WO2022213643A1 - 一种大尺寸化合物半导体单晶生长系统及方法 - Google Patents

一种大尺寸化合物半导体单晶生长系统及方法 Download PDF

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Publication number
WO2022213643A1
WO2022213643A1 PCT/CN2021/136318 CN2021136318W WO2022213643A1 WO 2022213643 A1 WO2022213643 A1 WO 2022213643A1 CN 2021136318 W CN2021136318 W CN 2021136318W WO 2022213643 A1 WO2022213643 A1 WO 2022213643A1
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raw material
crucible
crystal growth
single crystal
furnace body
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PCT/CN2021/136318
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English (en)
French (fr)
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王书杰
孙聂枫
史艳磊
邵会民
徐森锋
付莉杰
王阳
李晓岚
欧欣
宋瑞良
刘惠生
孙同年
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中国电子科技集团公司第十三研究所
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Publication of WO2022213643A1 publication Critical patent/WO2022213643A1/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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/20—Controlling or regulating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of single crystal preparation, and particularly relates to a preparation system and method for large-size, especially ultra-long-length compound semiconductor single crystals.
  • the volume of the confined space needs to be increased, especially the length of the space needs to be increased in the longitudinal direction.
  • Chinese Patent No. 200310108634.0 discloses a device and method for supplementing the growth of crystals with molten materials, using a plurality of connected crucibles to increase the supply of raw materials, which will greatly increase the volume of the furnace body.
  • Chinese Patent No. 201621248917.4 discloses a crystal growth furnace capable of continuous production. Multiple crucible assemblies are sequentially moved into the furnace body through a horizontal moving mechanism and a vertical lifting mechanism. This method may interrupt the crystal growth process and affect the crystal quality.
  • Chinese Patent 201720922581.3 adopts another technical route, and discloses a material supply device and a crystal growth system.
  • the disclosed material supply device supplies materials to the crucible inside the furnace body from the outside. Since two kinds of equipment are connected, the complexity of equipment control is increased; feeding materials from outside the furnace may cause material contamination in the feeding process.
  • the technical scheme adopted in the present invention is: a large-scale single crystal growth system, comprising a crucible, two or more main body columns, a main furnace body disposed between the main body columns and located on a support table .
  • the system also includes a control device for the crystal growth space and a raw material injection device in the furnace, wherein the raw material injection device includes a plurality of mutually independent raw material carrying injection systems.
  • the control device for the crystal growth space includes 1-4 movable furnace bodies arranged on the inner or outer side of the main furnace body, and the movable furnace bodies are arranged on the main column through the driving motor and the driving arm;
  • the top of the movable furnace body is sealed, the other movable furnace bodies are open cylinders, and the seed rod and the driving device of the seed rod are arranged on the movable furnace body sealed at the top.
  • the raw material injection device is arranged on the separator, and includes an annular raw material water cooling plate and a raw material carrying injection system.
  • the raw material water cooling plate is evenly provided with raw material grooves;
  • the raw material carrying and injection system includes a raw material carrier, a resistance wire arranged around the raw material carrier, a raw material injection pipe connected to the raw material carrier, and a raw material carrier upper cover.
  • the raw material carrying injection system is inserted into the raw material tank, and the raw material injection pipe protrudes from the injection pipe tank.
  • the raw material tank is provided with 6-12; the raw material injection pipe is provided with two lengths, the outlet of which is respectively higher and lower than the liquid level height of the melt in the crystal growth process.
  • the present invention also proposes a method for preparing a large-sized single crystal.
  • the preparation method comprises the following steps:
  • step A the crucible and the raw material carrying and injecting system are placed in the raw materials required for crystal growth, and a large-scale single crystal growth system is assembled.
  • Step B heating the crucible to form a melt in the crucible.
  • Step D Start crystal growth.
  • Step E Determine the remaining amount of raw materials in the crucible. If the remaining amount is less than 15-20% of the total amount of raw materials at the start of crystal growth, start necking, and perform step F after necking is completed, otherwise continue crystal growth.
  • Step F Start two or more raw material carrying injection systems to inject raw materials into the crucible.
  • step G the crystal growth is started, and the crystal growth space is adjusted according to the crystal length by using the control device of the crystal growth space.
  • the position range of the melt level in the crucible is determined according to the optimal seeding position range, and the total amount of melt below the position is determined according to the middle value of the position range of the melt level and the shape of the crucible, and a pair of raw material carrying The amount of raw materials injected into the system is 1/n of the total amount of the melt, n is a positive integer and n ⁇ 5.
  • control device of the crystal growth space includes 1-4 movable furnace bodies arranged on the inner or outer side of the main furnace body, and the movable furnace bodies are arranged on the main column through the driving motor and the driving arm;
  • the outer movable furnace body is sealed at the top, the other movable furnace bodies are open cylinders, and the seed rod and the driving device of the seed rod are arranged on the movable furnace body sealed at the top.
  • the raw material injection device includes an annular raw material water cooling plate and a raw material carrying injection system.
  • the raw material carrying injection system is inserted into the raw material tank, and the raw material injection pipe protrudes from the injection pipe tank.
  • the present invention designs a large-size single crystal preparation method, which is firstly a scalable single crystal growth system suitable for large-size crystal growth. Pure raw materials (such as phosphorus, indium) are cooled, and multiple independent raw material carrying and injection systems are set in the raw material water cooling tray.
  • Pure raw materials such as phosphorus, indium
  • control the raw material carrying injection system to start sequentially until the required amount of melt is reached, and then stop the injection; when the melt is nearly exhausted, start to neck the crystal to the size of the seed crystal, and then start the next group
  • the system is injected into the system for synthesis until the required amount of melt is reached, after which the crystal continues to grow, and the cycle of synthesis, single crystal growth, single crystal necking, resynthesis, and single crystal growth is repeated for multiple rounds of synthesis and single crystal growth.
  • the furnace body is continuously elongated to ensure that the crystal grows to a sufficient length.
  • the raw material carrier injection system can cool the carrier injection system to prevent the raw materials from melting and flowing out or sublimated by heat; multiple carrier injection systems can be placed in the device to realize continuous synthesis or intermittent synthesis.
  • the crystal growth can be carried out by continuous synthesis in a smaller crucible, and then the synthesis is stopped after the desired amount of melt is synthesized, and then the synthesis is re-crystallized, and the preparation of long single crystals can be achieved alternately in this way, while saving energy and related costs. consumables.
  • the optimal seeding position determine the amount of raw materials in a pair of raw material load-bearing injection systems to ensure that the liquid level in the crucible is at the optimal seeding position during seeding.
  • a single substance is placed in the raw material carrier injection system to grow single-crystal silicon, germanium and other elemental semiconductors; two substances are placed to grow crystals such as indium phosphide (InP) and gallium phosphide (GaP); three A kind of raw material is used for the growth of ternary or more compound semiconductor crystals such as phosphorus germanium zinc (ZnGeP 2 ), etc., the operation is flexible and the adaptability is strong.
  • Fig. 1 is the structural representation of the present invention
  • Figure 5-7 is a schematic diagram of the crystal growth process
  • Fig. 8 is a partial enlarged view of Fig. 1,
  • Fig. 9 is the structural schematic diagram of the raw material carrying injection system
  • Fig. 10 is the structural representation of the raw material carrier jacket
  • Fig. 11 is a sectional view of the raw material water cooling plate
  • Fig. 12 is a top view of the raw material water cooling plate
  • Figure 13 is the raw material water cooling tray cover.
  • 1 main furnace body; 2: primary furnace body; 3: secondary furnace body; 4: tertiary furnace body; 5: support table; 6: seed rod; 7: seed rod lifting motor; 8 : Seed rod rotating motor; 9: Crucible rod; 10: Crucible rod lifting motor; 11: Crucible rod rotating motor; 12: Vacuum pipeline; 13: Filling and discharging pipeline; 14: Pressure limiting valve; 15: Main body column; 16 : Primary drive motor; 16-1: Primary drive arm; 17: Secondary drive motor; 17-1: Secondary drive arm; 18: Tertiary drive motor; 18-1: Tertiary drive arm; 19: Main Furnace body drive motor; 19-1: main drive arm; 20: chassis; 20-1: column motor; 21: insulation jacket; 22: main heater; 23: auxiliary heater; 24: crucible; 25: crucible support; 30: seed crystal; 31: single crystal ingot; 33: sealing groove; 34: sealing ring; 26-1: raw material; 26-2: solid boron oxide; 1-1: separator;
  • a large-scale single crystal growth system includes two or more main body columns 15, the main body columns 15 are arranged on the chassis 20 through the column motor 20-1;
  • the main furnace body 1 on the table 5 has a crucible 24 and a crucible heating and supporting structure inside the main furnace body 1, and a seed rod 6 and a seed rod driving device above the crucible 24;
  • the main furnace body drive motor 19 and the main drive arm 19-1 are positioned on the main body column 15;
  • the main furnace body 1 is provided with a partition 1-1 in the middle, and the main furnace body 1 is divided into two parts by the partition plate 1-1.
  • the system also includes a control device for the crystal growth space matched with the main furnace body 1 and a raw material injection device arranged on the separator 1-1.
  • the crucible heating structure includes a heat preservation jacket 21, a main heater 22, and an auxiliary heater 23;
  • the crucible support structure includes a crucible rod 9 passing through the support table 5, a crucible rod lifting motor 10 connected to the crucible rod 9, and a crucible rod rotating motor 11.
  • the system also includes a vacuum pipe 12 and a gas charging and discharging pipe 13 that pass through the support table 5 to the main furnace body 1 , and the charging and discharging pipe 13 is connected to the pressure limiting valve 14 .
  • the main body column 15 moves around the chassis 20 through the column motor 20-1
  • Control device for crystal growth space
  • a sealing cover that can move up and down can also be arranged in the main furnace body 1 , but the sealing with the inner wall of the main furnace body 1 is not easy to achieve.
  • the control device of the crystal growth space of the present invention is 1-4 movable furnace bodies arranged inside or outside the main furnace body 1, and the movable furnace bodies are arranged on the main body column 15 through a driving motor and a driving arm.
  • the movable furnace body When the movable furnace body is arranged on the outside of the main furnace body 1, the top of the outermost movable furnace body is sealed, and the driving arm of the movable furnace body is arranged at the bottom of the outer side of the movable furnace body; when the movable furnace body is arranged on the main furnace body 1 When it is inside, the top of the innermost movable furnace body is sealed, and the driving arm of the movable furnace body is arranged on the outer top of the movable furnace body.
  • only one movable furnace body is sealed at the top, the other movable furnace bodies are open cylinders, and the seed rod 6 and the seed rod driving device are arranged on the movable furnace body sealed at the top.
  • three movable furnace bodies are arranged on the inside of the main furnace body 1: from the inside to the outside, they are the primary furnace body 2, the secondary furnace body 3, the third furnace body 4, and three movable furnace bodies.
  • the main body uprights 15 are respectively connected to the main body column 15 through the primary drive motor 16, the primary drive arm 16-1, the secondary drive motor 17, the secondary drive arm 17-1, the tertiary drive motor 18, and the tertiary drive arm 18-1.
  • the top of the primary furnace body 2 is sealed, and the seed rod 6 and the seed rod driving device are arranged on the primary furnace body 2 .
  • the main furnace body drive motor 19 is limited in the vertical track or spiral track (not shown in the figure) of the main body column 15, one end of the main drive arm 19-1 is connected to the main furnace body drive motor 19, and the other end is connected to the main furnace body 1 .
  • a main furnace body drive motor 19 , a main furnace body drive motor 19 and a main drive arm 19 - 1 are arranged on each main body column 15 , and at least two sets are provided according to the number of main body columns 15 .
  • each main furnace body driving motor 19 runs synchronously to ensure the horizontal position of the main furnace body 1 .
  • the main furnace body 1 and the furnace bodies at all levels move up and down along the main body column 15 through the matched drive motor and drive arm.
  • the setting of the drive motors and drive arms of the 3 movable furnace bodies is the same as above.
  • the inner diameter and outer diameter of the adjacent movable furnace bodies are matched, between the main furnace body 1 and the third-level furnace body 4, between the third-level furnace body 4 and the second-level furnace body 3, and between the second-level furnace body 3 and the first-level furnace body
  • the gap between the bodies 2 is 0.1-0.5mm.
  • a sealing groove 33 is also provided inside the main furnace body 1 and the movable furnace body, and there is a sealing ring 34 in the sealing groove 33 .
  • the sealing ring 34 is located in the inner wall of the main furnace body 1 and the sealing grooves 33 in the inner wall of each movable furnace, and the furnace bodies are sealed by two sealing rings 34, and the distance between the two sealing grooves 33 is 15-30mm.
  • the position of the upper sealing groove 33 is 15mm-30mm from the top of the furnace body, and the limit position of the movable furnace body is the vertical distance 15mm-30mm from the bottom end of the movable furnace body to the sealing groove 33 under the adjacent furnace body.
  • the main furnace body 1 is in close contact with the support table 5, and a gasket can be added if necessary; the top of the innermost primary furnace body 2 is sealed; the sizes of the adjacent furnace bodies are matched, and there is a sealing ring 34 sealed, thereby forming the confined space required for crystal growth.
  • the raw material injection device is provided above the crucible 24 in the main furnace body 1 .
  • the device includes an annular raw material water cooling plate 27 and a raw material carrying injection system 28, as shown in FIG. 1 .
  • the main furnace body 1 is provided with a circulating water circuit;
  • the raw material water cooling plate 27 is made of copper material, with a circulating water circuit inside, and an outlet and an inlet of the circulating water are set to communicate with the circulating water channel inside the main furnace body 1, which is a common water cooling structure.
  • the separator 1-1 is a part of the main furnace body 1, and since there is a circulating water channel connected to the main furnace body 1, it can withstand high temperature.
  • the circulating water in the partition plate 1-1 is sent to the circulating water channel of the raw material water cooling plate 27 through the water channel connection pad 32.
  • the raw material water cooling plate 27 is annular, its outer diameter is smaller than the inner diameter of the main furnace body 1, and its inner diameter is less than or equal to the inner diameter of the crucible 24, and the raw material grooves 27-1 are evenly arranged on it, and the number is 6-12; Inside the raw material water cooling plate 27, each raw material tank 27-1 is provided with an injection pipe groove 27-2; the raw material water cooling plate 27 also has a matching raw material water cooling plate cover 27-3.
  • the inside of the raw material tank 27 - 1 is cylindrical, and may be a through hole penetrating the raw material water cooling plate 27 or a hole that does not penetrate the raw material water cooling plate 27 .
  • the raw material tank 27-1 is not a pipe perforation.
  • the thickness of the water-cooled copper wall inside the raw material water-cooled plate 27 is 10-15mm.
  • the injection pipe groove 27-2 starts from the top of the raw material tank 27-1, and the length is greater than 4/5 of the height of the raw material water cooling plate 27.
  • the raw material carrier injection system 28 includes a raw material carrier 28-2, a resistance wire 28-4 arranged around the raw material carrier 28-2, and a raw material injection pipe 28-5 communicating with the raw material carrier 28-2. .
  • the upper cover of the raw material carrier is 28-6.
  • the raw material carrier injection system 28 further includes a jacket of the raw material carrier 28-2, the main body of the jacket is an insulating layer outer cylinder 28-9, the top of the insulating layer outer barrel 28-9 is open, and the supporting hole 28-9 is provided. 8 of the insulating layer upper cover 28-7; the insulating layer outer cylinder 28-9 has an injection tube placement groove 28-10 on the side, and is equipped with an insulating layer baffle 28-11; the raw material carrier 28-2 is placed on the insulating layer outer cylinder 28 In -9, the raw material injection pipe 28-5 protrudes from the injection pipe placement groove 28-10.
  • the raw material injection pipe 28-5 is arranged at the bottom of the raw material carrier 28-2 to facilitate the injection of liquid raw materials.
  • the raw material injection pipe 28-5 is set to two lengths, the outlet of which is higher and lower than the liquid level of the reaction melt during the crystal growth process, respectively, so as to meet the injection requirements of liquid and gaseous raw materials.
  • the raw material injection pipe 28-5 is set to have two lengths, respectively the height of the liquid level of the upper surface of the liquid sealing agent above the melt when its outlet is higher and lower than the optimal seeding position.
  • Metal elements or elements that are not easy to sublime are placed in the carrier 28-2 with the liquid level height of the upper surface of the boron oxide above the melt when it is higher than the optimal seeding position, and when it is lower than the optimal seeding position, the upper surface of the boron oxide above the melt is placed in the carrier 28-2.
  • the sublimable element is placed in the carrier 28-2 at the surface level.
  • the raw material water cooling plate 27 is 40-60mm higher than the raw material carrier 28-2, the interior of the raw material tank 27-1 is a cylinder, the distance between the centers of the adjacent raw material tanks 27-1 is greater than D+40mm, and D is the raw material tank 27-1 diameter of.
  • the raw material carrying injection system 28 is inserted into the raw material tank 27 - 1 , and the raw material water cooling plate cover 27 - 3 covers the raw material water cooling plate 27 .
  • the raw material injection pipe 28-5 protrudes from the injection pipe groove 27-2 and is aligned with the crucible 24 below. Since the inner diameter of the raw material water cooling plate 27 is less than or equal to the inner diameter of the crucible 24, it can be ensured that the raw material injection pipe 28-5 is aligned with the crucible 24, and the raw material does not leak.
  • the crystal growth raw material 28-3 is put into the raw material carrier 28-2, and then the raw material carrier upper cover 28-6 and the raw material carrier 28-2 are welded together. Both the raw material carrier upper cover 28-6 and the raw material carrier 28-2 are made of quartz.
  • the resistance wire 28-4 is wound on the outside of the raw material carrier 28-2, and is put into the insulating layer outer cylinder 28-9 together.
  • the raw material injection pipe 28-5 is assembled in the injection pipe placement groove 28-10, and then the insulation
  • the layer baffle 28-11 is inserted into the injection tube placement groove 28-10 and assembled together.
  • the seed crystal 30 is assembled on the seed rod 6 .
  • the gas in the furnace body is discharged through the gas charging and discharging pipeline 13 .
  • the primary furnace body 2 is raised again until it is separated from the secondary furnace body 3.
  • the secondary furnace body 3 and the tertiary furnace body 4 are sequentially lowered onto the separator 1-1, and the single crystal ingot 31 is taken out.
  • the raw material carrying injection system 28 is divided into a phosphorus injection system and an indium injection system according to the different carrying materials below. See Figures 5-7.
  • Example 1 Indium Phosphide (InP) was grown.
  • the raw material 26-1 is indium.
  • step A metal indium is placed in the crucible 24, and metal indium and phosphorus are respectively placed in the raw material carrying injection system to assemble a large-scale single crystal growth system.
  • Step B heating the crucible to form an indium melt in the crucible.
  • Step C starting the raw material carrying injection system for placing phosphorus, and injecting gaseous phosphorus into the crucible to form an indium phosphide melt.
  • Step D Start crystal growth.
  • Step E Determine the remaining amount of indium phosphide in the crucible. If the remaining amount is less than 15-20% of the total indium phosphide when the crystal growth starts, start necking, and perform step F after the necking is completed, otherwise continue the crystal growth.
  • step F two or more raw material carrying injection systems are activated, and liquid indium and gaseous phosphorus are injected into the crucible respectively to form an indium phosphide melt.
  • the raw material 26-1 metal indium is placed in the crucible, and the injection raw materials are phosphorus and indium, which are separately placed in the raw material carrier 28-2, and the raw material carrying injection system 28 for placing the two materials is inserted into the raw material tank 27-1 at intervals.
  • the raw material 26-1 metal indium in the crucible is the same amount of indium as in a single indium injection system.
  • the port of the raw material injection pipe 28-5 of the raw material carrying injection system 28 carrying phosphorus is located 1-5 mm from the bottom of the crucible, and is to be immersed in the melt during the crystal growth process.
  • the port of the raw material injection pipe 28-5 of the indium-carrying raw material carrying injection system 28 is higher than the liquid level of the molten boron oxide 26-2 by more than 10 cm.
  • the crucible rod 9 is activated to rotate the crucible 24 .
  • the seed rod 6 is lowered, the seed crystal 30 is brought into contact with the indium phosphide melt, and crystal growth is started.
  • the seed crystal 30 is pulled up by the seed rod 6 to grow a single crystal ingot 31 .
  • the single crystal ingot 31 begins to neck down; when 0.5-3% of the melt remains in the crucible, the single crystal ingot 31 is lifted by the seed rod 6, so that the necking interface rises to the maximum Near the best seeding location range.
  • the above process is called a growth cycle.
  • the single crystal ingot 31 begins to neck; when the melt remaining in the crucible is 0.5-3%, the single crystal ingot 31 is lifted by the seed rod 6, so that the necking interface rises to the maximum Near the best seeding location range.
  • the ascending movement of the primary furnace body 2 reaches its limit position, that is, the vertical distance between the bottom end of the primary furnace body 2 and the sealing groove 33 under the secondary furnace body 3 is 15mm-30mm.
  • the secondary furnace body 3 and the third furnace body 4 are sequentially activated until the growth of the single crystal ingot 31 is completed.
  • the primary furnace body 2 rises to the limit position, it rises synchronously with the secondary furnace body 3, and after the secondary furnace body 3 rises to the limit position, the three furnace bodies rise synchronously.
  • Example 2 growing indium phosphide (InP).
  • the raw material 26-1 is polycrystalline indium phosphide.
  • step A indium phosphide polycrystal is placed in the crucible 4, metal indium and phosphorus are placed in the raw material carrying and injection system, respectively, and a large-size single crystal growth system is assembled.
  • Step B heating the crucible to form an indium phosphide melt in the crucible.
  • Step D Start crystal growth.
  • Step E Determine the remaining amount of indium phosphide in the crucible. If the remaining amount is less than 15-20% of the total indium phosphide when the crystal growth starts, start necking, and perform step F after the necking is completed, otherwise continue the crystal growth.
  • step F two or more raw material carrying injection systems are activated, and liquid indium and gaseous phosphorus are injected into the crucible respectively to form an indium phosphide melt.
  • step G crystal growth is started, and the crystal growth space is adjusted according to the crystal length.
  • the ratio of indium to phosphorus is 1:1.1-1.3.
  • the amount of polycrystalline indium phosphide in the raw material 26-1 in the crucible 24 is determined as follows: after the indium phosphide is formed into a melt, the liquid level in the crucible is within the range of the optimum seeding position.
  • the raw material 26-1 indium phosphide polycrystalline in crucible 24 is equal to the total mass of indium and phosphorus placed in one phosphorus injection system and one indium injection system, or the aforementioned total mass is the raw material 26-1 indium phosphide in crucible 24 Polycrystalline 1/n, n ⁇ 5.
  • the position of the raw material injection pipe 28 - 5 of the raw material carrying injection system 28 is set as above.
  • the seed crystal rod 6 is lowered, the seed crystal 30 contacts the indium phosphide melt to start crystal growth, and the seed crystal 30 is pulled up by the seed crystal rod 6 to grow a single crystal ingot 31 .
  • the single crystal ingot 31 begins to neck; when the melt remaining in the crucible is 0.5-3%, the single crystal ingot 31 is lifted by the seed rod 6, so that the necking interface rises to the maximum Near the best seeding location range. .
  • the single crystal ingot 31 begins to neck; when the melt remaining in the crucible is 0.5-3%, the single crystal ingot 31 is lifted by the seed rod 6, so that the necking interface rises to the maximum near the best seeding location range.
  • the above process is called a growth cycle.
  • the single crystal ingot 31 begins to neck; when the melt remaining in the crucible is 0.5-3%, the single crystal ingot 31 is lifted by the seed rod 6, so that the necking interface rises to the maximum Near the best seeding location range.
  • the above work is repeated for synthesis and growth of the single crystal ingot 31 .
  • the above process is called the secondary growth cycle.
  • the gas is released, the primary furnace body 2 is raised until it is separated from the secondary furnace body 3, the single crystal ingot 31 is taken out, and then water is injected into the crucible 24 to dissolve the boron oxide and release the bonding between the injection pipe and the boron oxide. . Remove the synthesis system and single crystal growth heat field, and clean the furnace body.
  • the use of the raw material can be judged by adding a weighing mechanism on the seed rod 6 to weigh the grown crystal.
  • the necking in step E is performed before each injection of raw materials, that is, it is completed under the following conditions: 1.
  • the preset raw materials in the crucible are about to be used up (15-20% remaining).
  • the optimal seeding position range with the best yield and the lowest defect is experimentally determined, and the position range of the melt level in the crucible 24 is determined according to the optimal seeding position.
  • the middle value of the position range of the face and the shape of the crucible 24 determine the total amount of melt in the crucible below this position, that is, the volume of the crucible below this position range.
  • the optimal seeding position range is the crucible position range where the longitudinal temperature gradient near the surface of the solution is the highest and the transverse temperature gradient is symmetrical. This refers to a range of height positions within the crucible.
  • the amount of feedstock in a pair of feedstock-carrying injection systems is 1/n of the total amount of the melt, where n is a positive integer and n ⁇ 5.
  • the amounts of phosphorus and indium were calculated from the amounts after synthesizing indium phosphide.
  • the amount of indium and phosphorus in a pair of raw material carrying injection systems is 1/n of the total amount of the melt.
  • each raw material injection is matched with necking; when n>1, continuously start n to inject the raw material carrying injection system, that is, step F: start two or more raw material carrying injections system to inject the raw material into the crucible.
  • Synthesis and crystal growth are performed after implantation, followed by necking.
  • indium and phosphorus can be injected alternately, or all indium can be injected first, and then phosphorus can be injected.
  • the amount of raw materials in the raw material carrying injection system is determined according to the middle value of the position range of the melt level, plus the inevitable residual amount of indium phosphide (0.5-3%) in the crucible during the crystal growth process, the raw material in the crucible can be guaranteed. After the synthesis, the seeding is in the best position.
  • the amount of indium and phosphorus in a pair of raw material carrying injection systems is 1/n of the total amount of the melt, which can reduce the capacity requirement of the raw material carrying injection system and is easier to implement.
  • the crystal weight between adjacent necks is m times the total amount of phosphorus and indium in a pair of raw material carrying and injection systems, where m is a positive integer and m ⁇ 5.
  • the amount ratio of A to B is x: 1.1-1.3y, where B is a volatile element.
  • the raw material injection system is changed to a single substance, and single-crystal silicon, germanium and other elemental semiconductors can be grown.
  • a raw material injection system of three raw materials it is also possible to grow ternary or higher compound semiconductor crystals such as phosphorus germanium zinc (ZnGeP2).

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Abstract

一种大尺寸化合物半导体单晶生长系统及方法，属于单晶制备领域，特别涉及大尺寸尤其是超长长度化合物半导体单晶的制备系统和方法。大尺寸单晶生长系统包括晶体生长空间的控制装置和炉体内的原料注入装置。在原料合成和晶体生长过程中注入原料，并根据单晶的长度调节生长空间。由于存在多次缩颈处理，可以降低晶体本身的热应力，防止长得太长而断裂，同时大幅降低多次生长过程中缺陷的产生及原有缺陷的延伸；这种结构可以不受高压制备设备尺寸的限制。原料承载注入系统可以实现对承载注入系统的冷却，实现连续合成，或者间歇合成。

Description

一种大尺寸化合物半导体单晶生长系统及方法 技术领域
本发明属于单晶制备领域，特别涉及大尺寸尤其是超长长度化合物半导体单晶的制备系统和方法。
背景技术
作为半导体材料，单晶的生长需要高温高压环境。目前晶体的生长在一个密闭的固定空间内完成。
大尺寸、长单晶能够尽可能的制备出更多的大尺寸半导体单晶衬底，这样会大幅降低后续器件的成本，目前几乎所有的半导体单晶都在向着大尺寸、长单晶方向发展。
当需要生长制作大尺寸晶体，尤其是对长度有要求时，需要增大密闭空间体积，尤其是在纵向需要增加空间的长度。
对于需要在高压环境生长的化合物半导体来说，由于密闭空间内温度场分布不均匀，空间增大会造成热场内对流大，进行大容量合成及生长高品质、大尺寸、长单晶非常困难。而且随着晶体长度的增加，位错延伸增殖严重。
如生长InP时，由于磷的离解压高，热场内对流大，进行大容量合成及生长高品质、大尺寸、长单晶非常困难。目前未见有解决方案。
另外，当生长制作大尺寸晶体时，需要的原料相应增加。增加原料的一种手段是增大坩埚容积，带来的问题是坩埚内的温度场难以控制。
针对这一问题，目前有两种解决方案：多坩埚供料，炉体外增加供料装置。
中国专利200310108634.0披露了一种熔料补充生长晶体的装置和方法，使用多个连通的坩埚以增加原料的供应，这种方式会大大增加炉体的体积。
中国专利201621248917.4披露了可实现连续生产的晶体生长炉，多个坩埚组件经过水平移动机构和垂直提升机构依次移动到炉体内，这种方式有可能会中断晶体的生长过程，影响晶体质量。
中国专利201720922581.3采用另外一种技术路线，披露了物料供给设备与晶体生长系统，其公开的物料供给设备，从外部向炉体内部的坩埚中供给物料。由于是两种设备连接，增加了设备控制的复杂度；从炉体外供料，有可能造成供料过程中材料的污染。
发明内容
针对上述问题，提出了本发明。
为实现发明目的，本发明采用的技术方案是：一种大尺寸单晶生长系统，包括坩埚、2个或2个以上的主体立柱，设置在主体立柱之间、位于支撑台上的主炉体。
系统还包括晶体生长空间的控制装置和炉体内的原料注入装置，所述原料注入装置包括多个相互独立的原料承载注入系统。
所述晶体生长空间的控制装置包括设置在主炉体内侧或外侧的1-4个可移动炉体，可移动炉体通过驱动电机和驱动臂设置在主体立柱上；最内侧或最外侧的可移动炉体顶部密封，其它可移动炉体为开放的圆筒，籽晶杆及籽晶杆驱动装置设置在顶部密封的可移动炉体上。
所述原料注入装置设置在隔板上，包括环形原料水冷盘和原料承载注入系统。
原料水冷盘上均匀设置原料槽；原料承载注入系统包括原料承载器、设置在原料承载器周围的电阻丝、连通原料承载器的原料注入管、原料承载器上盖。
原料承载注入系统插入原料槽中，原料注入管从注入管槽中探出。所述原料槽设置6-12个；原料注入管设置成2种长度，分别为其出口高于和低于晶体生长过程中熔体的液面高度。
基于上述系统，本发明还提出了一种大尺寸单晶制备方法。
所述制备方法包括以下步骤：
步骤A、坩埚和原料承载注入系统内放置晶体生长所需原料，装配大尺寸单晶生长系统。
步骤B、加热坩埚，在坩埚内形成熔体。
步骤D、开始晶体生长。
步骤E、判断坩埚中的原料剩余量，如果剩余量小于开始晶体生长时的原料总量的15-20％，开始缩颈，缩颈完成后执行步骤F，否则继续晶体的生长。
步骤F、启动两个或两个以上原料承载注入系统，将原料注入到坩埚。
步骤G、开始晶体生长，同时根据晶体长度，使用晶体生长空间的控制装置调整晶体生长空间。
重复步骤E-G，直至所有原料注入完成。
进一步地，根据最优引晶位置范围确定坩埚内熔体液面的位置范围，根据熔体液面的位置范围的中间值和坩埚的形状确定该位置以下的熔体总量，一对原料承载注入系统中原料的量为所述熔体总量的1/n，n为正整数且n<5。
进一步地，所述晶体生长空间的控制装置包括设置在主炉体内侧或外侧的1-4个可移动炉体，可移动炉体通过驱动电机和驱动臂设置在主体立柱上；最内侧或最外侧的可移动炉体顶部密封，其它可移动炉体为开放的圆筒，籽晶杆及籽晶杆驱动装置设置在顶部密封的可 移动炉体上。
进一步地，所述原料注入装置包括环形原料水冷盘和原料承载注入系统。
原料承载注入系统插入原料槽中，原料注入管从注入管槽中探出。
本发明设计了一种大尺寸单晶制备方法，首先是一种适合大尺寸晶体生长的可伸缩单晶生长系统，设置多级炉体结构，且在单晶炉内设置原料水冷盘，对高纯原料(如磷、铟)进行降温，原料水冷盘内设置多个独立的原料承载注入系统。
在晶体生长过程中，控制原料承载注入系统依次启动，直至达到所需的熔体量后停止注入；当熔体接近用尽时，开始将晶体缩颈至接近籽晶尺寸，然后启动下一组注入系统进行合成，直至达到所需的熔体量，此后晶体继续长大，如此循环进行合成、单晶生长、单晶缩颈、再合成、再单晶生长的多轮次合成与单晶生长的交替连续制备，同时在单晶生长过程中，炉体不断伸长，以保证晶体生长到足够的长度。
有益效果：在晶体生长的初期，生长空间小，热场对流小，容易进行晶体生长的引晶和放肩过程；待晶体长大后，炉体开始随着晶体的长大而伸长，晶体本身的降温会提高晶体生长的稳定性，同时由于存在多次缩颈处理，可以降低晶体本身的热应力，防止长得太长而断裂，同时大幅降低多次生长过程中缺陷的产生及原有缺陷的延伸；这种结构可以不受高压制备设备尺寸的限制。
原料承载注入系统可以实现对承载注入系统的冷却，防止原料的熔化流出或者受热升华；装置内可以放置多个承载注入系统，实现连续合成，或者间歇合成。可以在较小的坩埚内通过连续合成进行晶体生长，然后合成至所需的熔体量后停止合成，然后再合成再晶体生长，如此交替进行实现长单晶的制备，同时节约能源和相关的耗材。
根据最优引晶位置确定一对原料承载注入系统中原料的量，保证引晶时，坩埚中的液面处在最佳引晶位置。
另外，原料承载注入系统中放置单质，可以生长单晶硅、锗等单质半导体；放置两种物质，可以生长如磷化铟(InP)和磷化镓(GaP)类的晶体；也可以放置三种原料进行磷锗锌(ZnGeP 2)等三元以上的化合物半导体晶体的生长，操作灵活，适应性强。
附图说明
图1是本发明的结构示意图，
图2-4是本发明的设备装配示意图，
图5-7是晶体生长过程示意图，
图8是图1的局部放大图，
图9是原料承载注入系统的结构示意图，
图10是原料承载器外套的结构示意图，
图11是原料水冷盘的剖面图，
图12是原料水冷盘的俯视图，
图13是原料水冷盘盖。
图中，1：主炉体；2：一级炉体；3：二级炉体；4：三级炉体；5：支撑台；6：籽晶杆；7：籽晶杆升降电机；8：籽晶杆转动电机；9：坩埚杆；10：坩埚杆升降电机；11：坩埚杆转动电机；12：真空管道；13：充放气管道；14：限压阀；15：主体立柱；16：一级驱动电机；16-1：一级驱动臂；17：二级驱动电机；17-1：二级驱动臂；18：三级驱动电机；18-1：三级驱动臂；19：主炉体驱动电机；19-1：主驱动臂；20：底盘；20-1：立柱电机；21：保温套；22：主加热器；23：辅助加热器；24：坩埚；25：坩埚支撑；30：籽晶；31：单晶锭；33：密封槽；34：密封圈；26-1：原材料；26-2：固体氧化硼；1-1：隔板；27：原料水冷盘；27-1：原料槽；27-2：注入管槽；27-3：原料水冷盘盖；28：原料承载注入系统；28-2：原料承载器；28-3：原料；28-4：电阻丝；28-5：原料注入管；28-6：原料承载器上盖；28-7：绝缘层上盖；28-8：导线孔；28-9：绝缘层外筒；28-10：注入管放置槽；28-11：绝缘层挡板；32水路连接垫。
具体实施方式
参看图1，一种大尺寸单晶生长系统，包括2个或2个以上的主体立柱15，主体立柱15通过立柱电机20-1设置在底盘20上；设置在主体立柱15之间、位于支撑台5上的主炉体1，主炉体1内部有坩埚24及坩埚加热、支撑结构，坩埚24上方有籽晶杆6及籽晶杆驱动装置；主炉体1为开放的圆筒，通过主炉体驱动电机19和主驱动臂19-1定位在主体立柱15上；主炉体1内部中间设置有隔板1-1，主炉体1通过隔板1-1分为两部分。系统还包括与主炉体1配合的晶体生长空间的控制装置以及设置在隔板1-1上的原料注入装置。
坩埚加热结构包括保温套21、主加热器22、辅助加热器23；坩埚支撑结构包括穿过支撑台5的坩埚杆9、连接坩埚杆9的坩埚杆升降电机10和坩埚杆转动电机11。
系统还包括穿过支撑台5至主炉体1的真空管道12和充放气管道13，充放气管道13连接限压阀14。
主体立柱15通过立柱电机20-1环绕底盘20运动
晶体生长空间的控制装置。
空间控制的装置有多种实现，如主炉体进行分段设计，每一段都可以伸缩。但这种 结构设备复杂，不易实现。还可以在主炉体1内设置上下可移动的密封盖，但与主炉体1内壁之间的密封不易实现。
本发明的晶体生长空间的控制装置为在主炉体1内侧或外侧设置的1-4个可移动炉体，可移动炉体通过驱动电机和驱动臂设置在主体立柱15上。
当可移动炉体设置在主炉体1外侧时，最外侧的可移动炉体顶部密封，可移动炉体的驱动臂设置在可移动炉体外侧底部；当可移动炉体设置在主炉体1内侧时，最内侧的可移动炉体顶部密封，可移动炉体的驱动臂设置在可移动炉体外侧顶部。
本实施例中，只有一个可移动炉体顶部密封，其它可移动炉体为开放的圆筒，籽晶杆6及籽晶杆驱动装置设置在顶部密封的可移动炉体上。
本实施例中，在主炉体1内侧设置3个可移动炉体：从内到外分别为,一级炉体2、二级炉体3、三级炉体4，3个可移动炉体分别通过一级驱动电机16、一级驱动臂16-1，二级驱动电机17、二级驱动臂17-1，三级驱动电机18、三级驱动臂18-1连接到主体立柱15上。
一级炉体2顶部密封，籽晶杆6及籽晶杆驱动装置设置在一级炉体2上。
主炉体驱动电机19限位在主体立柱15的竖直轨道或螺旋轨道(图中未标出)中，主驱动臂19-1一端连接主炉体驱动电机19，另一端连接主炉体1。在每个主体立柱15上都设置主炉体驱动电机19，主炉体驱动电机19和主驱动臂19-1，依主体立柱15的数量，至少设置两套。初始安装时，要保证各主炉体驱动电机19处于同一水平位置，工作时，各主炉体驱动电机19同步运行，保证主炉体1的水平位置。主炉体1和各级炉体通过配套的驱动电机和驱动臂沿主体立柱15上下运动。
3个可移动炉体的驱动电机和驱动臂的设置与上述相同。
相邻可移动炉体的内径和外径相匹配，主炉体1与三级炉体4之间、三级炉体4与二级炉体3之间、二级炉体3与一级炉体2之间的间隙为0.1-0.5mm。
为了增加实现密闭，在主炉体1和可移动炉体内部还设置了密封槽33，密封槽33里有密封圈34。
参看图8，本实施例中，密封圈34位于主炉体1内壁及各可移动炉体内壁密封槽33中，炉体间通过2条密封圈34来密封，两个密封槽33的距离为15-30mm。上面密封槽33的位置距炉体顶部15mm-30mm，可移动炉体运动的极限位置为该可移动炉体底端距离相邻炉体下面的密封槽33的竖直距离15mm-30mm。
本实施例中，主炉体1与支撑台5密切接触，必要时可以增加密封垫；最内侧的一 级炉体2顶部密封；各相邻炉体之间尺寸相配合，且有密封圈34密封，从而形成了晶体生长需要的密闭空间。
原料注入装置。
原料注入装置，设置在主炉体1内坩埚24的上方。所述装置包括环形原料水冷盘27和原料承载注入系统28，如图1所示。
主炉体1内部设置循环水路；原料水冷盘27为铜材质，内部设置循环水路，并且设置循环水的出口和进口，与主炉体1内部的循环水路连通，是普通的水冷却结构。
隔板1-1为主炉体1的一部分，因为内部有与主炉体1连接的循环水路，所以可以承受高温。隔板1-1内的循环水通过水路连接垫32送至原料水冷盘27的循环水路中，水路连接垫32中间是两个管路，连接隔板1-1和原料水冷盘27的循环水进水和出水。
上述是普通的设计结构，在图中没有标出。
参看图11-图13，原料水冷盘27为环形，其外径小于主炉体1的内径，其内径小于等于坩埚24的内径，上面均匀设置原料槽27-1，数量为6-12个；在原料水冷盘27内侧，每个原料槽27-1配套设置注入管槽27-2；原料水冷盘27还有配套的原料水冷盘盖27-3。
原料槽27-1内部为圆桶形，可以是贯穿原料水冷盘27的通孔，也可以是不贯穿原料水冷盘27的孔。为了减小下面坩埚热场的影响，本实施例中，原料槽27-1不是管穿孔。
原料水冷盘27内部水冷铜壁的厚度为10-15mm。
注入管槽27-2从原料槽27-1顶部起始，长度大于原料水冷盘27高度的4/5。
参看图1、图9，原料承载注入系统28包括原料承载器28-2、设置在原料承载器28-2周围的电阻丝28-4、连通原料承载器28-2的原料注入管28-5、原料承载器上盖28-6。
参看图10，原料承载注入系统28还包括原料承载器28-2的外套，外套的主体为绝缘层外筒28-9，绝缘层外筒28-9顶部开放，配套设置带有导线孔28-8的绝缘层上盖28-7；绝缘层外筒28-9侧面有注入管放置槽28-10，配套设置绝缘层挡板28-11；原料承载器28-2放置在绝缘层外筒28-9中，原料注入管28-5从注入管放置槽28-10探出。
原料注入管28-5设置在原料承载器28-2底部，便于液态原料注入。
原料注入管28-5设置成2种长度，分别为其出口高于和低于晶体生长过程中反应熔体的液面高度，满足液态和气态原料的注入需求。
原料注入管28-5设置成2种长度，分别为其出口高于和低于最佳引晶位置时熔体上方液封剂的上表面的液面高度。高于最佳引晶位置时熔体上方氧化硼的上表面的液面高度的承载器28-2中放置金属元素或不易升华元素，低于最佳引晶位置时熔体上方氧化硼的上表 面的液面高度的承载器28-2中放置易升华元素。
原料水冷盘27比原料承载器28-2高出40-60mm，原料槽27-1内部为圆筒，相邻原料槽27-1之间圆心间距大于D+40mm，D为原料槽27-1的直径。
原料承载注入系统28插入原料槽27-1中，原料水冷盘盖27-3覆盖在原料水冷盘27上。原料注入管28-5从注入管槽27-2中探出，对准下面的坩埚24。由于原料水冷盘27的内径小于等于坩埚24的内径，可以保证原料注入管28-5对准坩埚24，原料不外漏。
装配原料注入装置时，将晶体生长原料28-3放入原料承载器28-2，然后将原料承载器上盖28-6与原料承载器28-2焊接起来。原料承载器上盖28-6与原料承载器28-2均为石英材质。
将原料承载器28-2外侧缠绕电阻丝28-4，并将其一起放入绝缘层外筒28-9中，原料注入管28-5装配在注入管放置槽28-10中，再将绝缘层挡板28-11插入注入管放置槽28-10中并装配在一起。
将电阻丝28-4的两极导线穿过绝缘层上盖28-7上的两个导线孔28-8(图中未标出)。
装配生长系统
参看图2。
I：将一级炉体2、二级炉体3、三级炉体4降至可隔板1-1上，然后将一级炉体2、二级炉体3、三级炉体4与主炉体1一起升至主体立柱15最高位置。
II：将保温套21、主加热器22、辅助加热器23装配至支撑台5上；将坩埚支撑25与坩埚杆9相连，坩埚24置于坩埚支撑25内。在坩埚24内放置原材料26-1和固体氧化硼26-2。
将籽晶30装配至籽晶杆6上。
参看图3。
III：将主炉体1落至支撑台5上，此时一级炉体2、二级炉体3、三级炉体4与主炉体1分离，然后将原料水冷盘27通过水路连接垫32连接至隔板1-1上，然后放置原料承载注入系统28。
参看图4。
IV：将一级炉体2、二级炉体3、三级炉体4降至可隔板1-1上，封闭炉体。
通过真空管道12抽真空至10Pa-10 -5Pa。然后通过充放气管道13充入惰性气体至4.0MPa。
待单晶锭31生长完毕后，通过充放气管道13排出炉体内的气体。再次上升一级炉 体2直至其与二级炉体3分离，同时依次将二级炉体3和三级炉体4降至隔板1-1上，将单晶锭31取出。
交替连续生长与合成
为叙述方便，以下根据承载原料不同，将原料承载注入系统28分成磷注入系统和铟注入系统。参见图5-7。
实施例1，生长磷化铟(InP)。
本实施例中，原材料26-1为铟。
步骤A、坩埚24内放置金属铟，原料承载注入系统内分别放置金属铟和磷，装配大尺寸单晶生长系统。
步骤B、加热坩埚，在坩埚内形成铟熔体。
步骤C、启动放置磷的原料承载注入系统，将气态磷注入坩埚，形成磷化铟熔体。
步骤D、开始晶体生长。
步骤E、判断坩埚中的磷化铟剩余量，如果剩余量小于开始晶体生长时磷化铟总量的15-20％，开始缩颈，缩颈完成后执行步骤F，否则继续晶体的生长。
步骤F、启动两个或两个以上原料承载注入系统，将液态铟和气态磷分别注入到坩埚，形成磷化铟熔体。
具体描述如下：
将原材料26-1金属铟放置在坩埚中，注入原料为磷和铟，单独放置在原料承载器28-2中，放置两种材料的原料承载注入系统28间隔插入原料槽27-1中。
坩埚中的原材料26-1金属铟与单个铟注入系统中的铟数量相同。
原料承载器28-2中，铟和磷的比例为1：1.1-1.3。考虑到气化的磷在熔体中可能反应不充分，以气泡形式冒出熔体造成损失，为了保证化学配比，在原料配比时适当增加磷的数量。
承载磷的原料承载注入系统28的原料注入管28-5的端口位于坩埚底部1-5mm处，在晶体生长过程中，要浸入熔体。
承载铟的原料承载注入系统28的原料注入管28-5的端口高于氧化硼26-2熔化后的液面10cm以上。
I：通过主加热器22和辅助加热器23给坩埚24中的原材料26-1金属铟和固体氧化硼26-2加热至磷化铟熔点以上形成铟熔体。
启动坩埚杆9旋转坩埚24。
加热其中一个磷注入系统，将气化的磷注入到铟熔体中，形成近配比的磷化铟熔体。以上过程称为一次合成周期。
II：下降籽晶杆6，使籽晶30接触磷化铟熔体，开始晶体生长。通过籽晶杆6提拉籽晶30，生长出单晶锭31。
当坩埚内熔体剩余15-20％时，单晶锭31开始缩颈；当坩埚内熔体剩余0.5-3％时，通过籽晶杆6提起单晶锭31，使得缩颈界面升至最佳引晶位置范围附近。以上过程称为一次生长周期。
III：加热其中一个铟注入系统，将铟以熔体形式注入坩埚，直至全部注入，停止加热。
加热另外一个磷注入系统，将磷以气体形式注入坩埚，直至不再冒出气泡，停止加热。
由于按比例放置和注入原料，此时合成了近化学配比的熔体。以上过程称为二次合成周期。
IV：调整籽晶杆6，使得单晶锭31的缩颈处与熔体接触良好后，通过主加热器22和辅助加热器23控制坩埚24内的温度，开始通过上一次的缩颈开始引晶、放肩、等径，继续生长单晶锭31，参见图6。
当坩埚内熔体剩余15-20％时，单晶锭31开始缩颈；当坩埚内熔体剩余0.5-3％时，通过籽晶杆6提起单晶锭31，使得缩颈界面升至最佳引晶位置范围附近。
重复上面的工作，来进行合成和单晶锭31的生长。以上过程称为二次生长周期。
V：上述生长过程中，当晶体的长度接近一级炉体2顶部且籽晶杆6的长度升至极限后，通过一级驱动电机16和一级驱动臂16-1驱动一级炉体2向上运动，在一级炉体2不断的上升过程中，通过充放气管道13持续向炉体冲入惰性气体，保持压力恒定。
一级炉体2的上升运动直至其极限位置，即一级炉体2底端距离二级炉体3下面的密封槽33的竖直距离15mm-30mm。
晶体生长过程中，同理依次启动二级炉体3和三级炉体4，至单晶锭31生长完成。
一级炉体2升到极限位置后，与二级炉体3同步上升，二级炉体3升到极限位置后，3个炉体同步上升。
实施例2，生长磷化铟(InP)。
本实施例中，原材料26-1为磷化铟多晶。
步骤A、坩埚4内放置磷化铟多晶，原料承载注入系统内分别放置金属铟和磷，装配大尺寸单晶生长系统。
步骤B、加热坩埚，在坩埚内形成磷化铟熔体。
步骤D、开始晶体生长。
步骤E、判断坩埚中的磷化铟剩余量，如果剩余量小于开始晶体生长时磷化铟总量的15-20％，开始缩颈，缩颈完成后执行步骤F，否则继续晶体的生长。
步骤F、启动两个或两个以上原料承载注入系统，将液态铟和气态磷分别注入到坩埚，形成磷化铟熔体。
步骤G、开始晶体生长，同时根据晶体长度调整晶体生长空间。
重复步骤E-G，直至所有原料注入完成。
具体描述如下：
将原材料26-1磷化铟多晶放置在坩埚中，注入原料为磷和铟，单独放置在原料承载器28-2中，放置两种材料的原料承载注入系统28间隔插入原料槽27-1中。
原料承载器28-2中，铟和磷的比例为1:1.1-1.3。
坩埚24中的原材料26-1磷化铟多晶的量确定如下：磷化铟形成熔体后，坩埚中的液面处在最佳引晶位置范围内。
坩埚24中的原材料26-1磷化铟多晶与一个磷注入系统和一个铟注入系统中放置的铟和磷的总质量相等，或者前述总质量为坩埚24中的原材料26-1磷化铟多晶1/n,n<5。
原料承载注入系统28的原料注入管28-5的位置设置同上。
I：通过主加热器22和辅助加热器23给坩埚24中的原材料26-1磷化铟和固体氧化硼26-2加热至磷化铟熔点以上形成磷化铟熔体。
下降籽晶杆6，籽晶30接触磷化铟熔体开始晶体生长，通过籽晶杆6提拉籽晶30，生长出单晶锭31。
当坩埚内熔体剩余15-20％时，单晶锭31开始缩颈；当坩埚内熔体剩余0.5-3％时，通过籽晶杆6提起单晶锭31，使得缩颈界面升至最佳引晶位置范围附近。。
以上过程称为0次生长周期。
II：加热其中一个铟注入系统，将铟以熔体形式注入坩埚，直至全部注入，停止加热。
加热一个磷注入系统，将磷以气体形式注入坩埚，直至不在冒出气泡，停止加热。
两个加热的铟注入系统和磷注入系统注入的铟和磷放置是按化学计量比进行的，此时合成了近化学配比的熔体。以上过程称为一次合成周期。
III：下降籽晶杆6，使得单晶锭31的缩颈处与熔体接触良好后，通过主加热器22和辅助加热器23控制坩埚24内的温度，开始通过上一次的缩颈开始引晶、放肩、等径，继续 生长单晶锭31。
当坩埚内熔体剩余15-20％时，单晶锭31开始缩颈；当坩埚内熔体剩余0.5-3％时，通过籽晶杆6提起单晶锭31，使得缩颈界面升至最佳引晶位置范围附近。
以上过程称为一次生长周期。
IV：加热另外一个铟注入系统，将铟以熔体形式注入坩埚，直至全部注入，停止加热。加热另外一个磷注入系统，将磷以气体形式注入坩埚，直至不在冒出气泡，停止加热。
上述两个加热的铟注入系统和磷注入系统注入的铟和磷放置是按化学计量比进行的，此时合成了近化学配比的熔体。以上过程称为二次合成周期。
IV：调整籽晶杆6，单晶锭31的的缩颈处与熔体接触良好；通过主加热器22和辅助加热器23控制坩埚24内的温度，开始通过上一次的缩颈开始引晶、放肩、等径，继续生长单晶锭31。
当坩埚内熔体剩余15-20％时，单晶锭31开始缩颈；当坩埚内熔体剩余0.5-3％时，通过籽晶杆6提起单晶锭31，使得缩颈界面升至最佳引晶位置范围附近。
重复上面的工作，来进行合成和单晶锭31的生长。以上过程称为二次生长周期。
V：上述生长过程中，炉体的升降控制与实施例1一致。
晶体生长完毕后，放气，上升一级炉体2直至与二级炉体3分离，取出单晶锭31，然后向坩埚24注入水，使得氧化硼溶解，解除注入管与氧化硼的粘接。拆除合成系统和单晶生长热场，清洁炉体。
可以通过在籽晶杆6上加装称重机构，对长成的晶体称重来判断原料的使用情况。
上述两个实施例中，步骤E中的缩颈在每次原料注入前实施，即在以下情况下完成：1、坩埚内预置的原料即将用尽(剩余15-20％)。
2、每注入后，坩埚内原料即将用尽(剩余15-20％)。
在实际应用中，进行合成和生长前，实验测定最优成品率和最低缺陷的最优引晶位置范围，根据最优引晶位置确定坩埚24内熔体液面的位置范围，根据熔体液面的位置范围的中间值和坩埚24的形状确定该位置以下坩埚内的熔体总量即该位置范围以下坩埚的容积。
最优引晶位置范围为坩埚中溶体表面附近的纵向温度梯度最高且横向温度梯度对称的坩埚位置范围。这里是指坩埚内高度位置的一个范围。
一对原料承载注入系统中原料的量为所述熔体总量的1/n，n为正整数且n<5。磷和铟的量，按照合成磷化铟后的量推算获得。
上述实施例中，一对原料承载注入系统中铟和磷的量为所述熔体总量的1/n。
根据以上设置，当n＝1时，每次原料注入都配合缩颈；当n>1时，连续启动n对原料承载注入系统进行注入，即步骤F：启动两个或两个以上原料承载注入系统，将原料注入到坩埚。
注入完成后进行合成和晶体生长，然后再缩颈。
连续启动n对原料承载注入系统进行注入时，可以铟、磷交替注入，也可以先注入所有铟，再注入磷。
根据熔体液面的位置范围的中间值确定原料承载注入系统中中原料的量，加上晶体生长过程坩埚内不可避免的磷化铟的剩余量(0.5-3％)，可以保证坩埚内原料合成完毕后，引晶都处于最优位置。且一对原料承载注入系统中铟和磷的量为所述熔体总量的1/n，可以减小原料承载注入系统容量的要求，更易于实现。
根据以上设置，成品单晶中，相邻缩颈之间的晶体重量为一对原料承载注入系统中磷和铟总量的m倍，m为正整数且m<5。
一般情况下，如果每次都在最优位置引晶，则m＝n。
对于AxBy半导体，A与B的物质的量比例为x：1.1-1.3y，其中B为挥发性元素。
采用本发明提供的装置，将原料注入系统改为单质，可以生长单晶硅、锗等单质半导体。将其改为三种原料的原料注入系统，也可以进行磷锗锌(ZnGeP2)等三元以上的化合物半导体晶体的生长。
生长单质晶体时，一个原料承载注入系统中原料的量为所述熔体总量的1/n；生长三元化合物半导体晶体时，三个原料承载注入系统中原料的量为所述熔体总量的1/n。每次注入原料时，根据需要启动一个或三个一组的原料承载注入系统。

Claims (10)

  1. 一种大尺寸单晶生长系统，包括坩埚(24)、2个或2个以上的主体立柱(15)，设置在主体立柱(15)之间、位于支撑台(5)上的主炉体(1)；
    其特征在于：系统还包括晶体生长空间的控制装置和炉体内的原料注入装置，所述原料注入装置包括多个相互独立的原料承载注入系统。
  2. 根据权利要求1所述的大尺寸单晶生长系统，其特征在于：
    所述晶体生长空间的控制装置包括设置在主炉体(1)内侧或外侧的1-4个可移动炉体，可移动炉体通过驱动电机和驱动臂设置在主体立柱(15)上；最内侧或最外侧的可移动炉体顶部密封，其它可移动炉体为开放的圆筒，籽晶杆(6)及籽晶杆驱动装置设置在顶部密封的可移动炉体上；
    所述原料注入装置设置在隔板(1-1)上，包括环形原料水冷盘(27)和原料承载注入系统(28)；
    原料水冷盘(27)上均匀设置原料槽(27-1)；原料承载注入系统(28)包括原料承载器(28-2)、设置在原料承载器(28-2)周围的电阻丝(28-4)、连通原料承载器(28-2)的原料注入管(28-5)、原料承载器上盖(28-6)；
    原料承载注入系统(28)插入原料槽(27-1)中，原料注入管(28-5)从注入管槽(27-2)中探出；
    所述原料槽(27-1)设置6-12个；
    原料注入管(28-5)设置成2种长度，分别为其出口高于和低于晶体生长过程中熔体的液面高度。
  3. 一种大尺寸化合物半导体单晶制备方法，使用权利要求1或2所述的大尺寸单晶生长系统实现，其特征在于：所述制备方法包括以下步骤：
    步骤A、坩埚和原料承载注入系统内放置晶体生长所需原料，装配大尺寸单晶生长系统，
    步骤B、加热坩埚，在坩埚内形成熔体，
    步骤D、开始晶体生长，
    步骤E、判断坩埚中的原料剩余量，如果剩余量小于开始晶体生长时的原料总量的15-20％，开始缩颈，缩颈完成后执行步骤F，否则继续晶体的生长，
    步骤F、启动两个或两个以上原料承载注入系统，将原料注入到坩埚，
    步骤G、开始晶体生长，同时根据晶体长度，使用晶体生长空间的控制装置调整晶体生长空间，
    重复步骤E-G，直至所有原料注入完成。
  4. 根据权利要求3所述的大尺寸化合物半导体单晶制备方法，其特征在于：根据最优引晶位置范围确定坩埚(24)内熔体液面的位置范围，根据熔体液面的位置范围的中间值和坩埚(24)的形状确定该位置以下的熔体总量，一对原料承载注入系统中原料的量为所述熔体总量的1/n，n为正整数且n<5。
  5. 根据权利要求3所述的大尺寸化合物半导体单晶制备方法，其特征在于：
    步骤A中，坩埚(24)中放置金属铟，原料承载注入系统(28)的原料承载器(28-2)中分别放置磷和金属铟，
    在步骤B和步骤D之间，增加步骤C：
    步骤C、启动放置磷的原料承载注入系统(28)，将气态磷注入坩埚。
  6. 根据权利要求5所述的大尺寸化合物半导体单晶制备方法，其特征在于：
    放置在坩埚(24)中铟的数量和放置在一个原料承载注入系统(28)中铟的数量相同。
  7. 根据权利要求6所述的大尺寸化合物半导体单晶制备方法，其特征在于：
    步骤A中，坩埚(24)中放置磷化铟，原料承载注入系统(28)的原料承载器(28-2)中分别放置磷和金属铟。
  8. 根据权利要求6或7所述的大尺寸化合物半导体单晶制备方法，其特征在于：
    原料承载注入系统(28)中，铟和磷的比例为1:1.1-1.3。
  9. 根据权利要求8所述的大尺寸化合物半导体单晶制备方法，其特征在于：相邻缩颈之间的晶体重量为一对原料承载注入系统(28)中磷和铟总量的m倍，m为正整数且m<5。
  10. 根据权利要求4所述的大尺寸化合物半导体单晶制备方法，其特征在于：所述最优引晶位置范围为坩埚中溶体表面附近的纵向温度梯度最高且横向温度梯度对称的坩埚位置范围。
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Publication number Priority date Publication date Assignee Title
CN113249778B (zh) * 2021-04-08 2022-05-17 中国电子科技集团公司第十三研究所 一种大尺寸化合物半导体单晶制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110923806A (zh) * 2019-12-24 2020-03-27 西安奕斯伟硅片技术有限公司 一种单晶炉及单晶硅棒的制备方法
CN112410883A (zh) * 2020-11-16 2021-02-26 宇泽半导体(云南)有限公司 一种改进的磷化铟晶体合成和生长工艺及装置
CN113174630A (zh) * 2021-04-08 2021-07-27 中国电子科技集团公司第十三研究所 一种大尺寸半导体单晶生长系统
CN113249778A (zh) * 2021-04-08 2021-08-13 中国电子科技集团公司第十三研究所 一种大尺寸化合物半导体单晶制备方法
CN215050847U (zh) * 2021-04-08 2021-12-07 中国电子科技集团公司第十三研究所 一种晶体生长过程中炉内原料注入装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0494312B1 (en) * 1990-07-26 1996-10-09 Sumitomo Electric Industries, Ltd. Method and apparatus for making single crystal
CN1289721C (zh) * 2003-11-14 2006-12-13 中国科学院上海硅酸盐研究所 一种熔料补充生长晶体的装置和方法
CN102418140A (zh) * 2011-12-09 2012-04-18 曾泽斌 硅熔体连续加注的直拉硅单晶生长炉及其方法
CN206635452U (zh) * 2017-03-29 2017-11-14 天通吉成机器技术有限公司 单晶炉及其副室
CN110257901B (zh) * 2019-07-15 2021-05-28 乐山新天源太阳能科技有限公司 大直径高效n型单晶硅的制备工艺
CN110760931B (zh) * 2019-11-22 2024-03-19 中国电子科技集团公司第十三研究所 一种利用铟磷混合物制备磷化铟晶体的系统

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110923806A (zh) * 2019-12-24 2020-03-27 西安奕斯伟硅片技术有限公司 一种单晶炉及单晶硅棒的制备方法
CN112410883A (zh) * 2020-11-16 2021-02-26 宇泽半导体(云南)有限公司 一种改进的磷化铟晶体合成和生长工艺及装置
CN113174630A (zh) * 2021-04-08 2021-07-27 中国电子科技集团公司第十三研究所 一种大尺寸半导体单晶生长系统
CN113249778A (zh) * 2021-04-08 2021-08-13 中国电子科技集团公司第十三研究所 一种大尺寸化合物半导体单晶制备方法
CN215050847U (zh) * 2021-04-08 2021-12-07 中国电子科技集团公司第十三研究所 一种晶体生长过程中炉内原料注入装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHOU XIAOLONG, YANG KEWU, YANG RUIXIA, SUN TONGNIAN, SUN NIEFENG: "Growth of Large Diameter InP Single Crystal", SEMICONDUCTOR TECHNOLOGY, GAI-KAN BIANJIBU, SHIJIAZHUANG, CN, vol. 34, no. 4, 3 April 2009 (2009-04-03), CN , pages 311 - 314, XP055974902, ISSN: 1003-353X, DOI: 10.13290/j.cnki.bdtjs.2009.04.010 *

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