WO2023021814A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2023021814A1
WO2023021814A1 PCT/JP2022/023026 JP2022023026W WO2023021814A1 WO 2023021814 A1 WO2023021814 A1 WO 2023021814A1 JP 2022023026 W JP2022023026 W JP 2022023026W WO 2023021814 A1 WO2023021814 A1 WO 2023021814A1
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Prior art keywords
single crystal
semiconductor layer
gan
film
gas
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English (en)
French (fr)
Japanese (ja)
Inventor
守道 渡邊
宏之 柴田
潤 吉川
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NGK Insulators Ltd
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NGK Insulators Ltd
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Priority to JP2023542233A priority Critical patent/JP7612029B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials

Definitions

  • the present invention relates to laminates.
  • the present invention relates to a laminate having an ⁇ -Ga 2 O 3 -based semiconductor layer and a Group 13 nitride single crystal.
  • gallium oxide (Ga 2 O 3 ) has attracted attention as a semiconductor material.
  • Gallium oxide is known to have five crystal structures: ⁇ , ⁇ , ⁇ , ⁇ and ⁇ .
  • ⁇ -Ga 2 O 3 has a bandgap of about 5 eV and has high stability up to about 870° C., so it has attracted a great deal of attention as a next-generation power semiconductor material with high breakdown voltage and low power consumption.
  • Patent Document 1 Japanese Patent No. 6436538 discloses an ⁇ -Ga 2 O 3 single crystal with a low impurity concentration that is applicable to semiconductor devices and is produced using the HVPE method.
  • Non-Patent Document 1 Yamaichi Oshima et al. "Epitaxial growth of phase-pure ⁇ -Ga 2 O 3 by halide vapor phase epitaxy" J. Appl. Phys, 118, 085301 (2015)
  • ⁇ - Ga 2 O 3 is disclosed to be epitaxially grown.
  • Patent Document 2 Japanese Patent No. 6018360 discloses a compound semiconductor device (GaN-based HEMT) capable of obtaining an electron transit layer and an electron supply layer with good crystallinity. Also, in order to further increase the withstand voltage of HEMTs, the application of ⁇ -Ga 2 O 3 -based materials having a bandgap higher than that of GaN-based materials is attracting attention.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2019-46984 discloses a method of manufacturing a semiconductor device having excellent semiconductor characteristics using ⁇ -Ga 2 O 3 .
  • a first semiconductor film containing as a main component a semiconductor crystal having a metastable crystal structure and a hexagonal crystal structure different in composition from the main component of the first semiconductor film are formed by a mist CVD method. It is described that a second semiconductor film (main component is ⁇ -Ga 2 O 3 ) containing as a main component a semiconductor crystal having
  • ⁇ -Ga 2 O 3 is only known to be formed by heteroepitaxial growth, which requires film formation on a heterogeneous substrate such as GaN.
  • a GaN template used for such film formation is obtained by forming a GaN film on a sapphire substrate or a SiC substrate.
  • Non-Patent Document 2 Silicone et al. "Epitaxial growth of GaN/Ga 2 O 3 and Ga 2 O 3 /GaN heterostructures for novel high electron mobility transistors" Journal of Crystal Growth 534 (2020) 125511
  • Patent Document 1 describes a method of forming an ⁇ -Ga 2 O 3 film on a GaN single crystal.
  • Patent Document 1 describes a method of forming an ⁇ -Ga 2 O 3 layer on an AlN template, but if the ⁇ -Ga 2 O 3 film is formed in a size of 2 inches or more, the number of peeling parts increases. There's a problem.
  • the present inventors recently found that the ⁇ -Ga 2 O 3 -based semiconductor layer was formed on a high-resistivity and thick group 13 nitride single crystal as a base substrate by forming an ⁇ -Ga 2 O 3 -based semiconductor layer on the base substrate.
  • the inventors have found that it is possible to provide a laminate that is difficult to separate from the substrate.
  • an object of the present invention is to provide a laminate in which the ⁇ -Ga 2 O 3 based semiconductor layer is less likely to separate from the base substrate.
  • Aspect 1 a semiconductor layer composed of ⁇ -Ga 2 O 3 or an ⁇ -Ga 2 O 3 -based solid solution; a high-resistivity group 13 nitride single crystal having a resistivity of 1.00 ⁇ 10 2 ⁇ cm or more at 25° C. and a thickness of 200 ⁇ m or more; A laminate having a two-layer structure composed of [Aspect 2] The laminate according to aspect 1, wherein the high-resistivity group 13 nitride single crystal is any one single crystal selected from GaN, AlN and BN.
  • Aspect 3 Aspect 2, wherein the high resistance group 13 nitride single crystal is a GaN single crystal and contains Zn as a dopant at a concentration of 1.00 ⁇ 10 18 to 2.00 ⁇ 10 19 atoms/cm 3 . laminate.
  • Aspect 4 Aspect 2 or 3, wherein the high-resistivity group 13 nitride single crystal is a GaN single crystal and contains Fe as a dopant at a concentration of 1.00 ⁇ 10 18 to 2.00 ⁇ 10 19 atoms/cm 3 .
  • FIG. 2 is a cross-sectional view of the upper part of the crystal plate manufacturing apparatus 10 taken horizontally.
  • FIG. 2 is a cross-sectional view taken along the line AA of FIG. 1;
  • 2 is a cross-sectional view of the pressure-resistant container 12 for explaining the overall structure of the pressure-resistant container 12.
  • FIG. 4 is a cross-sectional view of the pressure-resistant container 12 when the pressure-resistant container 12 is tilted by the rocking device 70.
  • FIG. It is a schematic cross-sectional view showing the configuration of a vapor phase growth apparatus using the HVPE method.
  • 1 is a schematic cross-sectional view showing the configuration of a mist CVD apparatus;
  • the laminate of the present invention has a two-layer structure composed of a semiconductor layer composed of an ⁇ -Ga 2 O 3 or ⁇ -Ga 2 O 3 solid solution and a high-resistivity Group 13 nitride single crystal.
  • the high-resistivity group 13 nitride single crystal has a resistivity of 1.00 ⁇ 10 2 ⁇ cm or more at 25° C. and a thickness of 200 ⁇ m or more.
  • the ⁇ -Ga 2 O 3 -based semiconductor layer is separated from the underlying substrate. It is possible to provide a laminate that is difficult to resist.
  • ⁇ -Ga 2 O 3 has a problem that the ⁇ -Ga 2 O 3 film formed on a different substrate such as GaN by heteroepitaxial growth tends to peel off from the underlying substrate. can conveniently solve this problem.
  • the ratio t 1 /t 2 of the thickness t 1 of the semiconductor layer to the thickness t 2 of the high-resistance group 13 nitride single crystal is preferably small, for example, 1.00 or less. It is preferably 0.1 or less, more preferably 0.1 or less. Although there is no particular lower limit to t 1 /t 2 , it is preferably 1.00 ⁇ 10 ⁇ 5 or more. That is, t 1 /t 2 is preferably 1.00 ⁇ 10 ⁇ 5 to 1.00, more preferably 1.00 ⁇ 10 ⁇ 5 to 1.00 ⁇ 10 ⁇ 1 . By doing so, the effect of suppressing peeling of the semiconductor layer is improved.
  • a larger diameter of the laminate is preferable because a larger number of chips can be produced, and is preferably 50.8 mm or more, more preferably 100 mm or more, and even more preferably 150 mm or more. Although the upper limit of this size is not particularly limited, it is preferably 200 mm or less.
  • the high resistance Group 13 nitride single crystal included in the laminate of the present invention has a specific resistance at 25° C. of 1.00 ⁇ 10 2 ⁇ cm or more and a thickness of 200 ⁇ m or more. be.
  • GaN templates and GaN single crystals which have conventionally been used as base substrates, have low resistance.
  • the resistance is lowered due to the lack of N and the presence of O as an impurity.
  • the GaN single crystal of Patent Document 1 and the GaN template of Non-Patent Document 2 are n-type doped, but even if they are non-doped, the resistance is considered to be low.
  • the group 13 nitride single crystal included in the laminate of the present invention has a high resistivity of 1.00 ⁇ 10 2 ⁇ cm or more at 25° C. Such a high resistance Group 13 nitride single crystal cannot be obtained from a conventional underlying substrate. The higher the specific resistance at 25° C.
  • the better preferably 1.00 ⁇ 10 4 ⁇ cm or more, more preferably 1.00 ⁇ 10 5 ⁇ cm or more, and even more preferably. is 1.00 ⁇ 10 8 ⁇ cm or more, particularly preferably 1.00 ⁇ 10 11 ⁇ cm or more. Although there is no particular upper limit to this specific resistance, it is preferably 1.00 ⁇ 10 18 ⁇ cm or less.
  • the thickness of the high-resistance group 13 nitride single crystal is desirably thick from the viewpoint of suppressing peeling of the ⁇ -Ga 2 O 3 based semiconductor layer, preferably 300 ⁇ m or more, more preferably 500 ⁇ m or more, and the upper limit is particularly do not have.
  • the thickness is desirably thinner from the viewpoint of improving cost and heat dissipation, preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less.
  • the thickness of the high resistance group 13 nitride single crystal is preferably 300 to 1000 ⁇ m.
  • the high-resistivity group 13 nitride single crystal is preferably a single crystal selected from GaN, AlN and BN, more preferably GaN or AlN.
  • GaN is preferable from the viewpoint of single crystal size and cost.
  • AlN is preferable from the viewpoint of insulation.
  • the high resistance Group 13 nitride single crystal When the high resistance Group 13 nitride single crystal is a GaN single crystal, it preferably contains a dopant.
  • dopants include Be, Mg, Zn, Fe, Mn and Cd, preferably Zn, Fe or Mn.
  • This dopant is preferably contained in the high resistance group 13 nitride single crystal at a concentration of 1.00 ⁇ 10 18 to 2.00 ⁇ 10 19 atoms/cm 3 . That is, the high resistance group 13 nitride single crystal is a GaN single crystal and contains Zn, Fe or Mn as a dopant at a concentration of 1.00 ⁇ 10 18 to 2.00 ⁇ 10 19 atoms/cm 3 . is preferred.
  • the dopant concentration is 1.00 ⁇ 10 18 atoms/cm 3 or more, it is possible to prevent excessive decrease in resistance, and when the dopant concentration is 2.00 ⁇ 10 19 atoms/cm 3 or less, GaN Single crystal quality can be maintained.
  • the resistance of the GaN template and GaN single crystal conventionally used as the base substrate is low even in a non-doped state.
  • the present invention by counter-doping the group 13 nitride single crystal with Zn or the like, a high resistance group 13 nitride single crystal can be obtained efficiently.
  • a semiconductor layer (hereinafter sometimes referred to as a semiconductor film) constituting the laminate of the present invention is composed of ⁇ -Ga 2 O 3 or ⁇ -Ga 2 O 3 based solid solution. Therefore, this semiconductor layer can be called an ⁇ -Ga 2 O 3 -based semiconductor layer.
  • the ⁇ -Ga 2 O 3 solid solution is a solid solution of ⁇ -Ga 2 O 3 with other components.
  • the ⁇ -Ga 2 O 3 based semiconductor layer includes ⁇ -Ga 2 O 3 , Cr 2 O 3 , Fe 2 O 3 , Ti 2 O 3 , V 2 O 3 , Ir 2 O 3 and Rh 2 O 3 . , In 2 O 3 and Al 2 O 3 .
  • the solid solution amount of these components can be appropriately changed according to the desired properties.
  • Non-Patent Document 3 (Ildiko Cora et al. "The real structure of ⁇ -Ga 2 O 3 and its relation to ⁇ -phase," CrystEngComm, 2017, 19, 1509-1516), depending on the resolution of the probe technology have suggested that the crystal structure of ⁇ -Ga 2 O 3 (hexagonal) and that of ⁇ -Ga 2 O 3 (rectangular) may be confused.
  • ⁇ -Ga 2 O 3 refers not only to ⁇ -Ga 2 O 3 but also to ⁇ -Ga 2 O 3 . That is, in the present specification, even those identified as having the crystal structure of ⁇ -Ga 2 O 3 are regarded as “ ⁇ -Ga 2 O 3 ”, and are referred to as “ ⁇ -Ga 2 O 3 ”. shall be included in the term.
  • Zn, Fe or Mn-doped high resistance group 13 nitride single crystals are added to the ⁇ -Ga 2 O 3 -based semiconductor layer. , Fe or Mn are not diffused. In other words, it is desirable that the concentration of Zn, Fe or Mn in the ⁇ -Ga 2 O 3 based semiconductor layer is low. From this point of view, the concentration of Zn, Fe or Mn in the ⁇ -Ga 2 O 3 based semiconductor layer is preferably 1.00 ⁇ 10 16 atoms/cm 3 or less.
  • Zn, Fe or Mn can be a p-type dopant of Ga 2 O 3 and may be contained in the semiconductor layer. Alternatively, by preventing Mn from diffusing into the semiconductor layer, the semiconductor characteristics can be easily controlled.
  • the orientation of the ⁇ -Ga 2 O 3 -based semiconductor layer of the present invention in the approximate normal direction is not particularly limited, but c-axis orientation is preferred.
  • a typical ⁇ -Ga 2 O 3 -based semiconductor layer is composed of ⁇ -Ga 2 O 3 or a mixed crystal of ⁇ -Ga 2 O 3 and a different material, and has It is oriented.
  • the ⁇ -Ga 2 O 3 -based semiconductor layer may be a mosaic crystal as long as it is biaxially oriented.
  • Mosaic crystals are aggregates of crystals that do not have distinct grain boundaries but have slightly different crystal orientations in one or both of the c-axis and a-axis.
  • a method for evaluating the biaxial orientation is not particularly limited, and known analysis techniques such as an EBSD (Electron Back Scatter Diffraction Patterns) method and an X-ray pole figure can be used.
  • EBSD Electro Back Scatter Diffraction Patterns
  • X-ray pole figure inverse pole figure mapping of the surface (film surface) of the biaxially oriented ⁇ -Ga 2 O 3 layer or a cross section orthogonal to the surface is measured.
  • the approximate normal direction is in the approximate in-plane direction perpendicular to the normal direction.
  • the film is oriented along two axes, ie, the approximate normal direction and the approximate film surface direction, when the two conditions are satisfied.
  • the crystal is oriented along two axes, the c-axis and the a-axis.
  • the substantially normal direction of the film surface is aligned with the c-axis
  • the substantially in-plane direction of the film may be aligned with a specific direction (for example, the a-axis) perpendicular to the c-axis.
  • the semiconductor layer can contain a Group 14 element as a dopant at a rate of 1.0 ⁇ 10 15 to 1.0 ⁇ 10 21 /cm 3 .
  • the group 14 element is a group 14 element according to the periodic table formulated by IUPAC (International Union of Pure and Applied Chemistry), specifically carbon (C), silicon (Si), germanium (Ge ), tin (Sn), and lead (Pb).
  • the dopant amount can be appropriately changed according to the desired properties, but is preferably 1.0 ⁇ 10 15 to 1.0 ⁇ 10 21 /cm 3 , more preferably 1.0 ⁇ 10 17 to 1.0. ⁇ 10 19 /cm 3 .
  • these dopants are uniformly distributed in the layer, and that the concentrations of one surface (front surface) and the opposite surface (back surface) are approximately the same. That is, it is preferable that the semiconductor layer uniformly contains the Group 14 element as a dopant in the above ratio.
  • the thickness of the semiconductor layer can be adjusted as appropriate from the viewpoint of cost and required characteristics. That is, if the thickness is too large, it takes a long time to form a film, so from the viewpoint of cost, it is preferable that the thickness is not extremely thick. However, it is preferable to have a moderately thick layer according to the necessity of the target semiconductor properties. Although the thickness of the layer may be appropriately adjusted according to the desired properties, it is preferably 0.01 to 400 ⁇ m, more preferably 0.1 to 50 ⁇ m. By setting the thickness in such a range, it is possible to achieve both cost and semiconductor characteristics.
  • the laminate preferably has an area of 20 cm 2 or more, more preferably 70 cm 2 or more, even more preferably 170 cm 2 or more. By increasing the area of the laminate in this way, it is possible to obtain a large number of semiconductor elements from one laminate, thereby reducing the manufacturing cost.
  • the upper limit of the size of the laminate is not particularly limited, it is typically 700 cm 2 or less on one side.
  • FIG. 1 is a cross-sectional view of the upper part of the crystal plate manufacturing apparatus 10 cut horizontally
  • FIG. 2 is a cross-sectional view of AA in FIG. 1
  • FIG. 4 is a cross-sectional view of the pressure-resistant container 12 when the pressure-resistant container 12 is tilted by the rocking device 70.
  • peripheral devices such as the nitrogen gas cylinder 22 and the vacuum pump 26 are omitted for convenience.
  • the crystal plate manufacturing apparatus 10 includes a pressure-resistant container 12 and a swing device 70 capable of swinging the pressure-resistant container 12 .
  • the pressure-resistant container 12 includes a container body 12a with a flange and a container lid 12b also with a flange.
  • the pressure-resistant container 12 has a heating space 16 surrounded by a heater cover 14 inside.
  • the heating space 16 has an upper heater 18a, a middle heater 18b, and a lower heater 18c arranged vertically on the side surface of the heater cover 14, and a bottom heater 18d arranged on the bottom surface of the heater cover 14, so that the internal temperature can be adjusted. It has become.
  • the heat insulating property of the heating space 16 is enhanced by a heater heat insulating material 20 covering the heater cover 14 .
  • the pressure vessel 12 is connected to the nitrogen introduction pipes 24 a and 24 b of the nitrogen gas cylinder 22 and to the evacuation pipe 28 of the vacuum pump 26 .
  • the nitrogen introduction pipe 24 a can pass through the pressure-resistant container 12 , the heater heat insulating material 20 , the heater cover 14 and the container 42 to introduce nitrogen gas into the container 42 .
  • the nitrogen introduction pipe 24 b can pass through the pressure container 12 and introduce nitrogen gas into the pressure container 12 .
  • a portion of the nitrogen introduction pipes 24a and 24b from the nitrogen gas cylinder 22 to the pressure vessel 12 is composed of a flexible pipe.
  • a mass flow controller 25 capable of adjusting the flow rate is attached to the nitrogen introduction pipe 24a, and a valve 27 capable of opening and closing the pipe is attached to the nitrogen introduction pipe 24b.
  • the evacuation pipe 28 passes through the pressure vessel 12 and opens into the gap between the pressure vessel 12 and the heater heat insulating material 20 . Since the heater cover 14 is not completely sealed, when the outside of the heater cover 14 is evacuated, the inside of the heater cover 14 is also evacuated.
  • This evacuation pipe 28 is composed of a flexible pipe.
  • a nitrogen exhaust pipe 48 with a valve 49 is also attached to the pressure vessel 12 . This nitrogen exhaust pipe 48 communicates the inside of the container 42 with the outside air by opening the valve 49 . A portion of the nitrogen exhaust pipe 48 outside the pressure vessel 12 is composed of a flexible pipe.
  • a container 42 is arranged on a raised table 30.
  • the container 42 has a bottomed cylindrical container body 42a made of Inconel, and an Inconel container lid 42b that closes an upper opening of the container body 42a.
  • the container lid 42b is also provided with a nitrogen exhaust pipe 48 for discharging the introduced nitrogen that overflows from the internal space of the container 42, together with the nitrogen introduction pipe 24a.
  • An intermediate container 60 having a cylindrical body with a bottom and a lid is housed inside the container 42. Inside the intermediate container 60 is an alumina container having a cylindrical body with a bottom and a lid.
  • a growth container 50 is arranged.
  • the growth vessel 50 contains a mixed melt of growth raw materials (for example, sodium/gallium/zinc/carbon), and a disk-shaped seed crystal substrate tray 52 made of alumina is placed in the mixed melt. .
  • the seed crystal substrate tray 52 has one end in contact with the tray base 56 and the other end in contact with the bottom surface of the growth container 50 .
  • the seed crystal substrate tray 52 has a recess for fitting a disk-shaped seed crystal substrate 54 in the central portion.
  • the seed crystal substrate 54 may be a sapphire substrate on which a GaN thin film is formed by a vapor phase method, or may be a GaN substrate.
  • the rocking device 70 is mounted above a base 72 on which the pressure-resistant container 12 is placed and four pillars 73 erected around the base 72 . and a telescoping mechanism 76 connected between each bracket 74 and the base 72 .
  • the base 72 is a plate-like member having a substantially rectangular shape when viewed from above, and the pressure-resistant container 12 can be placed in the center thereof.
  • a bracket 74 supports an actuator 78 having a servomotor so that it can swing about a horizontal shaft.
  • the expansion and contraction mechanism 76 includes an actuator 78 having a cylinder 77 attached to its lower portion, a movable shaft 80 attached to the cylinder 77 and capable of extending and contracting in the vertical direction via a ball screw, and a universal joint 82 attached to the lower end of the movable shaft 80. and a support shaft 84 that is fixed to the base 72 and supports the universal joint 82 .
  • an actuator 78 having a cylinder 77 attached to its lower portion, a movable shaft 80 attached to the cylinder 77 and capable of extending and contracting in the vertical direction via a ball screw, and a universal joint 82 attached to the lower end of the movable shaft 80. and a support shaft 84 that is fixed to the base 72 and supports the universal joint 82 .
  • each support shaft 84 is fixed to the base 72 , but a universal joint 82 corresponding to angles in all directions is interposed between the support shaft 84 and the movable shaft 80 . is attached to the bracket 74 so as to be able to swing, the base 72 can be tilted obliquely without any trouble.
  • the base 72 can be rotated while being inclined at a predetermined angle with respect to the horizontal plane. As a result, it is possible to rotate the mixed melt in the growth vessel 50 in the pressure vessel 12 placed on the base 72 and to cause vertical convection in the mixed melt.
  • This crystal plate manufacturing apparatus 10 is used for manufacturing a high-resistivity Group 13 nitride single crystal by, for example, the flux method.
  • a Zn-doped high-resistivity Group 13 nitride single crystal (hereinafter sometimes referred to as a Zn-doped GaN single crystal) will be described below as an example.
  • a GaN template is prepared as the seed crystal substrate 54
  • metallic gallium is prepared as the Group 13 metal
  • metallic sodium is prepared as the flux.
  • a seed crystal substrate 54 is immersed in a mixed melt containing metallic gallium, metallic sodium, metallic zinc and carbon in a growth container 50 .
  • the pressure vessel 12 is evacuated to a level of 1 ⁇ 10 ⁇ 2 Pa by the vacuum pump 26 to reduce moisture and oxygen remaining inside.
  • nitrogen gas is introduced up to a predetermined pressure, and nitrogen gas is continuously supplied to the mixed melt while controlling the heaters 18a to 18d so that the heating space 16 reaches a predetermined crystal growth temperature.
  • the actuator 78 is controlled to tilt the base at a predetermined angle (for example, 5 to 15 degrees) with respect to the horizontal plane, while switching clockwise or counterclockwise at a predetermined cycle (for example, 30 to 300 seconds).
  • the contents of growth vessel 50 are forcibly agitated by rotating at a speed (eg, a speed of 1-10 rpm).
  • a speed eg, a speed of 1-10 rpm.
  • the mixed melt can be constantly moved with respect to the seed crystal substrate 54 .
  • the surface of the seed crystal substrate 54 where crystal growth is fastest faces upward.
  • the raw material in which nitrogen is dissolved at the gas-liquid interface is always supplied to the seed crystal, making it easy to obtain a high-quality Group 13 metal nitride.
  • a Zn-doped GaN single crystal grows on the seed crystal substrate 54 in the mixed melt.
  • an appropriate amount of carbon is added to the mixed melt, inhibition of nitridation of the gallium raw material by zinc is suppressed.
  • an organic solvent for example, a lower alcohol such as isopropanol or ethanol
  • a lower alcohol such as isopropanol or ethanol
  • the crystal growth temperature is preferably set to 800 to 950.degree. C., more preferably 850 to 900.degree.
  • the temperature of the upper heater 18a, the middle heater 18b, the lower heater 18c, and the bottom heater 18d may be set to increase in order, or the upper heater 18a and the middle heater 18b may be set to the same temperature T. 1 , and the lower heater 18c and the bottom heater 18d are preferably set to a temperature T2 higher than the temperature T1 .
  • the pressure of the nitrogen gas is preferably set to 2 to 5 MPa, more preferably 2.5 to 4 MPa.
  • the vacuum pump 26 is driven to bring the internal pressure of the pressure-resistant container 12 into a high vacuum state (for example, 1 Pa or less or 0.1 Pa or less) via the evacuation pipe 28, and then
  • the evacuation pipe 28 is closed by a valve (not shown), and nitrogen gas is supplied from the nitrogen gas cylinder 22 to the heating space 16 through the nitrogen introduction pipe 24a.
  • nitrogen gas is supplied to the heating space 16 by the mass flow controller 25 during the crystal growth. continue to supply so as to achieve a predetermined flow rate.
  • the nitrogen introduction pipe 24b is closed by the valve 27. The overflowed nitrogen gas is released to the atmosphere through the nitrogen exhaust pipe 48 .
  • a thick Zn-doped GaN single crystal with a high specific resistance value can be preferably obtained.
  • Zn tends to be uniformly dispersed, and the Zn-doped GaN single crystal tends to become homogeneous.
  • the bottom heater 18d is arranged in addition to the upper, middle, and lower heaters 18a to 18c, the entire heating space 16, including the vicinity of the bottom where the temperature tends to be uneven, can be maintained at a uniform temperature.
  • Fe-doped GaN single crystals or Mn-doped GaN single crystals can also be produced by the same method as for Zn-doped GaN single crystals.
  • the method for producing a high-resistivity group 13 nitride single crystal is not limited to the production mode described above, and can be carried out in various ways as long as it falls within the technical scope of the present invention.
  • the melt in the growth container 50 in the pressure-resistant container 12 placed on the base 72 is rotated or caused to convect by the rocking device 70 .
  • a rotating mechanism for rotating the base 72 may be employed to rotate or convect the melt.
  • the AlN single crystal can be produced by an existing method such as a sublimation method or a HVPE method.
  • the semiconductor layer can be manufactured by using a high resistance group 13 nitride single crystal as a base substrate and forming a film of an ⁇ -Ga 2 O 3 based material thereon.
  • the method for producing the ⁇ -Ga 2 O 3 -based semiconductor layer is not particularly limited, but vapor phase methods such as mist CVD, HVPE, MOCVD, and sputtering, and liquid phase methods such as hydrothermal and flux methods are available.
  • a mist CVD method, an HVPE method, or a hydrothermal method is particularly preferred. Among these methods, the HVPE method and the mist CVD method are described below.
  • the HVPE method (halide vapor phase epitaxy) is a kind of CVD, and is a method applicable to film formation of compound semiconductors such as Ga 2 O 3 and GaN.
  • a Ga raw material and a halide are reacted to generate a gallium halide gas, which is supplied onto a base substrate for film formation.
  • O 2 gas is supplied onto the underlying substrate for film formation, and the gallium halide gas reacts with the O 2 gas to grow Ga 2 O 3 on the underlying substrate for film formation. It is a method that enables high - speed and thick film growth and has a wide track record in the industrial field .
  • FIG. 5 shows an example of a vapor phase growth apparatus using the HVPE method.
  • a vapor phase growth apparatus 90 using the HVPE method includes a reactor 100, a susceptor 108 on which a base substrate 106 for film formation is placed, an oxygen raw material supply source 101, a carrier gas supply source 102, and a Ga raw material supply source 103. , a heater 104 , and a gas discharge section 107 .
  • Any reactor that does not react with the raw material is applied as the reactor 100, such as a quartz tube.
  • Any heater capable of heating up to at least 700° C. (preferably 900° C. or higher) is applied as the heater 104, for example, a resistance heating type heater.
  • Metal Ga 105 is placed inside the Ga raw material supply source 103, and halogen gas or hydrogen halide gas such as HCl is supplied.
  • the halogen gas or halogenated gas is preferably Cl2 or HCl.
  • the supplied halogen gas or halogenated gas reacts with the metal Ga 105 to produce gallium halide gas, which is supplied to the base substrate for film formation.
  • the gallium halide gas preferably contains GaCl and/or GaCl3 .
  • Oxygen source 101 can supply an oxygen source selected from the group consisting of O2 , H2O and N2O , with O2 being preferred. These oxygen source gases are supplied to the underlying substrate for film formation at the same time as the gallium halide gas.
  • the Ga source gas and the oxygen source gas may be supplied together with a carrier gas such as N2 or a rare gas.
  • the gas discharge unit 107 may be connected to a vacuum pump such as a diffusion pump or a rotary pump, and not only discharges unreacted gas in the reactor 100 but also controls the pressure in the reactor 100. may This can improve the suppression of gas phase reactions and the growth rate distribution.
  • a vacuum pump such as a diffusion pump or a rotary pump
  • ⁇ -Ga 2 O 3 is formed on the film formation base substrate 106 by heating the film formation base substrate 106 to a predetermined temperature using the heater 104 and simultaneously supplying a gallium halide gas and an oxygen source gas. be done.
  • the deposition temperature is not particularly limited as long as ⁇ -Ga 2 O 3 is deposited, but is typically 250° C. to 900° C., for example.
  • the partial pressures of the Ga raw material gas and the oxygen raw material gas are also not particularly limited.
  • the partial pressure of the Ga source gas may be in the range of 0.05 kPa to 10 kPa
  • the partial pressure of the oxygen source gas may be in the range of 0.25 kPa to 50 kPa.
  • a separate supply source may be provided to supply the halides or the like, or the halides may be mixed and supplied from the Ga raw material supply source 103 .
  • a material containing a group 14 element, In, Al, or the like may be placed in the same location as the metal Ga 105, reacted with a halogen gas or hydrogen halide gas, and supplied as a halide.
  • mist CVD a raw material solution is atomized or dropletized to generate mist or droplets, the mist or droplets are transported to a film formation chamber equipped with a substrate using a carrier gas, and the mist or droplets are generated in the film formation chamber. It is a method of thermally decomposing and chemically reacting droplets to form and grow a film on a substrate. It does not require a vacuum process and can produce a large amount of samples in a short time.
  • FIG. 6 shows an example of a mist CVD apparatus.
  • a control valve 113a for adjusting the flow rate of the carrier gas sent from the carrier gas source 112b, a mist generation source 114 containing the raw material solution 114a, a container 115 containing water 115a, and a container
  • An ultrasonic transducer 116 attached to the bottom surface of 115 , a quartz tube 117 serving as a film forming chamber, a heater 118 installed around the quartz tube 117 , and an exhaust port 121 are provided.
  • the susceptor 120 is made of quartz, and the surface on which the substrate 119 is placed is inclined from the horizontal plane.
  • the raw material solution 114a used in the mist CVD method is not limited as long as it is a solution from which an ⁇ -Ga 2 O 3 based semiconductor layer can be obtained.
  • Examples include those obtained by dissolving an organic metal complex or a halide in a solvent.
  • organometallic complexes include acetylacetonate complexes.
  • a dopant component solution may be added to the raw material solution.
  • an additive such as hydrochloric acid may be added to the raw material solution. Water, alcohol, or the like can be used as the solvent.
  • the obtained raw material solution 114a is atomized or dropletized to generate mist or droplets 114b.
  • a preferable example of a method of atomizing or forming droplets is a method of vibrating the raw material solution 114a using an ultrasonic oscillator 116 .
  • the obtained mist or droplets 114b are transported to the film forming chamber using a carrier gas.
  • the carrier gas is not particularly limited, one or more of oxygen, ozone, inert gas such as nitrogen, and reducing gas such as hydrogen can be used.
  • a substrate 119 is provided in the deposition chamber (quartz tube 117).
  • the mist or droplets 114b conveyed to the film formation chamber are thermally decomposed and chemically reacted there to form a film on the substrate 119.
  • FIG. Although the reaction temperature varies depending on the type of raw material solution, it is preferably 300 to 800°C, more preferably 400 to 700°C.
  • the atmosphere in the deposition chamber is not particularly limited as long as a desired semiconductor film can be obtained, and may be an oxygen gas atmosphere, an inert gas atmosphere, a vacuum or a reducing atmosphere, but an air atmosphere is preferred. In this way, a semiconductor layer can be deposited on the underlying substrate.
  • a horizontal element such as HEMT is formed by providing a device structure such as an electron traveling layer on the semiconductor layer composed of ⁇ -Ga 2 O 3 or ⁇ -Ga 2 O 3 based solid solution obtained as described above. can be done. It is also possible to use the semiconductor layer itself as an electron transit layer.
  • Example 1 Fabrication of high resistance group 13 nitride (GaN) single crystal substrate First, on the surface of a c-plane sapphire substrate with a diameter of 50.8 mm (2 inches) and a thickness of 0.43 mm, a GaN low-temperature buffer layer was formed at 550°C. was deposited to a thickness of 70 nm, and then a GaN thin film having a thickness of 10 ⁇ m was deposited at 1050° C. in the vapor phase to obtain a GaN template that can be used as the seed crystal substrate 54 .
  • GaN gallium nitride
  • a Zn-doped GaN single crystal was formed on this GaN template by the flux method.
  • a method for forming a GaN single crystal will be specifically described below with reference to FIGS.
  • a tray stand 56 is placed in an alumina crucible as the growth container 50 having an inner diameter of 70 mm, and the seed crystal substrate tray 52 is leaned against the tray stand 56 to grow at an angle of 10°. It was obliquely placed in the center of the bottom surface of the container 50 .
  • the GaN template was placed as a seed crystal substrate 54 in the center of the seed crystal substrate tray 52 .
  • the growth vessel 50 was filled with 34 g of metallic sodium (Na), 38 g of metallic gallium (Ga), 90 mg of carbon (C), and 175 mg of zinc (Zn).
  • the ratio of Ga to Na was 27 mol%
  • the ratio of Zn to Na was 0.18 mol%
  • the ratio of Zn to Ga was 0.49 mol%
  • the ratio of C to Na was 0.5 mol%.
  • an appropriate amount of wire-like material having a diameter of 1 mm and cut to a length of about 3 mm was used as the raw material of Zn.
  • This growth container 50 is placed in the intermediate container 60, and after the intermediate container 60 is placed in the container main body 42a and the container lid 42b is closed, the container 42 is placed in the container main body 12a of the pressure-resistant container 12, and the container lid 12b is closed. It was installed on the stand 72 . Subsequently, after the internal pressure of the pressure vessel 12 was set to a high vacuum state, the valve (not shown) of the evacuation pipe 28 was closed. Subsequently, nitrogen gas was supplied from the nitrogen gas cylinder 22 into the pressure vessel 12 and the container 42 through the nitrogen introduction pipes 24a and 24b, and the nitrogen gas pressure was adjusted to 13.2 MPa. Further, the temperature of each heater 18a to 18d was controlled so that the internal temperature of the container 42 was 870.degree.
  • the temperature was increased and pressurized over 2 hours until the internal temperature reached 870° C. and the nitrogen gas pressure reached 13.2 MPa. After that, by controlling the four actuators 78 using a sequencer, the pressure container 12 is tilted at 10° with respect to the horizontal direction, and the clockwise and counterclockwise directions are alternately switched in a cycle of 60 seconds. , crystal growth was performed by holding the melt in the growth vessel 50 for 100 hours while stirring. At this time, the rotation speed of the pressure vessel 12 was set to 5 rpm. Then, it was gradually cooled to room temperature over 30 hours. Thereafter, the growth vessel 50 was removed from the pressure vessel 12, the flux was removed using ethanol, and the Zn-doped GaN crystal plate grown on the seed crystal substrate 54 was recovered. In this way, a Zn-doped high-resistivity group 13 nitride (GaN) single crystal was produced as a base substrate for film formation.
  • GaN high-resistivity group 13 nitride
  • the obtained high resistance group 13 nitride (GaN) single crystal was a substrate with a diameter of 50.8 mm (2 inches) and a thickness of 1000 ⁇ m.
  • the specific resistance at 25° C. was measured by Hall measurement, it exceeded the upper limit of measurement. Since the upper limit of measurement at this time was 1.00 ⁇ 10 4 ⁇ cm, it was found that the single crystal had a high resistance above this value.
  • ohmic electrodes were formed on the front and back surfaces of the high-resistivity group 13 nitride (GaN) single crystal, and the specific resistance at 25°C was measured by the two-probe method. there were.
  • SIMS analysis also revealed that the Zn concentration in the GaN single crystal was 4.00 ⁇ 10 18 atoms/cm 3 . Table 1 shows the results.
  • FIG. 6 schematically shows the mist CVD apparatus 111 used in this example.
  • the mist CVD apparatus 111 includes a diluent gas source 112a, a carrier gas source 112b, flow control valves 113a and 113b, a mist generation source 114, a container 115, an ultrasonic transducer 116, a quartz tube 117, a heater 118, a susceptor 120, and an exhaust port. 121.
  • a substrate 119 is placed on the susceptor 120 .
  • the flow control valve 113a is configured to be able to adjust the flow rate of the diluent gas sent from the diluent gas source 112a, while the flow control valve 113b is configured to be able to adjust the flow rate of the carrier gas sent from the carrier gas source 112b.
  • the mist source 114 contains the raw material solution 114a, while the container 115 contains water 115a.
  • An ultrasonic transducer 116 is attached to the bottom surface of the container 115 .
  • a quartz tube 117 forms a film forming chamber, and a heater 118 is installed around the quartz tube 117 .
  • the susceptor 120 is made of quartz, and the surface on which the substrate 119 is placed is inclined from the horizontal plane.
  • the flow rate of the diluent gas and the carrier gas were adjusted to 0.5 L/min and 1 L/min, respectively. Nitrogen gas was used as the diluent gas and carrier gas.
  • the ultrasonic oscillator 116 was vibrated at 2.4 MHz, and the vibration was propagated through the water 115a to the raw material solution 114a, thereby misting the raw material solution 114a and generating the mist 114b.
  • the mist 114b is introduced into the quartz tube 117, which is a film forming chamber, by the diluent gas and carrier gas, reacts in the quartz tube 117, and forms a film on the substrate 119 by CVD reaction on the surface of the substrate 119. rice field.
  • a crystalline semiconductor film semiconductor layer
  • the film formation time was 9 minutes.
  • the Ga oxide film had a biaxially oriented crystal structure in which the c-axis was oriented in the substrate normal direction and the in-plane orientation was also oriented. From these results, it was confirmed that the obtained semiconductor film was an oriented film with a crystal structure composed of ⁇ -Ga 2 O 3 .
  • Example 2 A laminate was produced in the same manner as in Example 1 except that the thickness of the high-resistance group 13 nitride single crystal was set to 350 ⁇ m by polishing in the above (1), and the film formation time was set to 300 minutes in the above (3d). , various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 3 A laminate was produced in the same manner as in Example 1, except that the film formation time was set to 1 minute in (3d) above, and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 4 A laminate was produced in the same manner as in Example 1, except that the film formation was repeated 50 times, and the film formation time was set to 1 hour per film formation in (3d) above, and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 5 A laminate was produced in the same manner as in Example 1, except that the amount of zinc in (1) was changed to 70 mg, and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 6 A laminate was produced in the same manner as in Example 1, except that 1200 mg of zinc was used in (1) above, and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 7 A laminate was produced in the same manner as in Example 3, except that in (1) above, the high resistance GaN single crystal substrate was changed to a commercially available AlN single crystal substrate (thickness: 450 ⁇ m), and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 8 (Comparison) A laminate was produced in the same manner as in Example 3, except that zinc was not used in (1) above, and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 9 (Comparison) A laminate was produced in the same manner as in Example 3, except that in (1) above, the thickness of the high-resistance GaN single crystal was reduced to 180 ⁇ m, and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 10 (Comparison) A laminate was produced in the same manner as in Example 5 except that 20 mg of zinc was used in (1) above, and the film formation time was set to 1 minute in (3d) above, and various evaluations were performed. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 11 A laminate was produced in the same manner as in Example 1 except that 750 mg of iron (Fe) was used instead of zinc in (1) above, and the Fe concentration was measured in (2) and (4c) above. made an evaluation. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.
  • Example 12 A laminate was produced in the same manner as in Example 1 except that 750 mg of manganese (Mn) was used in place of zinc in (1) above, and the Mn concentration was measured in (2) and (4c) above. made an evaluation. The film obtained was confirmed to be ⁇ -Ga 2 O 3 . The results were as shown in Table 1.

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