WO2019109367A1 - 一种水平注入合成后旋转连续vgf晶体生长的装置及方法 - Google Patents

一种水平注入合成后旋转连续vgf晶体生长的装置及方法 Download PDF

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Publication number
WO2019109367A1
WO2019109367A1 PCT/CN2017/115469 CN2017115469W WO2019109367A1 WO 2019109367 A1 WO2019109367 A1 WO 2019109367A1 CN 2017115469 W CN2017115469 W CN 2017115469W WO 2019109367 A1 WO2019109367 A1 WO 2019109367A1
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Prior art keywords
synthesis
crystal
temperature
furnace body
thermocouple
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PCT/CN2017/115469
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English (en)
French (fr)
Inventor
王书杰
孙聂枫
刘惠生
孙同年
史艳磊
邵会民
李晓岚
王阳
付莉杰
Original Assignee
中国电子科技集团公司第十三研究所
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Priority claimed from CN201711295529.0A external-priority patent/CN108360060B/zh
Priority claimed from CN201711295536.0A external-priority patent/CN108360061B/zh
Application filed by 中国电子科技集团公司第十三研究所 filed Critical 中国电子科技集团公司第十三研究所
Priority to US16/475,842 priority Critical patent/US10519563B2/en
Priority to JP2019541269A priority patent/JP6837566B2/ja
Publication of WO2019109367A1 publication Critical patent/WO2019109367A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • 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
    • C30B11/001—Continuous growth
    • 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
    • C30B11/006—Controlling or regulating
    • 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
    • C30B11/007—Mechanisms for moving either the charge or the heater
    • 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
    • C30B27/00—Single-crystal growth under a protective fluid
    • 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
    • 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

Definitions

  • the invention relates to a device and a method for synthesizing and growing a semiconductor crystal, in particular to a device and a method for growing a continuous continuous VGF crystal after horizontal injection synthesis, and is particularly suitable for a semiconductor with volatile element synthesis such as indium phosphide or gallium phosphide. Synthesis of crystalline materials and growth of VGF crystals.
  • Compound semiconductors are widely used in the electronics industry and are important compound semiconductor materials. For example, InP, GaP, GaAs, and the like. Since the elemental composition contains volatile elements, the synthesis methods include horizontal diffusion synthesis and injection synthesis.
  • the crystal growth method includes a LEC (Liquid Encapsulated Czochralski) method, a VGF (Vertical gradient freezing) method, etc., because the LEC method requires high equipment cost, large crystal stress, and high dislocation density. The crystal growth process is complicated, which is not conducive to the growth of high quality and large size single crystal. Therefore, the VGF method is currently used more.
  • LEC Liquid Encapsulated Czochralski
  • VGF Very gradient freezing
  • VGF method In the 1980s, Bell Labs of the United States first used the VGF method to prepare III-V compounds. The method is to vertically place the container containing the indium phosphide polycrystalline raw material in the corresponding temperature gradient set in the furnace, and distribute around the container. There is a red phosphorus, a crystal growth method in which the polycrystalline raw material is completely melted, slowly crystallizing from the lower end and continuing to the upper end.
  • the VGF method has a slow growth rate and a small temperature gradient, so the crystal is less stressed, so that a crystal material having a relatively low dislocation density can be grown.
  • this method requires the seed crystal to be placed first in the crucible before crystal growth.
  • the invention solves the technical problem that the growth of the VGF crystal after the synthesis by the injection method needs to be put into the polycrystalline material before the synthesis, the growth process is cumbersome and complicated, and the industrialization is difficult, and the device and the method for the rotation continuous VGF crystal growth after the horizontal injection synthesis are provided.
  • the horizontally-injected composite and vertical gradient solidification (VGF) crystals are realized by horizontally setting the volatile element carrying container and the crystal growth crucible, and the horizontally injecting and synthesizing the volatile element and the pure metal element, and further controlling the overall slow rotation of the furnace body by means of the rotating mechanism.
  • the present invention provides a device for rotating a continuous VGF crystal after horizontal injection and synthesis, comprising a furnace body, a synthesis and crystal growth system positioned in the furnace chamber, and a supporting heating system, a temperature measurement system, a heat preservation system and a control system.
  • the synthesis and crystal growth system comprises a crucible provided with a seed crystal accommodating chamber on the side and a volatile element carrier disposed on a horizontal side thereof, and the volatile element carrier is connected to the crucible by means of the injection tube to realize horizontal injection synthesis.
  • the furnace body has a rotational degree of freedom by means of a matching rotating mechanism, and realizes vertical vertical temperature gradient crystal growth after horizontal injection synthesis.
  • the end of the injection tube faces away from or obliquely away from the volatile element carrier.
  • the injection tube is of a multi-stage type, and the end section is inclined away from the volatile element carrier and has an angle of 60°-85° with the volatile element carrier.
  • the synthesis and crystal growth system further includes a loading rack for loading the crucible and the volatile element carrier, the loading frame is provided with a sealing cover, and the sealing cover is provided with an exhaust port, and the loading frame is quartz. , silicon carbide, boron nitride or ceramic material.
  • the heating system structure comprises a multi-stage heater sleeved on the periphery of the synthesis and crystal growth system;
  • the insulation system structure comprises an insulation sleeve sleeved outside the heating system;
  • the temperature measurement system structure comprises respectively A thermocouple a, a thermocouple c and/or a thermocouple d and/or a thermocouple e, a thermocouple b for determining the temperature of the seed chamber accommodating chamber region, the synthesis and crystal growth portion region, and the volatile element carrier region.
  • the rotating mechanism drives a motor and a speed reducer connected to the output shaft of the driving motor, and the output shaft of the speed reducer is connected to the rotating shaft of the furnace body via a coupling, and the furnace body is limited to the bracket by the rotating shaft of the furnace body.
  • the present invention also provides a method for rotating a continuous VGF crystal after horizontal injection synthesis, based on a crystal synthesis growth system including a furnace body, positioned in a furnace chamber, and a supporting heating system, a temperature measurement system, an insulation system, and
  • a crystal synthesis growth system including a furnace body, positioned in a furnace chamber, and a supporting heating system, a temperature measurement system, an insulation system, and
  • the crystal synthesis growth system includes a crucible having a seed crystal accommodating chamber on the side and a volatile element disposed on the horizontal side of the crucible and connected thereto by the injection tube.
  • a carrier, the furnace body is provided with a rotating mechanism, and the method comprises the following steps:
  • the furnace body is rotated to a vertical state by means of a rotating mechanism, and the temperature distribution of the region where the crucible is located is adjusted to realize continuous VGF crystal growth after synthesis.
  • the volatilized element carrier and the crucible are positioned in the cavity of the furnace, and the injection tube of the volatilization element carrier is first inserted into the crucible, and then placed in the sealing chamber provided with the exhaust port. The capsule is then positioned within the oven cavity.
  • the temperature required for the heating of the metal element and the boron oxide in the step (3) is controlled such that the temperature of the metal element is higher than the melting point of the compound by 30-70 ° C, and the temperature of the seed crystal accommodating cavity region is lower than the melting point of the compound.
  • the step (4) heating to make the volatile element through the injection tube into the metal element melt, the temperature of the volatile element is heated to ensure that the pressure in the volatile element carrier is higher than the dissociation pressure of the compound melt;
  • the compound melt is first cooled to a temperature higher than the melting point of the compound by 5-20 ° C, and the interface temperature of the control compound melt surface and the seed crystal accommodating chamber side of the ruthenium is higher than the crystallization point of the compound 3- In the range of 5 ° C, while maintaining the temperature of the seed crystal accommodating chamber region is stable; after the furnace body is rotated in the vertical state in the step (5), the compound melt is allowed to stand for 10-30 min.
  • the rotation rate is controlled at 20-40°/h; during the rotation, the temperature of the seed crystal accommodating cavity region is kept stable; after rotating to the vertical state, the temperature distribution of the region where the raft is located is adjusted, and the temperature measurement system is adjusted.
  • the utility model comprises a driving motor and a speed reducer connected to the output shaft of the driving motor, wherein the output shaft of the speed reducer is connected to the rotating shaft of the furnace body via a coupling, and the furnace body is limited to the bracket by the rotating shaft of the furnace body.
  • the end of the injection tube is away from or inclined away from the volatile element carrier, and is at an angle of 60°-85° with the volatile element carrier.
  • the heating system structure comprises a multi-stage heater sleeved on the periphery of the crystal synthesis growth system; the insulation system structure comprises sleeved outside the heating system
  • the thermal insulation system includes thermocouple a, thermocouple c and/or thermocouple d for determining the temperature of the seed crystal accommodating cavity region, the crystal growth region and the volatile element carrier region, respectively, in the crystal growth ⁇ And / or thermocouple e, thermocouple b.
  • a device for rotating a vertical temperature gradient crystal growth after compound crystal synthesis comprising a furnace body in which a synthesis and crystal growth system and a heating of a supporting synthesis and a crystal growth system are positioned in a furnace cavity of the furnace body.
  • the furnace body is provided with a rotating mechanism for its rotation, which has a rotational freedom;
  • the synthesis and crystal growth system includes a crucible and a volatile element carrier, A seed crystal accommodating chamber is arranged on one side, and the positional relationship between the crucible and the volatile element carrier is horizontally juxtaposed, wherein the crucible is placed like a funnel in a horizontal position, and the structure includes a horizontal strip of seed crystal accommodating chamber.
  • the volatile element carrier is provided with an injection tube, and the injection tube extends into the crucible through the injection insertion hole.
  • the volatile elements are assembled in the volatile element carrier and the volatile element carrier is sealed.
  • the seed crystal is placed in the seed crystal accommodating cavity of the crucible, and the pure metal and boron oxide are placed in the crucible, wherein the amount of each substance is controlled by the amount of the pure metal element, and the metal element melt height formed after heating and melting is accommodated in the seed crystal. Below the cavity, it is not in contact with the seed crystal; after the boron is heated and melted, the height is higher than the seed crystal accommodating cavity, thereby covering the seed crystal, and the volatile element is heated and then enters the metal element melt through the injection tube to realize horizontal injection synthesis to form a compound melt.
  • the amount of the compound melt is such that it is not in contact with the seed crystal.
  • the rotating mechanism is started to control the rotation of the furnace body by 90°, and the temperature distribution of each heated region is simultaneously adjusted during the rotation of the furnace body to ensure that the temperature of the seed crystal end is lower than the melting point of the seed crystal.
  • the body is rotated horizontally to the vertical direction.
  • the volatilized element carrier is located above, the crucible is located below, and the compound melt is in contact with the seed crystal.
  • the temperature distribution of each heated region is adjusted again to ensure crystal growth. Vertical gradient crystal growth is achieved.
  • a method for rotating the continuous VGF crystal growth after horizontal injection synthesis wherein the device structure comprises a furnace body, and the crystal body is grown in the furnace cavity of the furnace body.
  • the system, the crystal synthesis growth system is provided with a heating system, a temperature measuring system, a heat preservation system and a control system.
  • the furnace body is provided with a rotating mechanism for rotating, and has a rotational freedom;
  • the crystal synthesis growth system Including the crucible and volatile element carrier, the seed crystal receiving cavity is arranged on one side of the crucible, and the positional relationship between the crucible and the volatile element carrier is horizontally juxtaposed, wherein the crucible is placed like a funnel in a horizontal position, in the structure.
  • the invention comprises a horizontal strip-shaped seed crystal accommodating cavity, a synthesis and crystal growth part connected to the seed crystal accommodating cavity, and an injection insertion hole;
  • the volatilization element carrier is provided with an injection pipe, and the injection pipe extends through the injection insertion hole into the crucible.
  • the method of horizontally injecting and rotating a continuous VGF crystal growth comprises the following steps:
  • the element carrier and the crucible are positioned together in the furnace cavity; the amount of each material is controlled during the preparation as follows: the amount of the metal element is below the seed crystal accommodating cavity after heating and melting, and is not in contact with the seed crystal; the protective agent boron oxide is melted by heat. After the completion, the height is higher than the seed crystal accommodating cavity, so as to cover the seed crystal.
  • the volatile element After the volatile element is heated, it enters the molten metal element through the injection tube, and is injected into the compound to form a compound melt.
  • the liquid level of the compound melt is lower than the height of the seed crystal accommodating cavity, and it is necessary to ensure Not in contact with the seed crystal.
  • the molten metal element melt and the volatile element volatilize to form a compound melt, and the protective agent such as boron oxide melts to seal the compound melt and the liquid level is higher than the seed crystal receiving cavity;
  • the protective gas which may be an inert gas such as nitrogen, argon, etc., generally need to control the synthesis gas and the protective gas during crystal growth.
  • the pressure is greater than the dissociation pressure of the compound melt;
  • the heating temperature range is generally controlled to ensure that the temperature of the metal element reaches 30-70 ° C above the melting point of the compound, and the temperature of the seed crystal accommodating cavity region is lower than the melting point of the compound 5-15. °C, after melting, the boron oxide seals the molten metal element and the seed crystal;
  • the invention has the beneficial effects that the device for horizontally injecting and synthesizing the continuous continuous VGF crystal growth after the synthesis, by intelligently setting the rotating mechanism, scientifically arranging the positional structure of the volatile element carrying container and the crucible in the furnace body, controlling the volatile element carrying container and the crucible
  • the positional change realizes the ingenious combination of the horizontal injection synthesis and the vertical gradient crystal growth method, and the horizontal injection synthesis and the rotation continuous vertical gradient crystal growth;
  • the method for horizontally injecting and synthesizing the rotary continuous VGF crystal growth provided by the invention and the matching device thereof are simplified
  • the process avoids the melting of the seed crystal by the pure metal before the growth of the VGF; the method is simple, easy to operate and control, the device has a simple structure and is easy to operate, and the synthesized semiconductor crystal has a controllable shape and uniform quality, which is beneficial to realize the semiconductor crystal.
  • Industrial production is simple, easy to operate and control, the device has a simple structure and is easy to operate, and the synthe
  • Figure 1 is a schematic view showing the overall structure of the furnace body of the device on the bracket;
  • Figure 2 is a schematic view showing the structure of the crucible when the device is horizontally placed
  • FIG. 3 is a schematic view of a crystal synthesis growth system in a horizontal placement preparation stage of the device
  • FIG. 4 is a schematic view showing a crystal synthesis growth system in a horizontal stage of the device
  • Figure 5 is a schematic view of the crystal synthesis growth system after the horizontal placement of the device is completed
  • FIG. 6 is a schematic diagram of a crystal synthesis growth system of a VGF crystal growth stage after the device is rotated vertically;
  • thermocouple c 1, heat insulation board; 3, multi-stage heater; 4, thermocouple b; 5, loading compartment; 5-1, sealing cover, 5-1-1, venting hole; , volatile element carrier; 7, volatile element; 8, injection tube; 9, ⁇ ; 9-1, seed crystal chamber; 9-2, synthesis and crystal growth; 9-3, injection insertion hole; Element; 11, boron oxide; 12: thermocouple e; 13, thermocouple d; 14, thermocouple a; 15, seed crystal; 16, ruthenium support; 17, furnace body; 17-1, furnace body rotation axis; - 2, bracket; 18: insulation sleeve.
  • the present embodiment provides a device for rotating a vertical temperature gradient crystal growth after compound crystal synthesis.
  • the device structure includes a furnace body 17, a synthesis and crystal growth system positioned in the furnace body 17, and a supporting heating system thereof.
  • the temperature measuring system, the heat preservation system and the control system, the furnace body 17 is provided with a sealed cover to form a closed cavity, and the furnace body 17 is provided with a synthesis and crystal growth system, and the heating system is set on the periphery of the crystal synthesis growth system for The various parts of the synthesis and crystal growth system are precisely heated.
  • a multi-stage heater 3 is used; the heat preservation system is disposed on the outer layer of the heating system.
  • the heat insulation jacket 18 is used for integrally insulating the synthesis and crystal growth system;
  • the system may be a plurality of thermocouples, dispersed or interspersed in the synthesis and crystal growth system and the heating system or the insulation system structure, for determining the temperature of the corresponding area in real time, in the embodiment, the temperature measurement system structure
  • a thermocouple a 14 for determining the temperature of the seed crystal accommodating chamber 9-1 in the crystal growth ⁇ 9, for measuring synthesis and crystal growth, respectively 9-2 regional temperature thermocouple c 1 and thermocouple d13 and thermocouple e 12, thermocouple b 4 for measuring the temperature of the volatile element carrier 6;
  • control system for transmitting and receiving signals, integrated control coordinated heating system, measurement Temperature system, etc., specifically, can be a PLC controller.
  • the furnace body 17 is provided with a rotating mechanism, so that the rotation of the furnace body 17 can be realized, the positioning and connection relationship between the furnace body 17 and the rotating mechanism, and the rotating mechanism can be selected for conventional rotation.
  • the furnace body 17 is limited to the bracket 17-2 by means of the furnace body rotating shaft 17-1, wherein the rotating mechanism includes a driving motor and a speed reducer connected to the output shaft of the driving motor, The output shaft of the reducer is coupled to the furnace rotating shaft 17-1 via a coupling to control the rotation of the furnace body 17.
  • the synthesis and crystal growth system comprises a crucible 9 and a volatile element carrier 6 disposed on a horizontal side thereof, wherein the crucible 9 is placed like a funnel in a horizontal position when placed horizontally, and the shape is shown in Fig. 2, and the structure includes A seed crystal accommodating chamber 9-1 having a horizontal rectangular parallelepiped shape or a cylindrical shape on the side, a synthesis and crystal growth portion 9-2 connected to the seed crystal accommodating chamber 9-1, an injection insertion hole 9-3, and an injection insertion tube 9-3. Located at the upper or end of the synthesis and crystal growth portion 9-2, the diameter of which is required to ensure that the compound melt height is lower than the lower edge of the injection insertion tube 9-3, so that the compound melt is not inserted from the injection.
  • the tube 9-3 flows out of the crucible 9; the volatile element carrier 6 is provided with an injection tube 8, and the injection tube 8 extends through the injection insertion hole 9-3 into the crucible 9, and the volatile element 7 in the volatile element carrier 6 is heated by injection.
  • the tube 8 enters the crucible 9, and the metal melt in the crucible 9 can realize horizontal injection synthesis; after the synthesis is completed, the rotating mechanism rotates the furnace body 17 from the horizontal to the vertical state, and adjusts the temperature distribution of each heated region to ensure the seed crystal accommodation.
  • the temperature in cavity 9-1 is lower than the seed crystal
  • the melting point of 15 is such that after the furnace body 17 is vertical, the temperature distribution of each heated region is adjusted again to ensure that the compound melt in the crucible 9 is in contact with the seed crystal 15 to achieve vertical gradient crystal growth.
  • the compound melt in the crucible 9 is poured into the volatile element carrier 6, the note
  • the inlet pipe 8 is arranged in a multi-stage manner, as shown in Fig. 3, and the end portion is inclined away from the volatilization element carrier 6, preferably, the end portion is offset from the volatilization element carrier 6 and is clipped at 60°-85° to the side edge line thereof. angle.
  • the synthesis and crystal growth system further includes a loading rack 5 for loading the crucible 9 and the volatile element carrier 6.
  • the loading rack 5 can be For the quartz, silicon carbide, boron nitride or ceramic materials
  • the loading frame 5 is provided with a sealing cover 5-1
  • the sealing cover 5-1 is provided with an exhaust port 5-1-1.
  • the sealing cover 5-1 is installed to fix the sealing cover 5-1 and the loading frame 5, and the exhaust port 5-1-1 is used to balance the air pressure in the loading frame 5 during the synthesis.
  • the excess gas generated by the pressure increase in the loading frame 5 during the process of forming the compound melt after the volatile element is injected into the metal melt can be discharged.
  • the crucible 9 is separated from the volatile element carrier 6 by means of a heat shield 2, which is arranged on the one hand to separate the crucible 9 from the volatile element carrier 6 to avoid temperature interaction; on the other hand, when the furnace body After the rotation is in the vertical state, the heat shield 2 is supported on the upper end surface of the crucible 9, preventing the volatile element carrier 6 from accidentally falling into the crucible 9.
  • the crucible 9 is provided with a support 16 for supporting and protecting the seed crystal receiving chamber 9-1 and the crucible 9 as a whole.
  • the injection pipe 8 is a "B-shaped" multi-segment pipe whose end faces away from the volatile element carrier 6.
  • the loading tube 5 is made of quartz.
  • Example 1 Taking the apparatus described in Example 1 as an example, a method of growing a continuous continuous VGF crystal after horizontal injection synthesis according to the present invention will be described.
  • the volatile element 7 (the red phosphorus in this embodiment) is assembled in the volatile element carrier 6 and sealed, and the seed crystal 15 and the metal element 10 of the indium phosphide are
  • This embodiment is a pure indium metal) together with a dopant (high purity sulfur or high purity iron) and boron oxide 11 placed in the crucible 9, and then the injection tube 8 of the volatile element carrier 6 is inserted into the injection insertion hole 9 of the crucible 9 - 3, the volatile element carrier 6 and the synthesis and crystal growth ⁇ 9 are separated by a heat insulating plate 2, and then the volatile element carrier 6, the ⁇ 9 and the heat insulating plate 2 between the two are placed together in the sealed compartment.
  • the sealing chamber is placed in the furnace chamber as a whole.
  • the loading compartment 5 is selected, and the loading compartment 5 is provided with the sealing cover 5-1 to form a sealed compartment, and the sealing connection manner is welding or set sealing.
  • the amount of pure indium metal is loaded to ensure that the indium is not contacted with the seed crystal 15 after completion of melting, and that the seed crystal 15 is covered after the boron oxide 11 is melted, and the synthesis is completed.
  • the formed indium-phosphorus melt is not in contact with the seed crystal 15.
  • thermocouple e and / or thermocouple c and / or thermocouple d The pressure is too high, through the control system and thermocouple e and / or thermocouple c and / or thermocouple d, to ensure that the temperature of the metal element 10 (pure indium) in the crucible 9 reaches 1112 ° C (the melting point of the compound indium phosphide is 1062 ° C), while the temperature of the region of the seed crystal accommodating chamber 9-1 is lower than the melting point of the compound 5-15 ° C, this embodiment always controls the temperature of the thermocouple e at 1050 by the cooperation of the thermocouple e and the control system and the heating system. °C.
  • the boron oxide 11 is heated to a melt, and the pure indium melt and the seed crystal 15 are sealed.
  • thermocouple a and/or the thermocouple c and/or the thermocouple d is 1062 ° C or more and 10 ° C
  • the temperature of the thermocouple b and the thermocouple d is controlled to be a thermoelectric Even b ⁇ thermocouple d> 1062 ° C can be, while ensuring the temperature of the thermocouple e in the region of the seed receiving chamber 9-1 is unchanged; then, the entire furnace body 17 is slowly rotated to vertical at 30 ° / h speed
  • the melt is allowed to stand for 10 to 30 minutes, so that boron oxide and melt in the injection pipe 8 are dropped into the synthesis and crystal growth portion 9-2, in which the temperature of the thermocouple e is kept constant, and the multi-stage heater 3 is controlled.
  • thermocouple b>thermocouple c>thermocouple e>thermocouple d>thermocouple a at this time, The temperature gradient of the solid-liquid interface is ensured to be about 5 K/mm, and then VGF crystal growth is performed. As shown in FIG. 6, an indium phosphide semiconductor single crystal material is obtained.
  • the carrier concentration of the prepared sulfur-doped indium phosphide crystal ⁇ 1 ⁇ 10 18 cm -3 ; mobility: ⁇ 1000 cm 2 V -1 S -1 ; resistivity: (0.1-6) ⁇ 10 -3 ⁇ Cm; dislocation density ⁇ 1000/cm 2 .
  • the mobility of the prepared iron-doped indium phosphide crystal ⁇ 1000 cm 2 V -1 S -1 ; resistivity: 1 ⁇ 10 7 ⁇ ⁇ cm dislocation density ⁇ 5000 / cm 2 .
  • the heat insulation panels 2 are separated, and then the volatile element carrier 6, the crucible 9 and the heat insulation panel 2 are placed in the loading compartment 5, the sealing cover 5-1 is assembled with the loading compartment 5, and is integrally placed in the furnace cavity. .
  • the amount of pure gallium metal is loaded to ensure that the gallium is not contacted with the seed crystal 15 after the melting of the gallium is completed, and the seed crystal 15 is covered after the boron oxide 11 is melted, and the gallium-phosphorus melt formed after the synthesis is completed is not matched with the seed crystal 15 contact.
  • thermocouple b and thermocouple d are controlled to be thermoelectric Even b ⁇ thermocouple d> 1476 ° C, while ensuring the temperature of the thermocouple e in the region of the seed receiving chamber 9-1 is unchanged; then, the entire furnace body 17 is slowly rotated to a vertical speed of 35 ° / h In the state, the melt is allowed to stand for 20 minutes, so that the boron oxide in the injection pipe 8 is dropped into the compound melt, in which the temperature of the thermocouple e is kept constant, and the multi-stage heater 3 is controlled to contact the compound melt in the seed crystal 15.
  • thermocouple temperature is controlled as thermocouple b>thermocouple c>thermocouple e>thermocouple d>thermocouple a.
  • the temperature gradient of the solid-liquid interface is guaranteed to be 5K.
  • VGF crystal growth is performed to obtain a gallium phosphide semiconductor single crystal material.
  • the carrier concentration of the prepared sulfur-doped gallium phosphide crystal (1-8) ⁇ 10 17 cm -3 ; mobility ⁇ 100 cm 2 V -1 S -1 ; dislocation density ⁇ 5000 / cm 2 .
  • the carrier concentration of the prepared zinc-doped gallium phosphide crystal (5-200) ⁇ 10 17 cm -3 ; mobility ⁇ 25 cm 2 V -1 S -1 ; dislocation density ⁇ 5000 / cm 2 .
  • the method for horizontally injecting and synthesizing a continuous continuous VGF crystal growth and the accompanying horizontal injection and synthesis of a rotating continuous VGF crystal growth apparatus do not need to be placed before the injection method is synthesized and before the VGF crystal grows.
  • the crystal material simplifies the process and avoids the melting of the seed crystal 15 by the pure metal before the growth of the VGF; the method steps are simple, easy to operate and control, the device structure is simple and easy to operate, and the synthesized semiconductor crystal shape is controllable and uniform in quality, Conducive to the industrial production of semiconductor crystals.

Abstract

一种水平注入合成后旋转连续VGF晶体生长的装置和方法，属于半导体晶体合成与生长技术领域，采用的技术方案是装置包括炉体（17）、定位在炉腔内的合成与晶体生长系统及其配套的加热系统、测温系统、保温系统和控制系统，合成与晶体生长系统包括坩埚（9）和设置在其水平一侧的挥发元素承载器（6），挥发元素承载器（6）借助注入管（8）与坩埚（9）连通实现水平注入合成；炉体（17）借助配套的旋转机构具有旋转自由度，实现了易挥发元素和纯金属元素直接水平注入合成后，借助旋转机构控制炉体整体缓慢旋转，从而晶体合成后连续VGF晶体生长，制备高纯化合物半导体晶体，避免了VGF晶体生长前纯金属将籽晶熔掉，步骤简洁、易于操作和控制，有利于半导体晶体的产业化生产。

Description

一种水平注入合成后旋转连续VGF晶体生长的装置及方法 技术领域
本发明涉及半导体晶体合成与生长的装置和方法，具体涉及一种水平注入合成后旋转连续VGF晶体生长的装置及方法，尤其适用于磷化铟、磷化镓等带有挥发性元素合成的半导体晶体材料的合成和VGF晶体生长。
背景技术
化合物半导体广泛应用于电子行业，是重要的化合物半导体材料。例如，InP、GaP、GaAs等。由于元素组成中含有挥发性元素，合成方法有水平扩散合成和注入合成等。其晶体生长方法有LEC(Liquid Encapsulated Czochralski：液封直拉)法、VGF(Vertical gradient freezing：垂直梯度凝固)法等，由于LEC法需要设备成本较高，晶体应力较大，位错密度高，晶体生长工艺复杂，不利于生长高质量大尺寸的单晶，因此，目前应用较多的是VGF法。
美国贝尔实验室与上世纪80年代首次使用VGF法制备III-V族化合物，该方法是将装有磷化铟多晶原料的容器垂直置于炉中设定的相应温度梯度部位，容器周围分布有红磷，待多晶原料全熔后，从下部一端缓慢结晶并延续到上部一端的晶体生长方法。VGF方法生长速度较慢，温度梯度很小，因此晶体所受应力较小，所以可以生长出位错密度相对较低的晶体材料。但该方法在晶体生长前，需要将籽晶先放置在坩埚中。如果要想实现合成后连续VGF晶体生长就比较困难了，因为这样需要籽晶与纯金属直接接触，在高温纯金属熔体中，化合物籽晶会被纯金属或者正在合成的熔体熔化或者侵蚀掉。为了保护籽晶，需要事先在坩埚内放入多晶料并通过繁琐的控温程序来保护籽晶不被合成过程所熔化，但是这样会导致合成的晶体材料纯度降低，并且导致合成晶体生长过程耗时长、过程复杂繁琐、易失误，难于工业化和大规模生长，严重阻碍了半导体晶体材料的应用发展。
发明内容
本发明为解决目前注入法合成后VGF晶体生长需合成前需放入多晶料、生长过程繁琐复杂、工业化难度大的技术问题，提供一种水平注入合成后旋转连续VGF晶体生长的装置及方法，采用水平设置挥发元素承载容器和晶体生长坩埚，易挥发元素和纯金属元素的水平注入合成后，进一步借助旋转机构控制炉体整体缓慢旋转，实现了水平注入合成与垂直梯度凝固(VGF)晶体生长结合，晶体合成后连续VGF晶体生长，来制备高纯化合物半导体晶体，避免了VGF生长前纯金属将籽晶熔掉，该方法步骤简洁、装置结构简单、易于操作 和控制，有利于半导体晶体的产业化生产。
本发明采用的技术方案是：
首先，本发明提供一种水平注入合成后旋转连续VGF晶体生长的装置，包括炉体、定位在炉腔内的合成与晶体生长系统及其配套的加热系统、测温系统、保温系统和控制系统，关键在于，所述合成与晶体生长系统包括侧面设有籽晶容纳腔的坩埚和设置在其水平一侧的挥发元素承载器，所述挥发元素承载器借助注入管与坩埚连通实现水平注入合成；所述炉体借助配套的旋转机构具有旋转自由度，实现水平注入合成后旋转垂直温度梯度晶体生长。
优选的，所述注入管末端背离或倾斜式远离挥发元素承载器。
优选的，所述注入管为多段式，末段倾斜式远离挥发元素承载器，与挥发元素承载器呈60°-85°夹角。
优选的，所述合成与晶体生长系统中还包括装载所述坩埚和挥发元素承载器的装载架，所述装载架配套设置密封盖，密封盖上设有排气口，所述装载架为石英、碳化硅、氮化硼或陶瓷材质。
优选的，所述加热系统结构中包括套设在合成与晶体生长系统外围的多段加热器；所述保温系统结构中包括套设在加热系统外部的保温套；所述测温系统结构中包括分别用于测定坩埚内籽晶容纳腔区域、合成与晶体生长部区域和挥发元素承载器区域的温度的热电偶a、热电偶c和/或热电偶d和/或热电偶e、热电偶b。
优选的，所述旋转机构驱动电机和与驱动电机输出轴连接的减速器，所述减速器输出轴借助联轴器与炉体旋转轴连接，炉体借助炉体旋转轴限位在支架上。
第二，本发明还提供一种水平注入合成后旋转连续VGF晶体生长的方法，基于包括炉体、定位在炉腔内的晶体合成生长系统及其配套的加热系统、测温系统、保温系统和控制系统的注入合成后旋转连续VGF晶体生长的装置，关键在于，所述晶体合成生长系统包括侧面设有籽晶容纳腔的坩埚和设置在坩埚水平一侧、并借助注入管与其连通的挥发元素承载器，所述炉体配套设有旋转机构，所述方法包括以下步骤：
㈠备料和装置装配：将挥发元素装入挥发元素承载器内并密封，将籽晶、金属元素及氧化硼置于坩埚内，挥发元素承载器和坩埚一并定位于炉腔内；控制金属元素与挥发元素形成的化合物熔体液面低于籽晶容纳腔，氧化硼熔化后密封化合物熔体且液面高于籽晶容纳腔；
㈡密封炉体，抽真空后充入保护性气体；
㈢加热使金属元素和氧化硼熔化；
㈣加热使挥发元素通过注入管进入金属元素熔体，注入合成化合物熔体；
㈤合成完毕后，借助旋转机构将炉体旋转至竖直状态，调整坩埚所在区域的温度分布，实现合成后连续VGF晶体生长。
优选的，所述步骤㈠中挥发元素承载器和坩埚一并定位于炉腔内是先将挥发元素承载器的注入管伸入坩埚内，然后一并放入设有排气口密封舱中，再将密封舱定位于炉腔内。
优选的，所述步骤㈢中加热使金属元素和氧化硼熔化所需控制的温度是：使金属元素的温度高于化合物熔点30-70℃，同时使籽晶容纳腔区域的温度低于化合物熔点5-15℃；所述步骤㈣中加热使挥发元素通过注入管进入金属元素熔体时，加热挥发元素所达到温度的条件是保证挥发元素承载器内的压力高于化合物熔体的离解压；所述步骤㈤中合成完毕后，首先对化合物熔体进行降温至高于化合物熔点5-20℃，控制化合物熔体液面与坩埚的籽晶容纳腔一侧的界面温度高于化合物结晶点3-5℃范围，同时保持籽晶容纳腔区域温度稳定；所述步骤㈤中炉体旋转呈竖直状态后，将化合物熔体静置10-30min。
优选的，所述步骤㈤中旋转速率控制在20-40°/h；旋转过程中保持籽晶容纳腔区域温度稳定；旋转至竖直状态后，调整坩埚所在区域的温度分布，借助测温系统及控制系统的协调控制，在籽晶与化合物熔体接触的界面及化合物熔体中建立温度梯度，实现注入合成后连续VGF晶体生长；所述注入合成旋转VGF晶体生长的装置中，旋转机构结构中包括驱动电机和与驱动电机输出轴连接的减速器，所述减速器输出轴借助联轴器与炉体旋转轴连接，炉体借助炉体旋转轴限位在支架上。
优选的，所述注入合成后旋转连续VGF晶体生长的装置中，，所述注入管末端背离或倾斜式远离挥发元素承载器，与挥发元素承载器呈60°-85°夹角。
优选的，所述注入合成后旋转连续VGF晶体生长的装置中，所述加热系统结构中包括套设在晶体合成生长系统外围的多段加热器；所述保温系统结构中包括套设在加热系统外部的保温套；所述测温系统结构中包括分别用于测定晶体生长坩埚内籽晶容纳腔区域、晶体生长区域和挥发元素承载器区域温度的热电偶a、热电偶c和/或热电偶d和/或热电偶e、热电偶b。
上述技术方案中，首先，提供一种化合物晶体合成后旋转垂直温度梯度晶体生长的装置，包括炉体，炉体的炉腔内定位有合成与晶体生长系统和配套合成与晶体生长系统设置的加热系统、测温系统、保温系统和控制系统，关键在于，炉体配套设置有供其旋转的旋转机构，具有旋转自由度；所述的合成与晶体生长系统中包括坩埚和挥发元素承载器，坩埚一侧设有籽晶容纳腔，坩埚与挥发元素承载器两者的位置关系为水平并列放置，其中，坩埚水平放置时类似卧倒放置的漏斗状，结构中包括水平条状的籽晶容纳腔、与籽晶容纳腔连接的 合成与晶体生长部、注入插入孔；挥发元素承载器设置有注入管，注入管穿过注入插入孔伸入至坩埚内。使用本装置时，将挥发性元素装配在挥发元素承载器内，并将挥发元素承载器进行密封。将籽晶放入坩埚的籽晶容纳腔内，纯金属及氧化硼放置在坩埚内，其中各物质的量需控制纯金属元素的量为加热熔化后形成的金属元素熔体高度在籽晶容纳腔以下，不与籽晶接触；氧化硼受热熔化完后高度高于籽晶容纳腔，从而覆盖籽晶，挥发元素受热后通过注入管进入金属元素熔体，实现水平注入合成，形成化合物熔体，化合物熔体的量要保证不与籽晶接触。更重要的是，水平注入合成完成后，启动旋转机构，控制炉体旋转90°，在炉体旋转过程中同时调节各受热区域的温度分布，保证籽晶端的温度低于籽晶的熔点，炉体由水平转动为竖直方向，此时挥发元素承载器位于上方，坩埚位于下方，化合物熔体与籽晶接触，待炉体处于垂直后，再次调节各受热区域的温度分布保证在晶体生长坩埚内实现垂直梯度晶体生长。
进一步的，基于注入合成后旋转连续VGF晶体生长的装置，提供一种水平注入合成后旋转连续VGF晶体生长的方法，所述装置结构中包括炉体，炉体的炉腔内定位有晶体合成生长系统，晶体合成生长系统配套设置有加热系统、测温系统、保温系统和控制系统，关键在于，炉体配套设置有供其旋转的旋转机构，具有旋转自由度；所述的晶体合成生长系统中包括坩埚和挥发元素承载器，坩埚一侧设有籽晶容纳腔，坩埚与挥发元素承载器两者的位置关系为水平并列放置，其中，坩埚水平放置时类似卧倒放置的漏斗状，结构中包括水平条状的籽晶容纳腔、与籽晶容纳腔连接的合成与晶体生长部、注入插入孔；挥发元素承载器设置有注入管，注入管穿过注入插入孔伸入至坩埚内。
基于上述装置，水平注入合成后旋转连续VGF晶体生长的方法包括以下步骤：
㈠备料和装置装配：将挥发元素装入挥发元素承载器内并密封，将籽晶、金属元素及保护剂如氧化硼置于坩埚内，挥发元素承载器的注入管插入坩埚内，然后将挥发元素承载器和坩埚一并定位于炉腔内；备料时控制各物料的量如下：金属元素的量为加热熔化后高度在籽晶容纳腔以下，不与籽晶接触；保护剂氧化硼受热熔化完后高度高于籽晶容纳腔，从而覆盖籽晶，挥发元素受热后通过注入管进入金属元素熔体，注入合成形成化合物熔体，化合物熔体液面低于籽晶容纳腔高度，要保证不与籽晶接触。加热熔化的金属元素熔体与挥发元素挥发后形成化合物熔体，保护剂如氧化硼熔化后能密封化合物熔体且液面高于籽晶容纳腔；
㈡密封炉体，对炉体抽真空，一般抽真空至10-3Pa，然后充入保护性气体，可以是惰性气体，如氮气、氩气等，一般需控制合成及晶体生长时保护性气体压力大于化合物熔体的离解压；
㈢加热使金属元素和氧化硼熔化，该步骤中一般控制加热温度范围是保证金属元素的温度达到化合物的熔点以上30-70℃，同时使籽晶容纳腔区域的温度低于化合物熔点5-15℃，熔化后氧化硼密封金属元素熔体和籽晶；
㈣加热使挥发元素通过注入管进入金属元素熔体，水平注入合成化合物熔体，加热过程中，对挥发元素所在区域的温度要精确检测和及时控制，以便于控制挥发元素的注入速率；㈤合成完毕后，借助旋转机构将炉体旋转至竖直状态，调整坩埚所在区域的温度分布，在籽晶与化合物熔体接触的界面及化合物熔体中建立温度梯度，从而进行注入合成后旋转连续VGF晶体生长。
本发明的有益效果是：本发明提供的水平注入合成后旋转连续VGF晶体生长的装置，通过巧妙设置旋转机构，科学布局炉体内挥发元素承载容器和坩埚的位置结构，控制挥发元素承载容器和坩埚的位置变化，实现了水平注入合成和垂直梯度晶体生长方法的巧妙结合，水平注入合成后旋转连续垂直梯度晶体生长；本发明提供的水平注入合成旋转连续VGF晶体生长的方法及其配套装置，简化了工艺，避免了VGF生长前纯金属将籽晶熔掉；该方法步骤简洁、易于操作和控制，装置结构简单，易于操作，所合成的半导体晶体形状可控、质量均一，有利于实现半导体晶体的产业化生产。
附图说明
图1为本装置炉体在支架上的整体结构示意图；
图2为本装置水平放置时坩埚结构示意图；
图3为本装置水平放置备料阶段晶体合成生长系统的示意图；
图4为本装置水平放置合成阶段晶体合成生长系统的示意图；
图5为本装置水平放置合成完毕后晶体合成生长系统的示意图；
图6为本装置旋转垂直后VGF晶体生长阶段晶体合成生长系统的示意图；
图中，1、热偶c；2、隔热板；3、多段加热器；4、热偶b；5、装载舱；5-1、密封盖，5-1-1、排气孔；6、挥发元素承载器；7、挥发元素；8、注入管；9、坩埚；9-1、籽晶容纳腔；9-2、合成与晶体生长部；9-3、注入插入孔；10、金属元素；11、氧化硼；12：热偶e；13、热偶d；14、热偶a；15、籽晶；16、坩埚支撑；17、炉体；17-1、炉体旋转轴；17-2、支架；18：保温套。
具体实施方式
以下通过具体实施例详细说明本发明提供的水平注入合成后旋转连续VGF晶体生长的装置及方法，以便于理解，但不以任何形式限制本发明，所属领域技术人员根据技术方案 所进行的改善修改或者类似替换，均应包含在本发明的保护范围之内。
装置实施例1
本实施例提供一种化合物晶体合成后旋转垂直温度梯度晶体生长的装置，参见图1，装置结构中包括炉体17、定位在炉体17内的合成与晶体生长系统及其配套的加热系统、测温系统、保温系统和控制系统，炉体17设有密封的盖子，形成密闭性腔体，炉体17内设有合成与晶体生长系统，加热系统套装于晶体合成生长系统外围，用于对合成与晶体生长系统的各部分精确加热，本实施例采用多段加热器3；保温系统设置在加热系统外层，本实施例是保温套18，用于对合成与晶体生长系统整体保温；测温系统可以是多个热电偶，分散或穿插设置在合成与晶体生长系统及加热系统或保温系统结构中，用于对实时测定对应区域的温度，本实施例中，所述的测温系统结构中包括分别用于测定晶体生长坩埚9内籽晶容纳腔9-1区域温度的热电偶a 14、用于测定合成与晶体生长部9-2区域温度的热电偶c 1和热电偶d13及热电偶e 12、用于测定挥发元素承载器6区域温度的热电偶b 4；控制系统用于收发信号，综合控制协调加热系统、测温系统等，具体的，可以是PLC控制器。
作为本实施例的关键设计是，所述炉体17配套设置有旋转机构，从而可实现炉体17的旋转，炉体17与旋转机构的定位及连接关系、旋转机构可选用常规旋转，本实施例中，参见图1，炉体17借助炉体旋转轴17-1限位在支架17-2上，所述的旋转机构中包括驱动电机和与驱动电机输出轴连接的减速器，所述的减速器输出轴借助联轴器与炉体旋转轴17-1连接，从而控制炉体17的旋转。
所述的合成与晶体生长系统包括坩埚9和设置在其水平一侧的挥发元素承载器6，其中，坩埚9水平放置时类似卧倒放置的漏斗状，形状参见图2，结构中包括设置在侧面的水平长方体状或圆柱状等的籽晶容纳腔9-1、与籽晶容纳腔9-1连接的合成与晶体生长部9-2、注入插入孔9-3，注入插入管9-3位于合成与晶体生长部9-2的上部或端部，其直径大小需保证合成完毕后，化合物熔体高度低于注入插入管9-3的下边缘，从而不会发生化合物熔体从注入插入管9-3流出坩埚9；挥发元素承载器6设置有注入管8，注入管8穿过注入插入孔9-3伸入至坩埚9内，挥发元素承载器6内的挥发元素7受热借助注入管8进入坩埚9，与坩埚9内的金属熔体可实现水平注入合成；合成完毕后，旋转机构使炉体17由水平旋转为竖直状态，调节各受热区域的温度分布，保证籽晶容纳腔9-1内的温度低于籽晶15的熔点，待炉体17处于竖直后，再次调节各受热区域的温度分布保证坩埚9内的化合物熔体与籽晶15接触实现垂直梯度晶体生长。
为避免炉体17旋转造成坩埚9内的化合物熔体向挥发元素承载器6倒灌，所述的注 入管8设置为多段式，如图3中折弯形状，末段部分倾斜式远离挥发元素承载器6，优选，末段部分偏离挥发元素承载器6并与其侧面边缘线呈60°-85°夹角。
为进一步保证合成与晶体生长系统的稳定性，所述的合成与晶体生长系统中还包括装载所述坩埚9和挥发元素承载器6的装载架5，参见图3至图6，装载架5可为石英、碳化硅、氮化硼或陶瓷材质，所述装载架5配套设置密封盖5-1，密封盖5-1上设有排气口5-1-1。装配装置时，将挥发元素承载器6的注入管8插入坩埚9的注入插入孔9-3中，挥发元素承载器6和坩埚9中间垫上隔热板2，然后将挥发元素承载器6和坩埚9一起放入装载架5中，然后安装密封盖5-1，使密封盖5-1与装载架5固定密封连接，排气口5-1-1用于平衡合成时装载架5内的气压，可排出挥发元素注入金属熔体后形成化合物熔体过程中，装载架5内压力增加所产生的多余气体。
所述坩埚9与挥发元素承载器6之间借助隔热板2隔开，隔热板2的设置一方面分隔坩埚9与挥发元素承载器6，避免温度互相影响；另一方面，当炉体17旋转呈竖直状态后，隔热板2支撑在坩埚9的上端面，避免了挥发元素承载器6意外落入坩埚9内。
所述坩埚9配套设置坩埚支撑16，对籽晶容纳腔9-1及坩埚9整体具有支撑和保护作用的。
装置实施例2
与实施例1不同的是，本实施例中注入管8为“乙字形”多段管，其末端背离挥发元素承载器6。
所述的装载管5为石英材质。
以实施例1所述的装置为例，说明本发明水平注入合成后旋转连续VGF晶体生长的方法。
合成方法实施例1——磷化铟半导体材料的合成
㈠首先进行备料和装置装配：如图3所示，将挥发元素7(本实施例为红磷)装配在挥发元素承载器6内并密封，将磷化铟的籽晶15、金属元素10(本实施例为纯铟金属)连同掺杂剂(高纯硫或者高纯铁)及氧化硼11置于坩埚内9内，然后将挥发元素承载器6的注入管8插入坩埚9的注入插入孔9-3中，挥发元素承载器6及合成与晶体生长坩埚9中间用隔热板2隔开，然后将挥发元素承载器6、坩埚9及两者之间的隔热板2一并放入密封舱内，再将密封舱整体放入炉腔内，本实施例中的密封舱选用装载舱5，装载舱5配套设置密封盖5-1从而形成密封舱，密封连接方式为焊接或套装密封等。装载纯铟金属的量为保证铟熔化完成后不与籽晶15接触，并保证氧化硼11熔化完后要覆盖籽晶15，同时保证合成完毕后 形成的铟-磷熔体不与籽晶15接触。
㈡密封炉体，抽真空至10-3Pa，充入保护性气体氮气1.5-1.8MPa，保证进行合成和晶体生长时保护气体压为3.0-4.0MPa(大于熔点附近磷化铟的离解压2.75MPa)。
㈢然后控制多段加热器3对坩埚9所在区域进行加热，使金属元素10温度高于化合物熔点30-70℃，温度过低将影响注入合成效率，温度过高将导致合成配比熔体所需的压力过高，通过控制系统和热电偶e和/或热电偶c和/或热电偶d，保证坩埚9内的金属元素10(纯铟)的温度达到1112℃(化合物磷化铟的熔点为1062℃)，同时使籽晶容纳腔9-1区域的温度低于化合物熔点5-15℃,本实施例总通过热电偶e及控制系统和加热系统的配合，约控制热电偶e温度在1050℃。氧化硼11受热变为熔体，密封纯铟熔体和籽晶15。
㈣再控制多段加热器3对挥发元素承载器6所在区域进行加热，使热电偶b所在区域温度控制在800℃左右。此时，红磷的离解压高于气氛压力(3.0-4.0MPa)，红磷受热挥发，磷气体注入到金属元素7熔体(纯铟熔体)中，如图4所示。由于挥发元素7注入后溢出，石英装载舱5内的压力会增加，多余的气体会通过装载舱5上的排气口5-1-1排出；随着合成的进行，化合物熔体的体积不断增加，此时籽晶15不会与化合物熔体接触，如图5所示。
㈤合成完毕后，对化合物熔体所在区域进行降温，至热电偶a和/或热电偶c和/或热电偶d温度为1062℃以上10℃，控制热电偶b、热电偶d的温度为热电偶b≥热电偶d>1062℃即可，同时保证籽晶容纳腔9-1区域的热电偶e的温度不变；然后，将整个炉体17以30°/h的速度缓慢旋转至竖直状态，将熔体静置10-30分钟，使得注入管8中的氧化硼和熔体滴入合成与晶体生长部9-2中，此过程中保证热电偶e温度恒定，控制多段加热器3在籽晶15与化合物熔体接触的界面及化合物熔体中建立温度梯度，控制热电偶温度高低关系为热电偶b>热电偶c>热电偶e>热电偶d>热电偶a，此时，保证固液界面的温度梯度在5K/mm左右，然后进行VGF晶体生长，如图6所示，获得磷化铟半导体单晶材料。
制备的掺硫磷化铟晶体的载流子浓度：≥1×1018cm-3；迁移率：≥1000cm2V-1S-1；电阻率：(0.1-6)×10-3Ω·cm；位错密度<1000/cm2。
制备的掺铁磷化铟晶体的迁移率：≥1000cm2V-1S-1；电阻率：1×107Ω·cm位错密度<5000/cm2。
合成方法实施例2——磷化镓半导体材料的合成
㈠首先进行备料和装置装配：如图3所示，将挥发元素7(红磷)装配在挥发元素承载器6内并密封，将磷化镓的籽晶15、金属元素10(纯镓金属)连同掺杂剂(高纯硫或者高纯 锌)及氧化硼11置于在坩埚9内，然后将挥发元素承载器6的注入管8插入合成与晶体生长坩埚9的注入插入孔9-3中，挥发元素承载器6与坩埚9中间用隔热板2隔开，然后将挥发元素承载器6、坩埚9及隔热板2放入装载舱5内，将密封盖5-1与装载舱5装配在一起，并整体放入炉腔内。装载纯镓金属的量为保证镓熔化完成后不与籽晶15接触，并保证氧化硼11熔化完后要覆盖籽晶15，同时保证合成完毕后形成的镓-磷熔体不与籽晶15接触。
㈡密封炉体，抽真空至10-3Pa，充入保护性气体3MPa，保证进行合成和晶体生长时保护气体压为5.0MPa。
㈢然后控制多段加热器3对坩埚9所在区域进行加热，通过控制系统和热电偶a和/或热电偶c和/或热电偶d，保证坩埚9内的金属元素7(纯镓)的温度达到1526℃(化合物磷化镓的熔点为1476℃，在其之上50℃)，同时保证籽晶容纳腔9-1所在区域(热电偶e)的温度低于化合物的熔点，约控制在1465℃。氧化硼11受热变为熔体，密封纯镓熔体和籽晶15。
㈣再控制多段加热器3对挥发元素承载器6所在区域进行加热，使热电偶b所在区域温度控制在900℃左右。此时，红磷的离解压高于气氛压力(5.0MPa)，红磷受热挥发，磷气体注入到金属元素7熔体(纯镓熔体)中，如图4所示。由于挥发元素7注入后溢出，石英装载舱5内的压力会增加，多余的气体会通过装载舱5的排气口5--1-1排出；随着合成的进行，化合物熔体的体积不断增加，此时籽晶15不会与化合物熔体接触，如图5所示。
㈤合成完毕后，对化合物熔体所在区域进行降温，至热电偶a和/或热电偶c和/或热电偶d温度为1476℃以上10℃，控制热电偶b、热电偶d的温度为热电偶b≥热电偶d>1476℃即可，同时保证籽晶容纳腔9-1区域的热电偶e的温度不变；然后，将整个炉体17以35°/h的速度缓慢旋转至竖直的状态，将熔体静置20分钟，使得注入管8中的氧化硼滴入化合物熔体中，此过程中保证热电偶e温度恒定，控制多段加热器3在籽晶15与化合物熔体接触的界面及化合物熔体中建立温度梯度，控制热电偶温度高低关系为热电偶b>热电偶c>热电偶e>热电偶d>热电偶a，此时，保证固液界面的温度梯度在5K/mm左右，进行VGF晶体生长，获得磷化镓半导体单晶材料。
制备的掺硫磷化镓晶体的载流子浓度：(1-8)×1017cm-3；迁移率≥100cm2V-1S-1；位错密度<5000/cm2。
制备的掺锌磷化镓晶体的载流子浓度：(5-200)×1017cm-3；迁移率≥25cm2V-1S-1；位错密度<5000/cm2。
综合上述内容，可知本发明提供的水平注入合成后旋转连续VGF晶体生长的方法及其配套的水平注入合成后旋转连续VGF晶体生长的装置，无需在注入法合成后、VGF晶体生长前放入多晶料，简化了工艺，避免了VGF生长前纯金属将籽晶15熔掉；方法步骤简洁、易于操作和控制，装置结构简单，易于操作，所合成的半导体晶体形状可控、质量均一，有利于实现半导体晶体的产业化生产。

Claims (13)

  1. 一种水平注入合成后旋转连续VGF晶体生长的装置，包括炉体(17)、定位在炉腔内的合成与晶体生长系统及其配套的加热系统、测温系统、保温系统和控制系统，其特征在于，所述合成与晶体生长系统包括侧面设有籽晶容纳腔(9-1)的坩埚(9)和设置在其水平一侧的挥发元素承载器(6)，所述挥发元素承载器(6)借助注入管(8)与坩埚(9)连通实现水平注入合成；所述炉体(17)借助配套的旋转机构具有旋转自由度，实现水平注入合成后旋转垂直温度梯度晶体生长。
  2. 根据权利要求1所述的装置，其特征在于，所述注入管(8)末端背离或倾斜式远离挥发元素承载器(6)。
  3. 根据权利要求2所述的装置，其特征在于，所述注入管(8)为多段式，末段倾斜式远离挥发元素承载器(6)，与挥发元素承载器(6)呈60°-85°夹角。
  4. 根据权利要求1所述的装置，其特征在于，所述合成与晶体生长系统中还包括装载所述坩埚(9)和挥发元素承载器(6)的装载架(5)，所述装载架(5)配套设置密封盖(5-1)，密封盖(5-1)上设有排气口(5-1-1)，所述装载架(5)为石英、碳化硅、氮化硼或陶瓷材质。
  5. 根据权利要求1所述的装置，其特征在于，所述加热系统结构中包括套设在合成与晶体生长系统外围的多段加热器(3)；所述保温系统结构中包括套设在加热系统外部的保温套(18)；所述测温系统结构中包括分别用于测定坩埚(9)内籽晶容纳腔(9-1)区域、合成与晶体生长部(9-2)区域和挥发元素承载器(6)区域的温度的热电偶a(14)、热电偶c(1)和/或热电偶d(13)和/或热电偶e(12)、热电偶b(4)。
  6. 根据权利要求1所述的装置，其特征在于，所述旋转机构驱动电机和与驱动电机输出轴连接的减速器，所述减速器输出轴借助联轴器与炉体旋转轴(17-1)连接，炉体(17)借助炉体旋转轴(17-1)限位在支架(17-2)上。
  7. 一种水平注入合成后旋转连续VGF晶体生长的方法，基于包括炉体(17)、定位在炉腔内的晶体合成生长系统及其配套的加热系统、测温系统、保温系统和控制系统的注入合成后旋转连续VGF晶体生长的装置，其特征在于，所述晶体合成生长系统包括侧面设有籽晶容纳腔(9-1)的坩埚(9)和设置在坩埚(9)水平一侧、并借助注入管(8)与其连通的挥发元素承载器(6)，所述炉体(17)配套设有旋转机构，所述方法包括以下步骤：
    ㈠备料和装置装配：将挥发元素(7)装入挥发元素承载器(6)内并密封，将籽晶(15)、金属元素(10)及氧化硼(11)置于坩埚(9)内，挥发元素承载器(6)和坩埚(9)一并定位于炉腔内；控制金属元素(10)与挥发元素(7)形成的化合物熔体液面低于籽晶容纳 腔(9-1)，氧化硼(11)熔化后密封化合物熔体且液面高于籽晶容纳腔(9-1)；
    ㈡密封炉体(17)，抽真空后充入保护性气体；
    ㈢加热使金属元素(10)和氧化硼(11)熔化；
    ㈣加热使挥发元素(7)通过注入管(8)进入金属元素(10)熔体，注入合成化合物熔体；
    ㈤合成完毕后，借助旋转机构将炉体(17)旋转至竖直状态，调整坩埚(9)所在区域的温度分布，实现合成后连续VGF晶体生长。
  8. 根据权利要求7所述的方法，其特征在于，所述步骤㈠中挥发元素承载器(6)和坩埚(9)一并定位于炉腔内是先将挥发元素承载器(6)的注入管(8)伸入坩埚(9)内，然后一并放入设有排气口(5-1-1)密封舱中，再将密封舱定位于炉腔内。
  9. 根据权利要求7所述的方法，其特征在于，所述步骤㈢中加热使金属元素(10)和氧化硼(11)熔化所需控制的温度是：使金属元素(7)的温度高于化合物熔点30-70℃，同时使籽晶容纳腔(9-1)区域的温度低于化合物熔点5-15℃；所述步骤㈣中加热使挥发元素(7)通过注入管(8)进入金属元素(10)熔体时，加热挥发元素(7)所达到温度的条件是保证挥发元素承载器(6)内的压力高于化合物熔体的离解压；所述步骤㈤中合成完毕后，首先对化合物熔体进行降温至高于化合物熔点5-20℃，控制化合物熔体液面与坩埚(9)的籽晶容纳腔(9-1)一侧的界面温度高于化合物结晶点3-5℃，同时保持籽晶容纳腔(9-1)区域温度稳定；所述步骤㈤中炉体(17)旋转呈竖直状态后，将化合物熔体静置10-30min。
  10. 根据权利要求7-9任一所述的方法，其特征在于，所述步骤㈤中旋转速率控制在20-40°/h；旋转过程中保持籽晶容纳腔(9-1)区域温度稳定；旋转至竖直状态后，调整坩埚(9)所在区域的温度分布，借助测温系统及控制系统的协调控制，在籽晶与化合物熔体接触的界面及化合物熔体中建立温度梯度，实现注入合成后连续VGF晶体生长。
  11. 根据权利要求7所述的方法，其特征在于，所述注入合成后旋转连续VGF晶体生长的装置中，旋转机构结构中包括驱动电机和与驱动电机输出轴连接的减速器，所述减速器输出轴借助联轴器与炉体旋转轴(17-1)连接，炉体(17)借助炉体旋转轴(17-1)限位在支架(17-2)上。
  12. 根据权利要求7或8所述的方法，其特征在于，所述注入合成连续VGF晶体生长的装置中，所述注入管(8)末端背离或倾斜式远离挥发元素承载器(6)，与挥发元素承载器(6)呈60°-85°夹角。
  13. 根据权利要求7-9任一所述的方法，其特征在于，所述注入合成后旋转连续VGF晶体生 长的装置中，所述加热系统结构中包括套设在晶体合成生长系统外围的多段加热器(3)；所述保温系统结构中包括套设在加热系统外部的保温套；所述测温系统结构中包括分别用于测定晶体生长坩埚(9)内籽晶容纳腔(9-1)区域、合成与晶体生长部(9-2)区域和挥发元素承载器(6)区域温度的热电偶a(14)、热电偶c(1)和/或热电偶d(13)和/或热电偶e(12)、热电偶b(4)。
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