CN117071068A - Low dislocation growth method for compound semiconductor single crystal - Google Patents

Low dislocation growth method for compound semiconductor single crystal Download PDF

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Publication number
CN117071068A
CN117071068A CN202311080535.XA CN202311080535A CN117071068A CN 117071068 A CN117071068 A CN 117071068A CN 202311080535 A CN202311080535 A CN 202311080535A CN 117071068 A CN117071068 A CN 117071068A
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recoverer
crystal
covering agent
seed
wafer
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Inventor
史艳磊
孙聂枫
徐成彦
秦敬凯
王书杰
岳琳清
邵会民
王阳
李晓岚
付莉杰
张鑫
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CETC 13 Research Institute
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CETC 13 Research Institute
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Priority to CN202311080535.XA priority Critical patent/CN117071068A/en
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method

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

Abstract

The application provides a low dislocation growth method for compound semiconductor single crystals, which belongs to the technical field of crystal preparation and is realized based on a crystal growth device, wherein the crystal growth device comprises a closed furnace body, a crucible of the furnace body, a seed rod, an observation window, a multi-section heater and a covering agent recovery device, and the covering agent recovery device comprises a recoverer and a recoverer pin; according to the application, after crystal growth and before annealing, the liquid covering agent is removed by the covering agent recovery device, and crystal defects caused by solidification of the covering agent can be avoided in the subsequent process. The method provided by the application has the advantages of large diameter and low cost of growth by the Czochralski method, and has the advantage of low dislocation defect of the crystal by the vertical gradient solidification method, thereby having strong practicability.

Description

Low dislocation growth method for compound semiconductor single crystal
Technical Field
The application belongs to the technical field of crystal preparation, and particularly relates to a low dislocation growth method for a compound semiconductor single crystal.
Background
Compound semiconductor materials, such as indium phosphide, gallium arsenide, and the like, have a certain dissociation pressure.
When preparing single crystals by the melt method, it is necessary to cover the melt with a covering agent.
In the process of pulling a single crystal by using the Czochralski method, boron oxide is pulled out of the crystal, and a low-temperature region is formed above the boron oxide, so that the temperature of the crystal is rapidly dissipated, and the temperature gradient in the crystal is greatly increased, thereby generating dislocation defects. In addition, in the case of the pulling method, the seed crystal is connected to the seed rod, and the seed rod plays a continuous role in heat conduction, so that a square dislocation region is formed around the seed crystal and extends into a certain depth of the crystal head, and the crystal quality is affected.
For the vertical gradient solidification method VGF and the vertical Bridgman method VB, the seed crystal is positioned below the melt, and the growth condition of the crystal growth cannot be judged through observation during growth, so that the yield of the crystal is affected; during the crystal growth process, covering the raw material melt with the covering agent can prevent impurities from entering, and at the same time, the temperature fluctuation of the melt can be slightly controlled, but when the covering agent is solidified, great stress is generated in the contacted crystal, and even the crystal is directly broken.
Disclosure of Invention
The present application has been made to overcome the drawbacks of the prior art.
The application adopts the following technical scheme to realize the aim of the application: the low dislocation growth method for compound semiconductor monocrystal is realized based on crystal growth apparatus comprising sealed furnace, crucible inside the furnace, seed rod capable of moving vertically and rotating horizontally while passing through the furnace, observation window in the top of the furnace, multistage heater around the crucible and heat insulating layer. The growth device further comprises a covering agent recovery device, the covering agent recovery device comprises a recoverer connected with a driving device penetrating through the top of the furnace body and a recoverer pin penetrating through the bottom of the recoverer, and the upper end of the recoverer pin is arranged at the top of the inner space of the recoverer.
The method comprises the following steps:
step 1: placing the compound semiconductor polycrystal material and the solid covering agent in a crucible, mounting seed crystals on seed rods, and mounting a furnace body.
Step 2: setting the internal environment of the furnace body.
Step 3: the compound semiconductor polycrystal material and the solid covering agent are heated by a multi-stage heater until a melt and a liquid covering agent are formed, and the temperature of the melt is regulated to a crystallization point of + -3 ℃.
Step 4: lowering a seed rod, immersing seed crystals into the liquid covering agent, and preheating at a position 1-3 mm away from the surface of the melt for 20-30 min; the seed crystal is contacted with the melt.
Step 5: gradually reducing the power of the multi-section heater, and cooling at a speed of 3-5 ℃/H to enable the crystal to grow gradually until the melt in the whole crucible is completely solidified.
Step 6: gradually reducing the power of the multi-section heater, setting the cooling speed of 5-10 ℃/H, and cooling to 600 ℃.
Step 7: the pins of the recoverer are inserted into the liquid covering agent and contacted with the surface of the crystal.
Step 8: the liquid covering agent is recovered into the recoverer through the pins of the recoverer.
Step 9: annealing; cooling the inside of the furnace body to room temperature, deflating and disassembling the furnace.
The volume of the recoverer is larger than 1.3 times of the dosage volume of the solid covering agent.
One possible implementation: the recoverer is provided with a recoverer inflation and deflation pipeline.
The step 8 is specifically as follows: the pressure of the recoverer is relieved through a charging and discharging pipeline of the recoverer, and the liquid covering agent is sucked into the recoverer through a pin of the recoverer.
Another possible implementation: an air source furnace is arranged at the periphery of the recoverer.
In the step 1, the air source material is placed in the recoverer.
The step 8 specifically includes:
step 8-1: and opening the gas source furnace to gasify the gas source material, and allowing the gas to emerge from the pins of the recoverer to enter the furnace body.
Step 8-2: when the gas source material is completely gasified, the gas source furnace is stopped to heat, the gas in the recoverer is condensed, the pressure of the recoverer is reduced, and the liquid covering agent is sucked into the recoverer through the pins of the recoverer.
Further, a lock tongue is arranged at the end part of the seed rod; the seed crystal is a wafer-shaped seed crystal, and a strip hole matched with the lock tongue is formed in the center of the seed crystal.
In the step 1, the strip holes of the wafer-shaped seed crystal are aligned with the lock bolts of the seed crystal rod to be inserted, the wafer-shaped seed crystal is rotated by 90 degrees, and the wafer-shaped seed crystal is mounted on the seed crystal rod.
In the step 4, after preheating for 20-30 min, the seed rod rotates at the rotating speed of 3-10 RPM, the wafer-shaped seed crystal rotates in the liquid covering agent, the wafer-shaped seed crystal and the seed rod are subjected to resistance opposite to the rotating direction, when the relative position rotates for 90 degrees, the wafer-shaped seed crystal falls off from the seed rod, and the wafer-shaped seed crystal falls to the surface of a melt; lifting the seed rod.
After the crystal growth is finished, the covering agent is separated from the crystal when the covering agent is in a liquid state, and crystal defects caused by solidification of the covering agent are avoided in the subsequent process; in addition, by adopting a further technical scheme, the seed rod is separated from the seed crystal in the crystal growth process, so that the heat conduction effect of the seed rod is eliminated, dislocation areas formed on the periphery of the seed crystal and the head of the crystal are avoided, and the crystal quality is improved. The method provided by the application has the advantages of large diameter and low cost of growth by the Czochralski method, and has the advantage of low dislocation defect of the crystal by the vertical gradient solidification method, thereby having strong practicability.
Drawings
Figure 1 is a schematic view of the state of the device prior to crystal growth,
figure 2 is a schematic view showing the state of the apparatus of another embodiment prior to crystal growth,
FIG. 3 is a schematic diagram of the end structure of a seed rod,
figure 4 is a schematic view of a wafer-like seed crystal structure,
FIG. 5 is a schematic view showing the state of the apparatus at the time of preheating a wafer-shaped seed crystal,
FIG. 6 is a schematic view showing the state of the apparatus when a wafer-shaped seed crystal is brought into contact with a melt,
figure 7 is a schematic view of the state of the device during crystal growth,
figure 8 is a schematic view of the device after removal of the liquid covering agent,
fig. 9 and 10 are schematic views showing the state of another embodiment device.
Wherein, 1: wafer-shaped seed crystal, 1-1: elongated hole, 2: seed rod, 2-1: bolt, 2-1-1: narrow edge, 2-1-2: long side, 3: recycler, 3-1: regenerator pins, 4: air source furnace, 5: air source material, 6: covering agent, 7: crucible, 8: heater, 9: viewing window, 10: furnace body, 11: inflation and deflation pipelines, 12: the recoverer fills gassing pipeline, 13: and (5) a crystal.
Detailed Description
The present application proposes a low dislocation growth method for a compound semiconductor single crystal, and in order to achieve the above method, the present application proposes a preferred embodiment of a crystal growth apparatus.
Referring to fig. 1 and 2, the crystal growing apparatus includes a closed furnace body 10, a crucible 7 provided in the furnace body 10, a seed rod 2 movable in a vertical direction and rotatable in a horizontal direction through the furnace body 10, an observation window 9 provided at the top of the furnace body 10, a plurality of heaters 8 provided around the crucible 7, and a heat insulating layer, the seed rod 2 being aligned with the center of the crucible 7.
The growth device also comprises a covering agent recovery device, comprising a recoverer 3 connected with a driving device penetrating through the top of the furnace body 10 and a recoverer pin 3-1 penetrating through the bottom of the recoverer 3, wherein the upper end of the recoverer pin 3-1 is arranged at the top of the inner space of the recoverer 3.
The volume of the recoverer 3 is 1.3 times larger than the volume of the solid covering agent in the crystal growing process, and the upper end of the recoverer pin 3-1 is arranged at the top of the inner space of the recoverer 3, so that the upper end of the recoverer pin 3-1 can be kept higher than the liquid level of the liquid covering agent entering the recoverer 3 all the time.
Based on the above crystal growth apparatus, the low dislocation growth method for a compound semiconductor single crystal includes the steps of:
step 1: the compound semiconductor polycrystal material and the solid covering agent are placed in a crucible 7, and a seed crystal is mounted on a seed rod 2, and a furnace body 10 is mounted.
In all examples, boron oxide was used as a capping agent.
Step 2: the internal environment of the furnace body 10 is set.
The environmental settings, including control of the pressure, temperature, etc. within the furnace body 10, are conventional techniques and are not of great interest to the present application, and are not described in detail in the specification and drawings of the present application, but do not affect the understanding of the present application to those skilled in the art.
Step 3: the compound semiconductor polycrystal material and the solid covering agent are heated by the multistage heater 8 until a melt and a liquid covering agent 6 are formed, the liquid covering agent 6 is above the melt to form a covering for the melt, and the temperature of the melt is adjusted to a crystallization point + -3 ℃, see fig. 1. In FIG. 1, the end of a seed rod 2 is attached to a seed.
Step 4: lowering a seed rod 2, immersing seed crystals into a liquid covering agent 6, and preheating at a position 1-3 mm away from the surface of a melt for 20-30 min; the seed crystal is contacted with the melt.
With the seed crystal shown in fig. 1, although the crystal growth step can be achieved, during the crystal growth process, the seed rod 2 is always in contact with the seed crystal, the seed rod 2 continuously conducts heat, and a square dislocation region is formed around the seed crystal.
For this reason, in this embodiment, the end of the seed rod 2 is provided with the lock tongue 2-1, and fig. 3 shows a schematic view of two directions of the lock tongue 2-1 provided at the end of the seed rod 2; the seed crystal is designed into a circular sheet seed crystal 1, and a strip hole 1-1 matched with a lock tongue 2-1 is formed in the center of the seed crystal, as shown in fig. 4.
In the step 1, the strip hole 1-1 of the wafer-shaped seed crystal 1 is aligned with the lock tongue 2-1 of the seed rod 2, and is inserted, rotated by 90 degrees, and the two sides of the narrow side of the strip hole 1-1 fall on the long side of the lock tongue 2-1, so that the wafer-shaped seed crystal 1 is mounted on the seed rod 2, as shown in fig. 2.
The wafer-shaped seed crystal 1 is preheated as shown in fig. 5.
In the step 4, after preheating for 20-30 min, the seed rod 2 rotates at a rotating speed of 3-10 RPM to drive the wafer-shaped seed crystal 1 to rotate in the liquid covering agent 6, the wafer-shaped seed crystal 1 receives resistance opposite to the rotating direction, the wafer-shaped seed crystal 1 and the seed rod 2 relatively rotate, when the relative position rotates for 90 degrees, the wafer-shaped seed crystal 1 falls off from the seed rod 2, and as the density of the wafer-shaped seed crystal 1 is greater than that of the liquefied covering agent 6, the wafer-shaped seed crystal 1 falls onto the surface of a melt.
Lifting the seed rod 2.
Indium phosphide crystalline density is slightly lower than melt density, and a small portion of the wafer-like seed crystal 1 can float above the melt and be immersed in the covering agent, and the lower surface of the wafer-like seed crystal 1 is brought into contact with the melt, as shown in fig. 6.
If the strip hole 1-1 is completely matched with the lock tongue 2-1, when the relative position is rotated by 90 degrees, the relative position is continuously changed due to friction force and rotation, and the wafer-shaped seed crystal 1 is not easy to fall off from the seed rod 2. For this reason, in this embodiment, the length of the narrow side of the elongated hole 1-1 is greater than the length of the narrow side 2-1-1 of the locking bolt 2-1 and less than the length of the long side 2-1-2 of the locking bolt 2-1, as shown in fig. 3 and 4. By the design, the wafer-shaped seed crystal 1 can be lapped on the long edge 2-1-2 of the lock tongue 2-1, and when the wafer-shaped seed crystal 1 rotates, the wafer-shaped seed crystal 1 starts to fall off from the seed rod 2 when the relative position rotation of the wafer-shaped seed crystal 1 and the seed rod 2 is smaller than 90 degrees.
If the wafer-shaped seed crystal 1 starts to fall off from the crystal rod 2 and then immediately lifts the crystal rod 2, the wafer-shaped seed crystal 1 is still in a rotating state, the liquid covering agent 6 is disturbed, and the wafer-shaped seed crystal 1 easily deviates from the original position.
In order to prevent the situation, in the embodiment, on the premise that the condition that seed crystals are immersed into the liquid covering agent 6 and are 1-3 mm away from the surface of the melt, the tail ends of seed crystal rods 2 are immersed into the melt; after the wafer-shaped seed crystal 1 is separated from the seed rod 2, the rotation of the seed rod 2 is stopped, and after 2-5min, the seed rod 2 is lifted.
After stopping rotating, the tail end of the seed rod 2 is still remained in the strip hole 1-1 of the wafer-shaped seed crystal 1, so that the wafer-shaped seed crystal 1 is limited to drift in the melt; after 2-5min, the disturbed liquid covering agent 6 is in a static state, the wafer-shaped seed crystal 1 is static, the seed rod 2 is lifted at the moment, and the position of the wafer-shaped seed crystal 1 is basically in the center of the crucible 7 because the aligned position of the seed rod 2 is the center of the crucible 7.
The above states, including the following crystal growth states, can be observed through the observation window 9.
The state after lifting the seed rod 2 is shown in fig. 6.
It should be noted that, when growing the indium phosphide crystal, the above-mentioned manner of placing the seed crystal is adopted; when gallium arsenide and other crystals are grown, the conventional method that seed crystals are fixed on seed rods all the time is adopted.
Step 5: gradually reducing the power of the multi-stage heater 8 at a cooling speed of 3-5 ℃/H, so that the crystal 13 gradually grows until the melt in the whole crucible is completely solidified, as shown in fig. 7.
The above is a conventional technique of crystal growth, and will not be described here in detail.
Step 6: gradually reducing the power of the multi-section heater 8, setting the cooling speed of 5-10 ℃/H, and cooling to 600 ℃. At this time, the liquid covering agent 6 is present on the surface of the crystal 13.
If the temperature is continuously lowered, the liquid covering agent 6 is solidified, which affects the crystal 13, affects the crystal quality, and even causes direct breakage of the crystal.
In this example, the liquid covering agent 6 is removed from the surface of the crystal 13 before continuing to cool down, eliminating the effect:
step 7: the retriever pin 3-1 is inserted into the liquid covering agent 6 to be in contact with the surface of the crystal 13.
Step 8: the liquid covering agent 6 is recovered into the recoverer 3 through the recoverer pin 3-1.
During the crystal growth phase, the retriever pin 3-1 is above the liquid capping agent 6.
To ensure recovery, the volume of the recoverer 3 is greater than 1.3 times the volume of the solid covering agent.
Pressurizing the inside of the furnace body 10 can be adopted to press the liquid covering agent 6 into the recoverer 3: and (3) opening a gas release valve, slowly reducing the internal pressure of the furnace body 10 from 3MPa to 0.1MPa, and then filling inert gas into the furnace body 10neural to increase the furnace body pressure to 0.6MPa. The pressure value at this time is related to the volume ratio of the recoverer 3 to the covering agent. In addition, the differential air pressure required by the capping reagent to overcome gravity is also considered.
The method is simple to realize, but the furnace body 10 needs to be vacuumized from the outside and then filled with inert gas, so that the surrounding environment of the crystal, such as temperature and pressure, can be drastically changed, and unpredictable influence is generated on the quality of the crystal.
The present application proposes the following two embodiments.
Example 1:
the recoverer 3 is provided with a recoverer charging and discharging pipeline 12, and the recoverer charging and discharging pipeline 12 moves up and down along with the recoverer 3.
The step 8 is specifically as follows: the pressure of the recoverer 3 is relieved through the charge and discharge pipeline 12 of the recoverer, and the liquid covering agent 6 is sucked into the recoverer 3 through the recoverer pin 3-1, as shown in fig. 8.
After the recoverer pin 3-1 is inserted into the liquid covering agent 6, the internal space of the recoverer 3 is isolated from the internal space of the furnace body 10 by the liquid covering agent 6, after the recoverer 3 is depressurized, the internal pressure of the furnace body 10 is larger than the internal pressure of the recoverer 3, and the liquid covering agent 6 is sucked into the recoverer 3 through the recoverer pin 3-1.
If the pressure inside the recoverer 3 is consistent with the ambient pressure, the liquid covering agent 6 is also arranged in the furnace body 10, and the recoverer 3 can be vacuumized through the charge and discharge pipeline 12 of the recoverer, so that the residual liquid covering agent 6 is extracted.
The above process can be observed through the observation window 9.
This embodiment removes the liquid covering agent 6 covering the crystal 13 without changing the internal environment of the furnace body 10.
Example 2:
an air source furnace 4 is arranged around the recoverer 3.
In step 1, a gas source material 5 is placed in a recoverer 3; the gas source material 5 is a nonmetallic element material in the compound semiconductor; in this embodiment, the compound semiconductor polycrystalline material is indium phosphide polycrystalline material, and the gas source material 5 is red phosphorus.
The dosage of red phosphorus: the volume of red phosphorus is greater than 1/200 of the volume of the recycler 3.
The state after step 7 is shown in fig. 9.
The step 8 specifically includes:
step 8-1: starting an air source furnace 4 to gasify the red phosphorus in the air source material 5, and enabling the air to emerge from the pins 3-1 of the recoverer to enter the furnace body 10;
step 8-2: when the red phosphorus in the gas source material 5 is completely gasified, the heating of the gas source furnace 4 is stopped, the gas in the recoverer 3 is condensed, the pressure of the recoverer 3 is reduced, and the liquid covering agent 6 is sucked into the recoverer 3 through the recoverer pin 3-1, as shown in figure 10. The volume of red phosphorus is greater than 1/200 of the volume of the recycler 3, and theoretically all of the covering agent 6 can be sucked into the recycler 3.
In the process of crystal growth, the annealing of the crystal needs to be completed under a certain atmosphere, for example, the indium phosphide crystal needs a phosphorus atmosphere.
In this embodiment, the liquid covering agent 6 is removed, and at the same time, phosphorus gas is injected into the furnace body 10, so as to conform to the following annealing process steps.
The two embodiments described above enable the removal of the liquid covering agent 6. The amount theoretically removed is related to the flatness of the crystal surface and the degree to which the pins 3-1 of the recycler are attached, and in the experiment, there is a thin layer of residue, but the small amount of covering agent has a low strength and has little effect on the crystal spalling.
After removal, step 9 is performed: annealing; the interior of the furnace body (10) is cooled to room temperature, the air is discharged, the furnace is disassembled, and the crystal 13 is taken out.
Comparison of crystal quality grown by various methods: taking a 4 inch InP crystal as an example:
the average dislocation density of the crystal grown by the traditional LEC method is 50000-100000 cm, and the average dislocation density of the 4-inch doped Fe InP crystal -2 4 inch S-doped InP crystals having an average dislocation density of 5000-50000 cm -2 。
The average dislocation density of the crystal grown by adopting the traditional VGF method is 3000-10000 cm, and the average dislocation density of the 4-inch Fe-doped InP crystal -2 The average dislocation density of the 4-inch doped InP crystal is 100-1000 cm -2 ；
The average dislocation density of the crystal grown by the method is 3000-10000 cm, and the average dislocation density of 4-inch Fe-doped InP crystal -2 4 inch S-doped InP crystal with dislocation density of 100-1000 cm -2 。
By using the method provided by the application, the advantage of low dislocation defect of the VGF method can be realized by using the LEC method with low cost.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same; while the application has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that: modifications and equivalents of some of the technical features of the specific embodiments of the present application may be made without departing from the spirit of the technical solutions of the present application, and they are all included in the scope of the technical solutions claimed in the present application.

Claims (10)

1. A low dislocation growth method for a compound semiconductor single crystal, based on a crystal growth apparatus comprising a closed furnace body (10), a crucible (7) provided in the furnace body (10), a seed rod (2) vertically movable and horizontally rotatable through the furnace body (10) in alignment with the center of the crucible (7), an observation window (9) provided at the top of the furnace body (10), a multi-stage heater (8) provided at the periphery of the crucible (7), and an insulating layer, characterized in that the growth apparatus further comprises a covering agent recovery apparatus comprising a recoverer (3) connected to a driving apparatus passing through the top of the furnace body (10) and a recoverer pin (3-1) passing through the bottom of the recoverer (3), the upper end of the recoverer pin (3-1) being provided at the top of the inner space of the recoverer (3);
the method comprises the following steps:
step 1: placing the compound semiconductor polycrystal material and the solid covering agent in a crucible (7), mounting seed crystals on a seed rod (2), and mounting a furnace body (10);
step 2: setting the internal environment of the furnace body (10);
step 3: heating the compound semiconductor polycrystal material and the solid covering agent through a multi-stage heater (8) until a melt and a liquid covering agent (6) are formed, and adjusting the temperature of the melt to a crystallization point of +/-3 ℃;
step 4: descending a seed rod (2), immersing seed crystals into the liquid covering agent (6), and preheating at a position 1-3 mm away from the surface of the melt for 20-30 min; contacting the seed crystal with the melt;
step 5: gradually reducing the power of the multi-section heater (8) at a cooling speed of 3-5 ℃/H, so that the crystal (13) is gradually grown up until the melt in the whole crucible is completely solidified;
step 6: gradually reducing the power of the multi-section heater (8), setting the cooling speed of 5-10 ℃/H, and cooling to 600 ℃;
step 7: inserting the recoverer pins (3-1) into the liquid covering agent (6) to be contacted with the surface of the crystal (13);
step 8: the liquid covering agent (6) is recycled into the recoverer (3) through the recoverer pin (3-1);
step 9: annealing; cooling the inside of the furnace body (10) to room temperature, deflating and disassembling the furnace;
the volume of the recoverer (3) is larger than 1.3 times of the dosage volume of the solid covering agent.
2. The method according to claim 1, characterized in that the recuperator (3) is provided with a recuperator charge-air vent line (12);
the step 8 specifically comprises the following steps: the pressure of the recoverer (3) is relieved through a charging and discharging pipeline (12) of the recoverer, and the liquid covering agent (6) is sucked into the recoverer (3) through a pin (3-1) of the recoverer.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the step 8 further includes: the recoverer (3) is vacuumized through a recoverer charging and discharging pipeline (12).
4. The method according to claim 1, characterized in that the recuperator (3) is peripherally provided with a gas source furnace (4);
in the step 1, an air source material (5) is placed in a recoverer (3);
the step 8 specifically includes:
step 8-1: starting an air source furnace (4) to gasify an air source material (5), and enabling air to emerge from a pin (3-1) of the recoverer to enter a furnace body (10);
step 8-2: when the air source material (5) is completely gasified, the air source furnace (4) is stopped to heat, the air in the recoverer (3) is condensed, the pressure of the recoverer (3) is reduced, and the liquid covering agent (6) is sucked into the recoverer (3) through the recoverer pin (3-1).
5. The method according to claim 4, characterized in that the volume of the gas source material (5) is greater than 1/200 of the volume of the recycler (3).
6. The method according to claim 4, characterized in that the gas source material (5) is a non-metallic elemental material in the compound semiconductor; the compound semiconductor polycrystal material is indium phosphide polycrystal material, and the gas source material (5) is red phosphorus.
7. Method according to claim 1, characterized in that the end of the seed rod (2) is provided with a locking tongue (2-1); the seed crystal is a wafer-shaped seed crystal (1), and a strip hole (1-1) matched with the lock tongue (2-1) is formed in the center of the seed crystal;
in the step 1, a strip hole (1-1) of a wafer-shaped seed crystal (1) is aligned with a lock tongue (2-1) of a seed rod (2) to be inserted, and the wafer-shaped seed crystal (1) is mounted on the seed rod (2) by rotating by 90 degrees;
in the step 4, after preheating for 20-30 min, the seed rod (2) rotates at the rotating speed of 3-10 RPM, the wafer-shaped seed crystal (1) rotates in the liquid covering agent (6) and receives resistance opposite to the rotating direction, the wafer-shaped seed crystal (1) and the seed rod (2) relatively rotate, when the relative position rotates for 90 degrees, the wafer-shaped seed crystal (1) falls off from the seed rod (2), and the wafer-shaped seed crystal (1) falls on the surface of a melt; lifting the seed rod (2).
8. The method according to claim 7, characterized in that the narrow side of the elongated hole (1-1) has a length that is greater than the length of the narrow side (2-1-1) of the bolt (2-1) and less than the length of the long side (2-1-2) of the bolt (2-1).
9. The method according to claim 7, wherein in step 4, after the wafer-shaped seed crystal (1) is detached from the seed rod (2), the rotation of the seed rod (2) is stopped, and after 2 to 5 minutes, the seed rod (2) is lifted.
10. The method of claim 1, wherein the capping agent is boron oxide.
CN202311080535.XA 2023-08-25 2023-08-25 Low dislocation growth method for compound semiconductor single crystal Pending CN117071068A (en)

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