CN113308739A - System for preparing compound semiconductor crystal by combining continuous LEC and VGF after injection synthesis - Google Patents

System for preparing compound semiconductor crystal by combining continuous LEC and VGF after injection synthesis Download PDF

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Publication number
CN113308739A
CN113308739A CN202110606846.XA CN202110606846A CN113308739A CN 113308739 A CN113308739 A CN 113308739A CN 202110606846 A CN202110606846 A CN 202110606846A CN 113308739 A CN113308739 A CN 113308739A
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crucible
vgf
synthesis
furnace body
heater
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CN113308739B (en
Inventor
王书杰
孙聂枫
卜爱民
付莉杰
邵会民
刘峥
徐森锋
史艳磊
李晓岚
王阳
孙同年
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CETC 13 Research Institute
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CETC 13 Research Institute
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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
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • 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
    • 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • 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
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
    • 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
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/10—Production of homogeneous polycrystalline material with defined structure from liquids by pulling from a melt
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/44—Gallium phosphide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a system for preparing compound semiconductor crystals by combining continuous LEC (low-energy carrier) and VGF (vacuum gas) after injection synthesis, which comprises a rack, a sealed furnace chamber arranged on the rack, a seed rod and a synthesis injection system, wherein the sealed furnace chamber comprises a main furnace body, a synthesis crucible positioned in the main furnace body, an upper furnace body, a VGF crucible positioned in the upper furnace body and a liquid suction pipe arranged at the bottom of the VGF crucible, and the lower end part of the liquid suction pipe is positioned above the bottom of the synthesis crucible; the synthesis injection system is positioned in the main furnace body, and the seed crystal in the seed rod is positioned in the VGF crucible. The invention has the beneficial effects that: the upper part is a VGF growth part, and the lower part is a synthesis part; enter the VGF growth part through the mode of suck-back, the VGF growth part configuration seed rod and observation system simultaneously can also gaseous control. And (3) carrying out crystal introduction and shouldering at the beginning of LEC high-temperature gradient, and then carrying out VGF crystal growth under low-temperature gradient by using the grown crystal, thereby realizing the preparation of high-quality low-defect crystals at higher yield.

Description

System for preparing compound semiconductor crystal by combining continuous LEC and VGF after injection synthesis
Technical Field
The invention relates to a system for preparing compound semiconductor crystals by combining continuous LEC and VGF after injection synthesis, which is particularly suitable for compound semiconductors with volatile elements, such as indium phosphide, gallium phosphide and other materials.
Background
Compound semiconductor materials such as indium phosphide and gallium phosphide. The method is widely applied to many high and new technical fields such as optical fiber communication, microwave and millimeter wave devices, solar cells and the like, and is widely applied to military and civil fields such as aerospace, network communication, radar and the like.
The synthesis method of the compound semiconductor mainly comprises the following steps: direct synthesis, diffusion synthesis, injection synthesis, and the like. For materials with high saturated vapor pressure such as indium phosphide and gallium phosphide, diffusion synthesis and injection synthesis are generally required. The injection synthesis can greatly shorten the synthesis time, avoid the introduction of impurities and improve the material purity. And the crystal is directly prepared after injection synthesis, so that the preparation time of the crystal can be reduced, the preparation steps can be reduced, and the physical quality of the crystal is greatly improved.
The most commonly used methods for growing semiconductor crystals are: liquid Encapsulated Czochralski (LEC), Vapor Pressure controlled Czochralski (VCZ), Hot screen Czochralski (HWC), and full Liquid Encapsulated Czochralski (FEC); the Bridgman technique is divided into: vertical Bridgman (VB), Horizontal Bridgman (HB), Vertical Gradient Freezing (VGF), and Horizontal Gradient Freezing (HGF), among others.
Among them, liquid encapsulation czochralski technology (LEC) and vertical gradient solidification technology (VGF) are the most important methods for producing compound semiconductors such as indium phosphide and gallium phosphide. The liquid seal Czochralski technology (LEC) can obtain high growth interface temperature gradient, and the prepared crystal has high yield but high defect density. The Vertical Gradient Freezing (VGF) technique can prepare a crystal with low defects due to the characteristics of low temperature of a growth interface, stable thermal field and the like, but the yield is low.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a system for preparing a compound semiconductor crystal by combining continuous LEC and VGF after injection synthesis, wherein the upper part realizes the combined crystal growth of LEC and VGF, and the lower part realizes melt injection synthesis; and the melt is sucked back into the VGF crucible through gas pressure control. According to the invention, LEC seeding and shouldering under high temperature gradient are carried out to inhibit twin crystals, and then VGF growth is carried out in the residual melt of the VGF crucible to prepare low-defect crystals. The high-quality low-defect crystal can be prepared at a higher yield.
In order to solve the technical problems, the invention adopts the technical scheme that: a system for preparing compound semiconductor crystals by combining continuous LEC and VGF after injection synthesis comprises a frame, a sealed furnace chamber arranged on the frame, a seed rod and a synthesis injection system, and is characterized in that: the sealed furnace chamber comprises a main furnace body, a synthetic crucible positioned in the main furnace body, an upper furnace body positioned above the main furnace body, a VGF crucible positioned in the upper furnace body and a liquid suction pipe arranged at the bottom of the VGF crucible, wherein the lower end part of the liquid suction pipe is positioned above the bottom of the synthetic crucible; the synthesis injection system is positioned in the main furnace body, and the seed crystal in the seed rod is positioned in the VGF crucible.
The invention has the beneficial effects that: the upper part is a VGF growth part, and the lower part is a synthesis part; enter the VGF growth part through the mode of suck-back, the VGF growth part configuration seed rod and observation system simultaneously can also gaseous control. Carrying out crystal introduction and shouldering at the beginning of LEC high-temperature gradient, and then carrying out VGF crystal growth under low-temperature gradient by using the grown crystal, thereby realizing the preparation of high-quality low-defect crystals at higher yield;
a VGF crucible was designed which sucks the synthesized first melt through a pipette, with an internally disposed storage tank for storing VGF and boron oxide required for LEC growth. The boron oxide at the position can be fully distributed on the inner wall of the VGF tube along with the rising of the melt, so that the integral separation of the crystal from the crucible at the later stage is facilitated;
a switching clamp is designed to connect an upper furnace cover and the VGF crucible, the inside of the switching clamp is heated to be water-cooled, meanwhile, the end face of the VGF crucible is sealed through a clamping ring and a rubber ring, and air flow is blocked through a cooling column and a retaining ring structure of the VGF crucible, so that the temperature near the rubber ring is further reduced;
during the synthesis process, if the optimal synthesis crucible position is such that the bottom of the liquid suction pipe is inserted into the first melt or the boron oxide I inside the synthesis crucible, the inert gas is injected through the VGF crucible to prevent the suck-back during the synthesis process.
The present invention will be described in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram of a system for producing a compound semiconductor crystal incorporating continuous LEC after implantation synthesis in conjunction with VGF in accordance with the present invention;
FIG. 2 is a schematic view of the main furnace structure;
FIG. 3 is a schematic view showing the assembly of the adapting fixture with the upper furnace cover and the VGF crucible;
figure 4 is a front view of the adapting fixture;
FIG. 5 is a rear view of the adapting jig;
FIG. 6 is a cross-sectional view taken along line A-A of FIG. 4;
FIG. 7 is a schematic diagram of an injection synthesis system;
FIG. 8 is a schematic view of charging;
FIG. 9 is a schematic diagram of the synthesis;
FIG. 10 is a schematic of suck-back;
FIG. 11 is a schematic illustration of LEC seeding and shouldering crystal growth;
FIG. 12 is a schematic illustration of VGF crystal growth.
In the drawings: 1: a main furnace body; 1-1 main furnace body opening; 2: an upper furnace body; 2-1: putting a furnace cover; 3: a base; 4: a main upright post; 4-1: an upper furnace body driving device; 4-2: a first auxiliary lever; 4-3: a main furnace body driving device; 4-4: a second auxiliary lever; 5: an upper furnace body supporting table; 5-1: cleaning holes of the upper furnace body; 5-2: an upper furnace body supporting table column; 6: a main furnace body support table; 6-1: a main furnace body cleaning hole; 6-2: a main furnace body supporting table column; 7: a seed rod driving device loading table; 8: a seed rod driving device; 9, a seed rod; 10: an upper observation window; 11: switching the fixture; 11-1: balancing the air pipe; 11-2: a first seal ring; 11-3: a second seal ring; 11-4: a snap ring; 11-5: a screw hole; 11-6: switching the hole; 11-7: a central bore; 11-8: a sealing groove; 11-9: an observation hole; 11-10: a crucible clamping groove; 11-11: cooling the column; 12: a first compound drive motor; 13: a second composite drive motor; 14: a lower observation window; 15: synthesizing a rotating rod; 16: a synthetic injection system; 16-1: injecting the synthetic heater; 16-2: a loader; 16-3: injecting into a synthesis tube; 17: synthesizing a crucible; 18: supporting a crucible; 19: a main heater; 19-1: an auxiliary heater; 20: melt I; 21: a first heat preservation sleeve; 22: a crucible rod; 23: driving a crucible rod; 24: the crucible rod drives the loading platform; 25: an inflation tube; 26: a vacuum tube; 27: a crucible rod thermocouple; 28: an upper insulating layer shell; 29: a VGF crucible; 29-1: a pipette; 29-2: an extension pipe; 29-3: a storage tank; 29-4: a VGF crucible support; 29-5: a VGF crucible baffle ring; 30: an upper heat-insulating layer; 31: a first heater; 32: a second heater; 33: a third heater; 34: a fourth heater; 35: fifth heating device; 36: a pipette heater; 37: a heat insulation layer of the pipette; 38: a first thermocouple; 39: a second thermocouple; 40: a third thermocouple; 41 a fourth thermocouple; 42: a seed rod thermocouple; 43: seed crystal clamping; 44: seed crystal; 45: a second melt; 46: a crystal; 47: boron oxide I; 47-1: boron oxide II; 48: pure indium; 49: fastening screws; 50: red phosphorus; 51: a differential pressure gauge; 52: a differential pressure tube.
Detailed Description
Referring to fig. 1, the present invention provides a system for preparing a compound semiconductor crystal by combining a continuous LEC with VGF after injection synthesis. The system comprises a frame, a sealed furnace chamber arranged on the frame, a seed rod 9 and a synthesis injection system 16. The sealed furnace chamber comprises a main furnace body 1, a synthesis crucible 17 positioned in the main furnace body 1, an upper furnace body 2 positioned above the main furnace body 1, a VGF crucible 29 positioned in the upper furnace body 2, and a liquid suction pipe 29-1 arranged at the bottom of the VGF crucible 29, wherein the lower end part of the liquid suction pipe 29-1 is positioned above the bottom of the synthesis crucible 17. The synthesis injection system 16 is located in the main furnace 1 and the seed crystal 44 in the seed rod 9 is located in the VGF crucible 29. The synthesis crucible 17 is filled with metal raw materials and boron oxide I47, the VGF crucible 29 is filled with boron oxide II47-1, and the synthesis injection system 16 is filled with non-metal raw materials.
The frame comprises a base 3, a main upright post 4, an upper furnace body supporting platform 5 and a main furnace body supporting platform 6. An upper furnace body driving device 4-1, a first auxiliary rod 4-2, a main furnace body driving device 4-3, a second auxiliary rod 4-3 and the like are arranged on the main upright post 4. The main furnace body 1 is connected with a main furnace body driving device 4-3 connected on a main upright post 4 through a second auxiliary rod 4-4. The main furnace body 1 is driven to carry out lifting and rotating motion by the motion of the main furnace body driving device 4-3, so that the main furnace body 1 is moved to the base 3 and the main furnace body supporting platform 6. An upper furnace cover 2-1 in the upper furnace body 2 is connected with an upper furnace body driving device 4-1 connected on the main upright post 4 through a first auxiliary rod 4-2. The upper furnace body driving device 4-1 drives the upper furnace cover 2-1 to move up and down and rotate, so that the upper furnace body 2 can move to the main furnace body 1 and the upper furnace body supporting platform 5. The main furnace body driving device 4-3 and the upper furnace body driving device 4-1 can be linear driving devices such as oil cylinders driven by a rotating motor. During assembly and disassembly of the furnace, the upper furnace body 2 is movable to an upper furnace body support platform 5 and the main furnace body 1 is movable to a main furnace body support platform 6. The upper furnace body supporting platform 5 is provided with an upper furnace body cleaning hole 5-1 and an upper furnace body supporting platform column 5-2. The main furnace body support table 6 is provided with a main furnace body cleaning hole 6-1 and a main furnace body support table column 6-2. The maximum height of the main upright post 4 is such that the lower end of the pipette 29-1 can be separated from the highest end of the main furnace body 1 after the upper furnace body 2 is lifted.
The seed rod 9 is moved up and down by the seed rod driving device 8. The seed rod driving device 8 is assembled on a seed rod driving loading platform 7 connected with the upper furnace cover 2-1 to drive the seed rod 9 to move up and down. The seed rod driving device 8 comprises a rotating assembly and a lifting assembly. The rotating assembly comprises a rotating motor and an intermediate plate connected with a rotating shaft of the rotating motor; the lifting component is fixed on the middle plate and comprises an electric push rod, and the tail end of the electric push rod is connected with the seed rod 9. The lifting assembly can also comprise an electric push rod, the tail end of the electric push rod is connected with the middle plate, and the rotating assembly comprises a rotating motor fixed on the middle plate and a seed rod 9 connected with a rotating shaft of the rotating motor.
The main furnace body 1 is fixed on a base 3. A crucible support 18 is provided in the main furnace body 1, and a synthesis crucible 17 is provided inside the crucible support 18. The main furnace body 1 is also provided with an upper observation window 10. The base 3 is provided with an inflation tube 25 and a vacuum tube 26.
A crucible support driving device for driving the crucible support 18 to rotate and move up and down is provided below the main furnace body 1. The crucible support driving means includes a crucible rod 22 and a crucible rod drive 23. The crucible rod 22 passes through the susceptor 3 upward into the interior of the main furnace body 1 and is connected to the crucible support 18. The crucible rod drive 23 is mounted on the crucible rod drive loading table 24 for up-and-down movement. A crucible rod thermocouple 27 is also provided on the crucible rod 22. The crucible rod driver 23 comprises an electric push rod fixed on the crucible rod driving loading platform 24, a connecting plate connected with the electric push rod, and a rotating motor fixed on the connecting plate, wherein a rotating shaft of the rotating motor is connected with the crucible rod 22.
A heating system is provided outside the crucible support 18. The heating system includes a main heater 19 and an auxiliary heater 19-1. The crucible support 18 and the composite crucible 17 are heated by a main heater 19 at the periphery of the crucible support 18 and an auxiliary heater 19-1 located below the main heater 19. Further, a first heat-retaining jacket 21 for retaining heat of the heating system is provided outside the main heater 19.
Referring to FIG. 7, the synthetic injection system 16 includes an injection synthetic heater 16-1, a loader 16-2, and an injection synthetic tube 16-3. The upper part of the main furnace body 1 is provided with a first synthetic driving motor 12 and a second synthetic driving motor 13, and the first synthetic driving motor 12 and the second synthetic driving motor 13 are both connected with a corresponding synthetic injection system 16 through a synthetic rotating rod 15 and drive the synthetic injection system 16 to lift so that the synthetic injection pipe 16-3 is inserted into the synthetic crucible 17. The synthetic injection system 16 is driven to lift up and down between the synthetic driving motor and the synthetic rotating rod 15 through a screw rod nut structure or a gear rack structure.
Referring to fig. 1 and 2, the upper furnace body 2 is disposed at a main furnace port 1-1 on the main furnace body 1. The upper furnace cover 2-1, the upper furnace body 2, the main furnace body 1 and the base 3 form a sealed furnace chamber.
Referring to fig. 1, 3-6, an inner side of the upper furnace cover 2-1 is provided with an adapter 11, and a VGF crucible 29 is disposed in the upper furnace body 2 by the adapter 11. Specifically, screw holes 11-5 are formed in the adapter jig 11, and fastening screws 49 penetrate through the screw holes 11-5 to fix the adapter jig 11 to the upper furnace cover 2-1. A sealing groove is arranged on the contact surface of the upper furnace cover 2-1 and the switching fixture 11, and a first sealing ring 11-2 is arranged in the sealing groove. The fastening screw 49 is connected with its nut facing inwards and the first sealing ring 11-2 is used to prevent air leakage along the gap between the two contact surfaces.
The upper part of the switching fixture 11 is connected with a balance gas pipe 11-1, and the balance gas pipe 11-1 passes through the upper furnace cover 2-1 upwards for adjusting the pressure in the VGF crucible 29. The upper furnace cover 2-1 is also provided with a differential pressure pipe 52, and the differential pressure pipe 52 is connected with the balance air pipe 11-1. A differential pressure gauge 51 is mounted on the differential pressure pipe 52 for measuring a pressure difference between the inside of the VGF crucible 29 and the inside of the furnace body.
The adapter fixture 11 is provided with a snap ring 11-4 and a cooling column 11-11, and an annular gap between the snap ring 11-4 and the cooling column 11-11 forms a crucible clamping groove 11-10. The inner side surface of the snap ring 11-4 is provided with a seal groove 11-8 for placing a second seal ring 11-3. The top of the VGF crucible 29 is arranged in the crucible clamping groove 11-10, and the clamping ring 11-4 and the VGF crucible 29 are sealed through the second sealing ring 11-3. When the VGF crucible 29 is filled with boron oxide II47-1, the thickness of boron oxide II47-1 is greater than 2.5cm for establishing a sufficiently high temperature gradient and reducing the temperature above boron oxide II 47-1. The distance between the surface of the boron oxide II47-1 and the lower ends of the snap ring 11-4 and the cooling column 11-11 is more than 15 cm. Meanwhile, the cooling column 11-11 is connected with an external water circulation device to realize that water cooling is arranged inside the snap ring 11-4 and the whole adapter clamp 11, so that the temperature of the second sealing ring 11-3 is reduced, and the temperature gradient in the boron oxide II47-1 can be improved. The seed rod thermocouple 42 is horizontally arranged in the clamping ring 11-4 and is used for detecting the atmosphere temperature of the rubber ring near the clamping ring 11-4. The lower end of the cooling column 11-11 is inserted into the VGF crucible 29 by a distance greater than the distance from the upper end of the VGF crucible 29-5 to the VGF crucible 29.
The adapting fixture 11 is provided with 4 adapting holes 11-6 for connecting thermocouples in the upper insulating layer 30. The seed crystal hole of the upper furnace cover 2-1 and the central hole 11-7 of the switching fixture 11 are concentric holes and are used for penetrating through the seed crystal rod 9. The observation hole of the upper furnace cover 2-1 and the observation hole 11-9 of the adapter fixture 11 are concentric holes and are used for penetrating through the upper observation window 10. The upper observation window 10 is connected with the upper furnace cover 2-1 in a sealing way.
The bottom of the VGF crucible 29 is provided with a pipette 29-1, through which the first melt is sucked back into the VGF crucible 29. The distance between the lower end surface of the pipette 29-1 and the bottom of the crucible 17 is 1-5 mm. The amount of the synthesized first melt 20 in the synthesis crucible 17 is designed to ensure that the amount of the second melt 45 is satisfied, and the remaining melt in the synthesis crucible 17 can be submerged above the lower end 10mm of the pipette 29-1. Where the VGF crucible 29 is connected to the pipette 29-1, there is an extension pipe 29-2 entering the inside of the VGF crucible 29, and the extension pipe 29-2 and the VGF crucible 29 may enclose a storage tank 29-3. The boron oxide II47-1 is placed in the storage tank 29-3, and the height of the extension pipe 29-2 is such that the volume of the storage tank 29-3 formed with the VGF crucible 29 is larger than the volume of the boron oxide II47-1 after melting, so that the boron oxide II47-1 cannot overflow. The inner wall of the VGF crucible 29 is provided with a VGF crucible retaining ring 29-5 which is used for preventing hot air flow from entering between the VGF crucible 29 and the cooling column 11-11 and reducing the temperature of the second sealing ring 11-3.
A VGF crucible support 29-4 is provided outside the VGF crucible 29. The outer side of the VGF crucible support 29-4 is provided with a heating system, and the heating system comprises a first heater 31, a second heater 32, a third heater 33, a fourth heater 34, a fifth heater 35 and a heater 36. The VGF crucible 29 is heated by a first heater 31, a second heater 32, a third heater 33, a fourth heater 34 and a fifth heater 35 outside the VGF crucible support 29-4; the pipette 29-1 is heated by the heater 36. The outer layers of the first heater 31, the second heater 32, the third heater 33, the fourth heater 34 and the fifth heater 35 are provided with an upper heat-insulating layer 30, and the outer side of the upper heat-insulating layer 30 is provided with an upper heat-insulating layer shell 28. A pipette insulation layer 37 is provided around the pipette heater 36. The VGF crucible 29 is heated by the first heater 31, the second heater 32, the third heater 33, and the fourth heater 34 inside the upper insulating layer 30. A first thermocouple 38, a second thermocouple 39, a third thermocouple 40 and a fourth thermocouple 41 are sequentially arranged near the first heater 31, the second heater 32, the third heater 33 and the fourth heater 34; a seed rod thermocouple 42 is arranged in the seed rod 9. The seed rod 9 can enter the VGF crucible 29 through the upper furnace cover 2-1 and the center hole 11-7 of the adapter fixture 11.
The system of the present invention will be described in detail below by taking the preparation of indium phosphide as an example. In this embodiment, the synthesis crucible 17 contains pure indium 48 and the loader 16-2 of the synthesis injection system 16 contains red phosphorus 50.
1. Assembly of the System
The upper furnace body 2 is connected with the upper furnace cover 2-1 and moves to the upper furnace body supporting platform 5, and the main furnace body 1 moves to the main furnace body supporting platform 6.
The insulating jacket I21, the main heater 19 and the auxiliary heater 19-1 are then assembled to the base 3, respectively. The synthesis crucible 17 is then fitted onto the crucible support 18, and the crucible support 18 is fitted onto the crucible rod 22. Boron oxide I47 and pure indium 48 and a dopant were placed inside the synthesis crucible 17.
While 2 synthetic injection systems 16 are fitted to the synthetic turning rods 15. The first and second compound drive motors 12 and 13 raise the 2 compound injection systems 16 to the uppermost position. The synthesis crucible 17 is brought to the lowermost position. Then, by this, the main furnace body 1 is placed on the susceptor 3.
Then the upper furnace body 2 is placed on the main furnace body support platform 6 through the upper furnace body driving device 4-1, then the upper furnace body 2 and the upper furnace cover 2-1 are opened, and then the upper furnace cover 2-1 is lifted above the upper furnace body support platform 5.
Boron oxide II47-1 was placed in storage tank 29-3. Then, the inner side surface of the snap ring 11-4 on the adapter fixture 11 is connected and sealed with the VGF crucible 29 through a second sealing ring 11-3, and the sealing condition is tested through vacuumizing by a pipette 29-1.
After the above process is completed, the first heater 31, the second heater 32, the third heater 33, the fourth heater 34, and the fifth heater 35 are assembled to the outside of the VGF crucible support 29-4, and then the upper insulating layer 30 is disposed around the 5 heaters, and then the heaters and the VGF crucible support 29-4 are enclosed in the upper insulating layer housing 28. The fastening screws 49 are inserted into the screw holes 11-5 of the adapter jig 11, the fastening screws 49 are screwed on the upper insulating layer 30 side, and then the upper insulating layer housing 28 and the VGF crucible support 29-4 are coupled to the adapter jig 11.
The pipette heater 36 is fitted around the pipette 29-1, and a pipette heat-insulating layer 37 is provided outside the pipette heater 36. A first thermocouple 38, a second thermocouple 39, a third thermocouple 40, and a fourth thermocouple 41 are sequentially disposed in the upper insulating layer 30 and pass through a transfer hole 11-6 of the transfer fixture 11.
Then, the adapting jig 11 connecting the VGF crucible 29 and the thermocouple and the upper insulating layer 30 is connected to the upper furnace cover 2-1 by the fastening screw 49, and the gas leakage along the gap is prevented by the first sealing ring 11-2. Meanwhile, thermocouple wires of the first thermocouple 38, the second thermocouple 39, the third thermocouple 40 and the fourth thermocouple 41 are connected to the outer side of the upper furnace cover 2-1, and sealing of the thermocouple wires and the upper furnace cover 2-1 is achieved. Connecting the differential pressure tube 52 with the balance gas tube 11-1.
Then the upper furnace cover 2-1 is moved to the upper part of the main furnace body support platform 6, then slowly descends, the whole growth system is placed in the upper furnace body 2, and then the upper furnace cover 2-1 and the upper furnace body 2 are connected.
The upper furnace cover 2-1, the upper furnace body 2 and the whole crystal growth system are hoisted to the upper side of the main furnace body 1 by the upper furnace body driving device 4-1, so that the assembly with the main furnace body 1 is realized, and the pipette 29-1 is inserted into the center of the synthesis crucible 17. The main furnace body 1 and the base 3 and the main furnace body 1 and the upper furnace body 2 are connected in sequence by screws, so that the furnace body is sealed
2. Preparation of indium phosphide
a. Referring to FIGS. 1 and 8, the entire system is evacuated to 10 via vacuum line 26-5Pa-10Pa, then filling inert gas into the system through an inflation tube 25, and filling gas with initial pressure of 1.5-2.0 MPa.
b. Starting a main heater 19 and an auxiliary heater 19-1, and heating the synthesis crucible 17 to a synthesis temperature (pure indium 48 and boron oxide I47 in the synthesis crucible 17 are molten); the synthesis crucible 17 is then raised to the crucible position required for synthesis.
c. Referring to fig. 9 and 10, the first heater 31, the second heater 32, the third heater 33, the fourth heater 34, the fifth heater 35, and the pipette heater 36 were simultaneously controlled so that the temperature in the VGF crucible 29 reached above the melting point of indium phosphide while melting boron oxide II 47-1. Then the 2 synthesis injection systems 16 are lowered in sequence for synthesis.
If the optimum synthesis crucible position at this time is such that pipette 29-1 enters first melt 20 or boron oxide I47, while synthesis is being performed while slowly flushing inert gas into VGF crucible 29 through equilibrium gas pipe 11-1, a bubble is injected into first melt 20 through pipette 29-1 so that the melt in pipette 29-1 can be discharged out to participate in the synthesis process and prevent suck-back of first melt 20 or boron oxide I47 from occurring at the time of synthesis. The bubble rate was 0.5 to 20 bubbles per second, and the bubbling into the synthesis tube 16-3 and the pipette 29-1 was observed through the lower observation window 14.
After synthesis is complete, the synthesis injection system 16 is raised so that the injection synthesis tube 16-3 is free from the first melt 20. The injection of the gas into the VGF crucible 29 was stopped so that the pipette 29-1 and the bottom of the synthesis crucible 17 were held by 1 to 5 mm.
d. The pressure in the VGF crucible 29 is slowly reduced through the balance gas pipe 11-1, so that the pressure in the VGF crucible 29 is lower than the pressure value in the main furnace body 1, the pressure reduction is stopped when the pressure difference reaches rhogh, rho is the density of the melt, h is the difference between the maximum rising value of the second melt 45 in the VGF crucible 29 and the liquid level of the first melt 20, the pressure difference between the inside of the VGF crucible 29 and the inside of the furnace body is measured through the pressure difference meter 51, and then the pressure in the VGF crucible 29 is slightly adjusted through the balance gas pipe 11-1 according to the change of the value of the pressure difference meter 51, so that the constant pressure difference is ensured.
e. Then the first heater 31, the second heater 32, the third heater 33, the fourth heater 34 and the fifth heater 35 are controlled to obtain a temperature gradient of more than 20-50K/cm in the second melt 45. Meanwhile, a temperature gradient of 100-150K/cm is obtained in the boron oxide II 47-1.
f. Referring to the attached figure 11, starting and stopping the seed crystal rotation and pulling, and descending the seed crystal until the seed crystal 44 contacts the second melt 45 for crystal growth, wherein the seeding rate is 0.5 mm/h-20 mm/h, and the corresponding cooling rate is 0.2K/h-25 ℃/h.
The seed rotation and pulling is stopped when the crystal 46 is approximately 5mm in size from the crucible wall of the VGF crucible 29.
g. Referring to fig. 12, the first heater 31, the second heater 32, the third heater 33, the fourth heater 34, and the fifth heater 35 are readjusted so that the second melt 45 has a temperature gradient of 3-5K/cm, and VGF growth is controlled. In this process, the pressure values in the VGF crucible 29 and the main furnace body 1 are always kept at ρ gh.
h. And after the temperature reduction is finished, the second melt 45 in the VGF crucible 29 is solidified. The synthesis crucible 17 was then lowered so that the pipette 29-1 was detached from the boron oxide I47. All system heating was stopped.
The entire system was vented to atmospheric pressure. Since the remaining crystals of the seed crystal 44 are joined together, the seed shaft 9 is inverted at this time to disengage the seed shaft 9 from the seed chuck 43, so that the subsequent adapting jig 11 is disengaged from the seed shaft 9. Then the screws between the upper furnace body 2 and the main furnace body 1 are loosened, and the upper furnace body 2 is lifted until the lower end of the liquid suction pipe 29-1 leaves the main furnace body 1. Then the main furnace body 1 is moved to a main furnace body support table 6 through a main furnace body moving motor 4-3. The first thermocouple 38, the second thermocouple 39, the third thermocouple 40 and the fourth thermocouple 41 are loosened from the connection wires to the transfer jig 11, and then the fastening screws 49 are loosened, and the entire crystal growth system is slowly taken out through the upper furnace body 2.
Then, the jig 11 and the VGF crucible 29 are transferred in the crystal growth system, and the jig 11 and the upper insulating layer housing 28 are disassembled, the VGF crucible 29 is taken out, then the VGF crucible 29 is broken, the crystal 46 is taken out, and the boron oxide and the adhered quartz residue on the surface of the crystal 46 are removed by ultrasonic cleaning or the like.
For a 4 inch indium phosphide crystal, the head dislocations were about 104cm-2(ii) a Dislocation 3cm below the shoulder is about 1000-3000cm-2The dislocation at the lower part 6cm below the shoulder is about 100-500cm-2。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.

Claims (10)

1. A system for producing a compound semiconductor crystal by injecting post-synthesis continuous LEC in combination with VGF, comprising a frame, a sealed furnace chamber provided on the frame, a seed rod (9), and a synthesis injection system (16), characterized in that: the sealed furnace chamber comprises a main furnace body (1), a synthesis crucible (17) positioned in the main furnace body (1), an upper furnace body (2) positioned above the main furnace body (1), a VGF crucible (29) positioned in the upper furnace body (2) and a liquid suction pipe (29-1) arranged at the bottom of the VGF crucible (29), wherein the lower end part of the liquid suction pipe (29-1) is positioned above the bottom of the synthesis crucible (17);
the synthesis injection system (16) is located in the main furnace body (1), and a seed crystal (44) in the seed rod (9) is located in the VGF crucible (29).
2. The system for producing compound semiconductor crystals by injecting post-synthesis continuous LEC in combination with VGF as claimed in claim 1, wherein the synthesis crucible (17) is disposed in the main furnace body (1) by means of a crucible support (18), and a crucible support driving means for driving the crucible support (18) to rotate and move up and down is provided below the main furnace body (1), said crucible support driving means comprising a crucible rod (22) connected to the crucible support (18) and a crucible rod drive (23) fixed to a crucible rod drive loading table (24).
3. The system for manufacturing a compound semiconductor crystal by combining continuous LEC after injection synthesis with VGF as claimed in claim 2, wherein a heating system is provided outside said crucible support (18), said heating system comprising a main heater (19) provided at the periphery of the crucible support (18) and an auxiliary heater (19-1) located at the lower part of the main heater (19).
4. The system for manufacturing a compound semiconductor crystal by combining continuous LEC after injection synthesis with VGF as claimed in claim 1, wherein said synthesis injection system (16) comprises an injection synthesis heater (16-1), a loader (16-2) and an injection synthesis tube (16-3).
5. The system for producing compound semiconductor crystals by injection-synthesized continuous LEC in combination with VGF as claimed in claim 4, wherein a driving means for driving the synthesis injection system (16) to move up and down is provided on said main furnace body (1).
6. The system for producing a compound semiconductor crystal by injecting post-synthesis continuous LEC in combination with VGF as claimed in claim 1, wherein an extension pipe (29-2) is provided on top of the pipette (29-1), the extension pipe (29-2) cooperates with the inner wall of the VGF crucible (29) to form a reservoir (29-3) for receiving boron oxide II (47-1), and the volume of the reservoir (29-3) is larger than the volume of boron oxide II (47-1) after melting.
7. The system for manufacturing a compound semiconductor crystal by combining continuous LEC after injection synthesis with VGF according to claim 1, wherein a VGF crucible support (29-4) and a heating system including a heater (36) for heating the VGF crucible (29) and the first heater (31), the second heater (32), the third heater (33), the fourth heater (34) and the fifth heater (35) and heating the pipette (29-1) are provided outside the VGF crucible (29).
8. The system for producing compound semiconductor crystals by injection-synthesized continuous LECs in combination with VGF as claimed in any one of claims 1 to 7, wherein the VGF crucible (29) is set in the upper furnace body (2) by means of an adapter jig (11), the adapter jig (11) is fixed to the inside of the upper furnace lid (2-1) in the upper furnace body (2) by means of fastening screws (49) and a first sealing ring (11-2) is provided between the contact surfaces of the adapter jig (11) and the upper furnace lid (2-1).
9. The system for manufacturing a compound semiconductor crystal by combining continuous LEC after injection synthesis with VGF as set forth in claim 8, wherein a balance gas pipe (11-1) for adjusting the pressure in the VGF crucible (29) is connected to the upper part of the adapting jig (11), and the balance gas pipe (11-1) is passed upward through the upper furnace cover (2-1) and connected to the differential pressure pipe (52).
10. The system for manufacturing compound semiconductor crystals using continuous post injection synthesis LECs in combination with VGFs as claimed in claim 8, wherein a snap ring (11-4) and a cooling column (11-11) are provided on the adapting jig (11), an annular gap between the snap ring (11-4) and the cooling column (11-11) forms a crucible clamping groove (11-10), the top of the VGF crucible (29) is placed in the crucible clamping groove (11-10), and a second sealing ring (11-3) is provided in the crucible clamping groove (11-10).
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WO2022252544A1 (en) * 2021-06-01 2022-12-08 中国电子科技集团公司第十三研究所 Method for preparing compound semiconductor crystal by combining continuous lec and vgf after injection synthesis

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JPH02212395A (en) * 1989-02-10 1990-08-23 Furukawa Electric Co Ltd:The Production of compound semiconductor crystal and producing device
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JPS62283895A (en) * 1986-06-02 1987-12-09 Mitsubishi Metal Corp Single crystal pulling up device
JPH02212395A (en) * 1989-02-10 1990-08-23 Furukawa Electric Co Ltd:The Production of compound semiconductor crystal and producing device
CN1692185A (en) * 2002-12-18 2005-11-02 株式会社日矿材料 Process for producing single crystal of compound semiconductor and crystal growing apparatus
CN110760931A (en) * 2019-11-22 2020-02-07 中国电子科技集团公司第十三研究所 System for preparing indium phosphide crystal by indium phosphide mixture

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Publication number Priority date Publication date Assignee Title
WO2022252544A1 (en) * 2021-06-01 2022-12-08 中国电子科技集团公司第十三研究所 Method for preparing compound semiconductor crystal by combining continuous lec and vgf after injection synthesis

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