型Ga2O3単結晶基板は、上記Rhおよび上記Irが3質量ppm未満であることにより、電気的特性および光学的特性の両者において優れることができる。
以下、グロー放電質量分析(GDMS)を用い、上記ベータ型Ga2O3単結晶基板中のRhおよびIrの濃度を測定する方法について説明する。GDMSとは、高純度のアルゴン雰囲気下で分析試料を陰極としてグロー放電プラズマを発生させ、上記プラズマ内で上記分析試料の表面をスパッタすることにより、イオン化した上記分析試料中の構成元素を質量分析計で測定する手法をいう。これにより、上記ベータ型Ga2O3単結晶基板中に含まれるGaおよびO以外の、RhおよびIrをはじめとする不純物元素の定性および定量を行うことができる。上記GDMSのイオン源としては、フラットセルとピン状セルとのどちらかを適用する。ピン状セルについては、形状を凡そ2mm角かつ長さ20mmの短冊状に形成することが可能な分析試料に適用することができる。具体的には、へき開によって試料作成が可能なSi単結晶、ヒ化ガリウム(GaAs)単結晶およびリン化インジウム(InP)単結晶などを分析する場合に使用される。フラットセルは、直径10mm程度の円盤状に形成可能な分析試料に適用することができ、たとえば多結晶体などを分析する場合を挙げることができる。いずれにしても、分析試料への外部からの不純物元素の汚染を避ける観点から、上記GDMSのイオン源としてフラットセルとピン状セルとのどちらかを選択することが好ましい。上記ベータ型Ga2O3単結晶基板は、へき開を長手方向としてピン状分析試料が作製できるため、上記ベータ型Ga2O3単結晶基板からピン状セルの形状とした分析試料を作製し、これをGDMSのイオン源とすることが好ましい。
装置:グロー放電質量分析装置(商品名(品番):VG-9000、VG Elemental社製)
イオン源:ピン状セル(分析時は液体窒素で冷却)
放電面積:直径10mm
放電ガス:高純度アルゴン(6Nグレード)
放電条件:2mA、1kV(定電流モード)
検出器:ファラデーカップおよびマルチプライヤー
質量分解能:4000以上のm/Δm(高分解能モード)。
上記ベータ型Ga2O3単結晶基板において、波長400nm以上430nm以下の光に対する透過率は、70%以上であることが好ましい。上記Van der Pauw法によるホール測定において25℃にて測定されるキャリア濃度は、1×1017cm-3以上1.0×1019cm-3以下であることが好ましい。これにより、電気的特性および光学的特性の両者においてより優れることができる。
本実施形態において、上記Van der Pauw法によるホール測定において25℃にて測定されるキャリア濃度は、1×1017cm-3以上1.0×1019cm-3以下であることが好ましい。具体的には、上記ベータ型Ga2O3単結晶基板の中心を測定対象としてVan der Pauw法によるホール測定において25℃にて求めたキャリア濃度は、1×1017cm-3以上1.0×1019cm-3以下であることが好ましい。上記キャリア濃度が1.0×1017cm-3未満である場合、半導体素子を作成した場合に電流が流れず、素子が動作しなくなる恐れがある。上記キャリア濃度が1.0×1019cm-3を超える場合、結晶中に不活性な不純物が1.0×1019cm-3以上含有していることを示唆し、素子動作時に悪影響を与える恐れがある。とりわけ上記キャリア濃度は、5.0×1017cm-3以上3.8×1018cm-3以下であることがより好ましい。これにより上記n型のベータ型Ga2O3単結晶基板は、各種の電子デバイスおよび光学デバイスに汎用させることが可能な良好な電気的特性を備えることができる。上記キャリア濃度は、次の測定方法により求めることができる。
本実施形態に係るベータ型Ga2O3単結晶基板は、電気的特性および光学的特性の両者においてより優れることから、光学デバイスおよび電子デバイスを形成するための基板として適用することができる。とりわけベータ型Ga2O3単結晶基板は、良好な電気的特性に基づいて電子デバイスを形成するための基板として適用することが好ましい。
<試料10A>
上記特許文献1に開示された方法に沿って、垂直ブリッジマン(VB:Vertical Bridgeman)法を用いることにより、成長方向を[001]方向としてベータ型Ga2O3単結晶を製造することを試みた。上記ベータ型Ga2O3単結晶を得る際には、Rhを30質量%含むPt-Rh合金からなる坩堝を用いた。上記坩堝の直胴部の内径は、105mmであった。さらに上記坩堝の側壁部の厚みは、0.2μmであり、上記側壁部の内周面側の表面の表面粗さRzは20μmであった。しかしながら結晶成長時に上記坩堝が割れたため、上記ベータ型Ga2O3単結晶を得ることができず、もって試料10Aのベータ型Ga2O3単結晶基板は得られなかった。
試料10Aのベータ型Ga2O3単結晶基板を得る方法と同じ要領により、成長方向を[001]方向としてベータ型Ga2O3単結晶を製造した。本試験例においては、坩堝の割れは認められなかった。上記ベータ型Ga2O3単結晶の結晶外径は、120mmであった。さらに上記ベータ型Ga2O3単結晶に対し、上述した切断工程、外周研削工程、および研磨工程をこの順に実行した。以上により、試料10Bのベータ型Ga2O3単結晶基板を得た。試料10Bのベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料10Bのベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて25質量ppmであり、Irの濃度は、上述したGDMSにおいて0.02質量ppmであった。
坩堝の側壁部の厚みを1.0mmとしたこと以外、試料10Aのベータ型Ga2O3単結晶基板を得る方法と同じ要領により、成長方向を[001]方向としてベータ型Ga2O3単結晶を製造した。本試験例において、坩堝の割れは認められなかった。上記ベータ型Ga2O3単結晶の結晶外径は、108mmであった。さらに上記ベータ型Ga2O3単結晶に対し、上述した切断工程、外周研削工程、および研磨工程をこの順に実行した。以上により、試料10Cのベータ型Ga2O3単結晶基板を得た。試料10Cのベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料10Cのベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて45質量ppmであり、Irの濃度は、上述したGDMSにおいて0.02質量ppmであった。
(準備工程S110)
まず単結晶成長装置100、ベータ型Ga2O3単結晶からなる種結晶8aおよび塊状のGa2O3多結晶を従来公知の方法により準備し、あるいは市販のものを入手することにより準備した。単結晶成長装置100を構成する坩堝5としては、CaOを10.8質量%含む純度89.2質量%の安定化ZrO2からなり、3mmの厚みを有する側壁部5a、および500μmの厚みを有する溶射膜5bを備える坩堝を用いた。より具体的には、坩堝5の直胴部の内径は、105mmであった。さらに側壁部5aの内周面側の表面の表面粗さRzは20μmであった。溶射膜5bの組成は、Rhを30質量%含むPt-Rh合金であり、溶射膜5bの空孔率は10%であった。
次に従来公知の方法により、坩堝5の種結晶収容部51に種結晶8aを収容し、かつこの種結晶8aよりも上部に塊状のGa2O3多結晶を収容した。具体的には、塊状のGa2O3多結晶を増径部52および直胴部53内に複数個収容し、積み重ねた。続いて種結晶8aおよび塊状のGa2O3多結晶を内部に収容した坩堝5を坩堝保持台6で支持させた。その後、加熱装置7に電流を供給して坩堝5を加熱し、Ga2O3多結晶および種結晶8aの一部をそれぞれ融解することによりGa2O3融液82を調製した。次いで種結晶8aの残部とGa2O3融液82とを、その界面にて接触させた。
次に、加熱装置7に対し坩堝5を、その軸に沿って下向き(底部側)に徐々に引下げていくことにより、坩堝5において種結晶8a側の温度が低く、Ga2O3融液82側の温度が高くなるような温度勾配とした。これによりGa2O3融液82から種結晶8a側の上記残部の上に、成長方向を[001]方向として結晶を成長させてベータ型Ga2O3単結晶81を得た。さらに、この操作を引き下げ距離が100mmとなるまで継続した。成長中のベータ型Ga2O3単結晶81とGa2O3融液82との界面の温度については1800~1820℃とした。上記界面における上記温度勾配については、5℃/cmとした。坩堝5をその軸に沿って下向きに引下げるスピードについては1mm/時とした。以上によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
最後に、Ga2O3単結晶成長工程S140において得たベータ型Ga2O3単結晶のインゴットに対し、切断工程、外周研削工程、および研磨工程の各工程において加工することによって、ベータ型Ga2O3単結晶基板を得た。まず切断工程においては、従来公知の方法を用いて上記インゴットを700μmの厚みを有するウェーハとなるようにスライスした。外周研削工程においては、従来公知の方法を用いて上記ウェーハの外周に面取り加工を施すように研削することにより、中心部と上記中心部の外周を囲む外周部とからなる主表面を有するウェーハを得た。さらに研磨工程においては、従来公知の研磨方法を用いて上記中心部を研磨し、上記中心部において、たとえばJIS B 0681-2:2018に規定される表面粗さRaを8nmとした。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bにおける空孔率が20%である坩堝を準備したこと以外、試料101のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料102のベータ型Ga2O3単結晶基板を得た。試料102のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料102のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて20質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bにおける空孔率が30%である坩堝を準備したこと以外、試料101のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料103のベータ型Ga2O3単結晶基板を得た。試料103のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料103のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて18質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bの厚みが200μmである坩堝を準備したこと以外、試料101のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料104のベータ型Ga2O3単結晶基板を得た。試料104のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料104のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて17質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bの厚みが200μmである坩堝を準備したこと以外、試料102のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料105のベータ型Ga2O3単結晶基板を得た。試料105のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料105のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて25質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bの厚みが200μmである坩堝を準備したこと以外、試料103のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料106のベータ型Ga2O3単結晶基板を得た。試料106のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料106のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて40質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが100μmである坩堝を準備したこと以外、試料104のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料107のベータ型Ga2O3単結晶基板を得た。試料107のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料107のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて28質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが100μmである坩堝を準備したこと以外、試料105のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料108のベータ型Ga2O3単結晶基板を得た。試料108のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料108のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて15質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが300μmである坩堝を準備したこと以外、試料104のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料109のベータ型Ga2O3単結晶基板を得た。試料109のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料109のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて22質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが300μmである坩堝を準備したこと以外、試料105のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料110のベータ型Ga2O3単結晶基板を得た。試料110のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料110のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて25質量ppmであり、Irの濃度は、上述したGDMSにおいて0.02質量ppmであった。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが300μmである坩堝を準備したこと以外、試料106のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料111のベータ型Ga2O3単結晶基板を得た。試料111のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料111のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて27質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
試料111のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料112のベータ型Ga2O3単結晶基板を得た。試料112のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料112のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて20質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程において、側壁部5aの内周面側を次の第1膜5b1および第2膜5b2からなる溶射膜にて被覆した坩堝を準備したこと以外、試料109のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。すなわち本試験例の準備工程においては、坩堝5における側壁部5aの内周面側の表面に対して第1溶射材を溶射することにより、Rhからなり、第1膜空孔率が30%であり、かつ厚みが50μmである第1膜5b1で上記表面を被覆した。さらに第1膜5b1に対して第2溶射材を溶射することにより、Ptからなり、第2膜空孔率が30%であり、かつ厚みが150μmである第2膜5b2で、第1膜5b1を被覆した。
試料113のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料114のベータ型Ga2O3単結晶基板を得た。試料114のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料114のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて0.08質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
試料113のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料115のベータ型Ga2O3単結晶基板を得た。試料115のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料115のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて2.9質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。
上記Ga2O3単結晶を得る際に用いる坩堝の直胴部の内径を156mmとしたこと以外、試料10Aおよび試料10Bのベータ型Ga2O3単結晶基板を得る方法と同じ要領により、試料20Aおよび試料20Bのベータ型Ga2O3単結晶基板をそれぞれ製造することを試みた。しかしながら結晶成長時に上記坩堝が割れたため、試料20Aおよび試料20Bのベータ型Ga2O3単結晶基板は得られなかった。
坩堝の側壁部の厚みを1.0mmとしたこと以外、試料20Aおよび試料20Bのベータ型Ga2O3単結晶基板を得る方法と同じ要領により、成長方向を[001]方向としてベータ型Ga2O3単結晶を製造した。本試験例において、坩堝の割れは認められなかった。上記ベータ型Ga2O3単結晶の結晶外径は、165mmであった。さらに上記ベータ型Ga2O3単結晶に対し、上述した切断工程、外周研削工程、および研磨工程をこの順に実行した。以上により、試料20Cのベータ型Ga2O3単結晶基板を得た。試料20Cのベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料20Cのベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて38質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。
準備工程において、直胴部の内径が156mmである坩堝を準備したこと以外、試料101のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料201のベータ型Ga2O3単結晶基板を得た。試料201のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料201のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて15質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bにおける空孔率が20%である坩堝を準備したこと以外、試料201のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料202のベータ型Ga2O3単結晶基板を得た。試料202のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料202のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて20質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、加熱される結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bにおける空孔率が30%である坩堝を準備したこと以外、試料201のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料203のベータ型Ga2O3単結晶基板を得た。試料203のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料203のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて23質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bの厚みが200μmである坩堝を準備したこと以外、試料201のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料204のベータ型Ga2O3単結晶基板を得た。試料204のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料204のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて27質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bの厚みが200μmである坩堝を準備したこと以外、試料202のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料205のベータ型Ga2O3単結晶基板を得た。試料205のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料205のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて15質量ppmであり、Irの濃度は、上述したGDMSにおいて0.02質量ppmであった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側を被覆する溶射膜5bの厚みが200μmである坩堝を準備したこと以外、試料203のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料206のベータ型Ga2O3単結晶基板を得た。試料206のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料206のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて35質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが100μmである坩堝を準備したこと以外、試料204のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料207のベータ型Ga2O3単結晶基板を得た。試料207のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料207のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて18質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが100μmである坩堝を準備したこと以外、試料205のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料208のベータ型Ga2O3単結晶基板を得た。試料208のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料208のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて25質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが300μmである坩堝を準備したこと以外、試料204のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料209のベータ型Ga2O3単結晶基板を得た。試料209のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料209のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて32質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程において、側壁部5aの内周面側の表面の表面粗さRzが300μmである坩堝を準備したこと以外、試料205のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料210のベータ型Ga2O3単結晶基板を得た。試料210のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料210のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて26質量ppmであり、Irの濃度は、上述したGDMSにおいて0.02質量ppmであった。
準備工程において、側壁部5aの内周面側を次の第1膜5b1および第2膜5b2からなる溶射膜にて被覆した坩堝を準備したこと以外、試料209のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。すなわち本試験例の準備工程においては、坩堝5における側壁部5aの内周面側の表面に対して第1溶射材を溶射することにより、Rhからなり、第1膜空孔率が30%であり、かつ厚みが50μmである第1膜5b1で上記表面を被覆した。さらに第1膜5b1に対して第2溶射材を溶射することにより、Ptからなり、第2膜空孔率が30%であり、かつ厚みが150μmである第2膜5b2で、第1膜5b1を被覆した。
試料211のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料212のベータ型Ga2O3単結晶基板を得た。試料212のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料212のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて0.01質量ppm未満であり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
試料211のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、157.1mmであった。さらに上記ベータ型Ga2O3単結晶から、試料213のベータ型Ga2O3単結晶基板を得た。試料213のベータ型Ga2O3単結晶基板の直径は、152.4mmであり、厚みは、650μmであった。試料213のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて2.8質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを11質量%含むPt-Rh合金としたこと以外、試料101のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料301のベータ型Ga2O3単結晶基板を得た。試料301のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料301のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて14質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを11質量%含むPt-Rh合金としたこと以外、試料102のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料302のベータ型Ga2O3単結晶基板を得た。試料302のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料302のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて21質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを11質量%含むPt-Rh合金としたこと以外、試料103のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料303のベータ型Ga2O3単結晶基板を得た。試料303のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料303のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて19質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを11質量%含むPt-Rh合金としたこと以外、試料104のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料304のベータ型Ga2O3単結晶基板を得た。試料304のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料304のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて18質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを11質量%含むPt-Rh合金としたこと以外、試料105のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料305のベータ型Ga2O3単結晶基板を得た。試料305のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料305のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて24質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを10質量%含むPt-Rh合金としたこと以外、試料106のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料306のベータ型Ga2O3単結晶基板を得た。試料306のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料306のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて22質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを10質量%含むPt-Rh合金としたこと以外、試料107のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料307のベータ型Ga2O3単結晶基板を得た。試料307のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料307のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて25質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを10質量%含むPt-Rh合金としたこと以外、試料108のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料308のベータ型Ga2O3単結晶基板を得た。試料308のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料308のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて17質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。なお坩堝5については、結晶成長時に割れは認められなかったものの、結晶成長後の冷却時に割れが認められた。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを10質量%含むPt-Rh合金としたこと以外、試料109のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料309のベータ型Ga2O3単結晶基板を得た。試料309のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料309のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて21質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを10質量%含むPt-Rh合金としたこと以外、試料110のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料310のベータ型Ga2O3単結晶基板を得た。試料310のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料310のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて26質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppmであった。
準備工程S110において、単結晶成長装置100を構成する坩堝5として、Y2O3を13.8質量%含む純度86.2質量%の安定化ZrO2からなり、9mmの厚みを有する側壁部5a、および坩堝5の側壁部5aの内周面側を被覆する溶射膜5bの組成を、Rhを10質量%含むPt-Rh合金としたこと以外、試料111のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料311のベータ型Ga2O3単結晶基板を得た。試料311のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料311のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて14質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
試料311のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。上記ベータ型Ga2O3単結晶の結晶外径は、105.8mmであった。さらに上記ベータ型Ga2O3単結晶から、試料312のベータ型Ga2O3単結晶基板を得た。試料312のベータ型Ga2O3単結晶基板の直径は、101.6mmであり、厚みは、650μmであった。試料312のベータ型Ga2O3単結晶基板におけるRhの濃度は、上述したGDMSにおいて13質量ppmであり、Irの濃度は、上述したGDMSにおいて0.01質量ppm未満であった。
準備工程において、側壁部5aの内周面側を次の第1膜5b1および第2膜5b2からなる溶射膜にて被覆した坩堝を準備したこと以外、試料309のベータ型Ga2O3単結晶基板を得る方法と同じ要領によりベータ型Ga2O3単結晶のインゴットを得た。すなわち本試験例の準備工程においては、坩堝5における側壁部5aの内周面側の表面に対して第1溶射材を溶射することにより、Rhからなり、第1膜空孔率が30%であり、かつ厚みが50μmである第1膜5b1で上記表面を被覆した。さらに第1膜5b1に対して第2溶射材を溶射することにより、Ptからなり、第2膜空孔率が30%であり、かつ厚みが150μmである第2膜5b2で、第1膜5b1を被覆した。
<製品収率>
試料10B~試料10C、試料101~試料115、試料20C、試料201~試料213、および試料301~試料313のベータ型Ga2O3単結晶基板を得るためのベータ型Ga2O3単結晶を対象として、次の方法により製品収率を求めた。上述のように「製品収率」とは、坩堝内で結晶成長させたベータ型Ga2O3単結晶のインゴットの質量のうち、冷却時に坩堝が割れたり、欠けたりし、あるいは結晶が割れたり、欠けたりすることにより、ベータ型三酸化二ガリウム単結晶基板に加工した場合に所望の直径が得られなくなる領域を除き、かつ、後述する評価方法によって上記基板として良品となり得ると評価された部分の質量が占める割合を意味する。当該単結晶の製品収率が良好であるほど、上記単結晶を成長させた坩堝において割れ、欠け等が発生しなかったと評価することができる。
試料10B~試料10C、試料101~試料115、試料20C、試料201~試料213、および試料301~試料313のベータ型Ga2O3単結晶基板に対し、上記基板の中央部を用いて作製したホール測定用サンプルに対し、上述した測定方法を実行することにより、各試料におけるキャリア濃度を求めた。また、グロー放電質量分析(GDMS)を用い、上記ベータ型Ga2O3単結晶基板中のSnまたはSiの不純物濃度を求めた。上記各試料におけるキャリア濃度をGDMSで求めた上記不純物濃度で除算することにより、各試料における活性化率を算出した。結果を、表4、表5、および表6に示す。
試料10B~試料10C、試料101~試料115、試料20C、試料201~試料213、および試料301~試料313のベータ型Ga2O3単結晶基板に対し、上記基板の中央部を用いて作製した透過率測定用サンプルに対し、上述した測定方法を実行することにより、各試料における波長427nmの光の透過率を求めた。結果を、表4、表5、および表6に示す。
表4によれば、試料101~試料115のベータ型Ga2O3単結晶基板における製品収率は、試料10B~試料10Cのベータ型Ga2O3単結晶基板におけるそれに比べ、良好であった。したがって試料101~試料115のベータ型Ga2O3単結晶基板を製造するための坩堝は、試料10B~試料10Cのベータ型Ga2O3単結晶基板を製造するためのそれに比べ、結晶成長時に割れ、欠けが発生することを抑制することができると評価することができる。表5によれば、試料201~試料213のベータ型Ga2O3単結晶基板における製品収率は、試料20Cのベータ型Ga2O3単結晶基板におけるそれに比べ、良好であった。したがって試料201~試料213のベータ型Ga2O3単結晶基板を製造するための坩堝は、試料10Cのベータ型Ga2O3単結晶基板を製造するためのそれに比べ、結晶成長時に割れ、欠けが発生することを抑制することができると評価することができる。表6によれば、試料301~試料313のベータ型Ga2O3単結晶基板における製品収率は、試料101~試料115のベータ型Ga2O3単結晶基板におけるそれと同様に、良好であった。したがって試料301~試料313のベータ型Ga2O3単結晶基板を製造するための坩堝は、結晶成長時に割れ、欠けが発生することを抑制することができると評価することができる。
Claims (12)
- ベータ型三酸化二ガリウム単結晶成長用の坩堝であって、
前記坩堝は、1mm以上10mm以下の厚みを有し、
前記坩堝の最大内径は、100mm以上であり、
前記坩堝の組成は、酸化イットリウムおよび酸化カルシウムの両方またはいずれか一方を含む安定化ジルコニアであり、
前記坩堝の内周面側の表面は、ロジウムおよび白金の両方またはいずれか一方を含む溶射膜により被覆され、
前記溶射膜の厚みは、100μm以上500μm以下であり、
前記安定化ジルコニアは、少なくとも前記酸化イットリウムを12.0質量%以上15.5質量%以下含み、または前記酸化カルシウムを10.2質量%以上11.4質量%以下含む、坩堝。 - 前記溶射膜は、ロジウムを10質量%以上30質量%以下含む白金-ロジウム合金からなる、請求項1に記載の坩堝。
- 前記溶射膜は、空孔を有し、
前記溶射膜に占める前記空孔の体積比率である空孔率は、30体積%以上50体積%以下である、請求項2に記載の坩堝。 - 前記表面の表面粗さRzは、300μm以上500μm以下であり、
前記溶射膜は、空孔を有し、
前記溶射膜に占める前記空孔の体積比率である空孔率は、10体積%以上30体積%未満である、請求項2に記載の坩堝。 - 前記表面の表面粗さRzは、300μm以上500μm以下である、請求項3に記載の坩堝。
- 前記溶射膜は、第1膜および第2膜からなり、
前記第1膜は、前記表面を被覆し、
前記第1膜は、ロジウム、またはロジウムを主成分とする白金-ロジウム合金からなり、
前記第2膜は、前記第1膜を被覆し、
前記第2膜は、白金、または白金を主成分とする白金-ロジウム合金からなり、
前記溶射膜の厚みは、前記第1膜と前記第2膜との合計で100μm以上500μm以下である、請求項1に記載の坩堝。 - 前記第1膜および前記第2膜は、いずれも空孔を有し、
前記第1膜に占める前記空孔の体積比率である第1膜空孔率、および前記第2膜に占める前記空孔の体積比率である第2膜空孔率は、いずれも30体積%以上50体積%以下である、請求項6に記載の坩堝。 - 前記表面の表面粗さRzは、300μm以上500μm以下であり、
前記第1膜および前記第2膜は、いずれも空孔を有し、
前記第1膜に占める前記空孔の体積比率である第1膜空孔率、および前記第2膜に占める前記空孔の体積比率である第2膜空孔率は、いずれも10体積%以上30体積%未満である、請求項6に記載の坩堝。 - 前記表面の表面粗さRzは、300μm以上500μm以下である、請求項7に記載の坩堝。
- 請求項1から請求項9のいずれか1項に記載の坩堝を用いたベータ型三酸化二ガリウム単結晶基板の製造方法であって、
前記坩堝を準備する工程と、
前記坩堝を用いた縦型ボート法によってベータ型三酸化二ガリウム単結晶を得る工程と、
前記ベータ型三酸化二ガリウム単結晶を加工することにより、円形状の主表面を有するベータ型三酸化二ガリウム単結晶基板を得る工程とを含む、ベータ型三酸化二ガリウム単結晶基板の製造方法。 - 円形状の主表面を有するベータ型三酸化二ガリウム単結晶基板であって、
前記ベータ型三酸化二ガリウム単結晶基板の直径は、100mm以上であり、
前記主表面は、
ベータ型三酸化二ガリウム単結晶の(001)面であるか、または
前記ベータ型三酸化二ガリウム単結晶の(001)面から0°より大きく10°以下のオフ角、および前記ベータ型三酸化二ガリウム単結晶の[010]方向もしくは前記[010]方向に直交する方向のオフ方向を有する面であり、
前記ベータ型三酸化二ガリウム単結晶基板は、ロジウムおよびイリジウムの両方またはいずれか一方を含み、
前記ロジウムの濃度および前記イリジウムの濃度は、グロー放電質量分析においていずれも3質量ppm未満である、ベータ型三酸化二ガリウム単結晶基板。 - 波長400nm以上430nm以下の光に対する透過率は、70%以上であり、
Van der Pauw法によるホール測定において25℃にて測定されるキャリア濃度は、1×1017cm-3以上1.0×1019cm-3以下である、請求項11に記載のベータ型三酸化二ガリウム単結晶基板。
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| PCT/JP2023/021100 WO2024252544A1 (ja) | 2023-06-07 | 2023-06-07 | 坩堝、それを用いたベータ型三酸化二ガリウム単結晶基板の製造方法、およびベータ型三酸化二ガリウム単結晶基板 |
| TW113106980A TW202507090A (zh) | 2023-06-07 | 2024-02-27 | 坩鍋、使用其之β型三氧化二鎵單晶基板之製造方法及β型三氧化二鎵單晶基板 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH042687A (ja) * | 1990-04-18 | 1992-01-07 | Fujikura Ltd | 酸化物単結晶育成用るつぼ |
| JP2000344593A (ja) * | 1999-06-02 | 2000-12-12 | Nippon Telegr & Teleph Corp <Ntt> | 単結晶育成用るつぼ |
| JP2016117606A (ja) * | 2014-12-19 | 2016-06-30 | 株式会社タムラ製作所 | Ga2O3系単結晶の育成方法、及び坩堝 |
| JP2020090403A (ja) * | 2018-12-04 | 2020-06-11 | Tdk株式会社 | 単結晶育成用ルツボ、単結晶製造方法及び単結晶 |
| JP2021134140A (ja) * | 2020-02-27 | 2021-09-13 | 不二越機械工業株式会社 | 酸化ガリウム結晶の製造装置 |
| CN114318503A (zh) * | 2021-12-30 | 2022-04-12 | 陕西旭光晶体科技有限公司 | 氧化嫁晶体用的铂铱合金坩埚以及制备方法 |
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- 2023-06-07 JP JP2025525512A patent/JPWO2024252544A1/ja active Pending
- 2023-06-07 WO PCT/JP2023/021100 patent/WO2024252544A1/ja not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH042687A (ja) * | 1990-04-18 | 1992-01-07 | Fujikura Ltd | 酸化物単結晶育成用るつぼ |
| JP2000344593A (ja) * | 1999-06-02 | 2000-12-12 | Nippon Telegr & Teleph Corp <Ntt> | 単結晶育成用るつぼ |
| JP2016117606A (ja) * | 2014-12-19 | 2016-06-30 | 株式会社タムラ製作所 | Ga2O3系単結晶の育成方法、及び坩堝 |
| JP2020090403A (ja) * | 2018-12-04 | 2020-06-11 | Tdk株式会社 | 単結晶育成用ルツボ、単結晶製造方法及び単結晶 |
| JP2021134140A (ja) * | 2020-02-27 | 2021-09-13 | 不二越機械工業株式会社 | 酸化ガリウム結晶の製造装置 |
| CN114318503A (zh) * | 2021-12-30 | 2022-04-12 | 陕西旭光晶体科技有限公司 | 氧化嫁晶体用的铂铱合金坩埚以及制备方法 |
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