CN113668044B - Single crystal regeneration method - Google Patents
Single crystal regeneration method Download PDFInfo
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- CN113668044B CN113668044B CN202110793429.0A CN202110793429A CN113668044B CN 113668044 B CN113668044 B CN 113668044B CN 202110793429 A CN202110793429 A CN 202110793429A CN 113668044 B CN113668044 B CN 113668044B
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- 239000013078 crystal Substances 0.000 title claims abstract description 238
- 238000011069 regeneration method Methods 0.000 title description 2
- 239000010453 quartz Substances 0.000 claims abstract description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000002844 melting Methods 0.000 claims abstract description 29
- 230000008018 melting Effects 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000007547 defect Effects 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 238000012546 transfer Methods 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 210000001787 dendrite Anatomy 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 13
- 229910052582 BN Inorganic materials 0.000 description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- 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
- 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
- C30B29/42—Gallium arsenide
Abstract
The invention relates to a single crystal regrowth method, which comprises the following steps: s1, packaging seed crystals and materials required by single crystal growth in a quartz tube, putting the quartz tube into a single crystal furnace, and discharging the quartz tube after the single crystal growth is finished once; s2, checking whether the tightness of the quartz tube is good, if so, entering S3, otherwise, entering S9; s3, heating the top of the quartz tube to gasify and transfer materials attached to the inner wall of the quartz cap; s4, observing whether defects exist at the tail of the crystal through a quartz cap, if so, entering S5, otherwise, entering S9; s5, putting the quartz tube into the single crystal furnace again, and adjusting the temperature to melt the crystal; s6, changing growth parameters of single crystal regrowth; s7, controlling the melting depth of seed crystals during the regrowth of single crystals; and S8, discharging the single crystal from the furnace after the single crystal regrowth is completed. On the basis of finishing one single crystal growth, the invention judges that the condition of re-growth is reached, and then the furnace is charged again to carry out the process of re-growth of the single crystal. The purity of the monocrystal is improved, and the utilization rate of raw materials is also improved.
Description
Technical Field
The invention relates to the technical field of crystal production, in particular to a single crystal regrowth method.
Background
Single crystal growth is an important link in the crystal production process and is also a link directly determining the crystal production efficiency. The main current method for single crystal growth is a vertical temperature gradient solidification method, which comprises the steps of firstly loading raw materials required by single crystal growth into a boron nitride crucible, then vertically placing the whole boron nitride crucible into a quartz tube, vacuumizing and sealing, then placing the sealed quartz tube into a single crystal furnace, carrying out single crystal growth through the process steps of heating, growing, cooling and the like, taking out the quartz tube after the single crystal growth is completed, cutting the quartz tube by using a cutting machine, and finally obtaining a single crystal after ultrasonic demoulding.
However, since the stacking fault energy of single crystal growth is low, very strict growth environment conditions are required, and the crystallization rate is very low, which is only about 30%. At present, after the single crystal growth is finished, the single crystal directly enters a subsequent process for cutting and demoulding, and the subsequent process is subjected to the processes of red phosphorus combustion, quartz tube collision, stress during ultrasonic demoulding and the like, so that an expensive boron nitride crucible is easily damaged, raw materials such as a quartz tube, seed crystals, boron oxide and the like are scrapped after being used once, and the raw materials are greatly wasted; after cutting and demoulding, the single crystal which is not grown or has defects can be subjected to cutting, acid washing, ultrasonic treatment and other processes, and then the single crystal is melted and separated into raw materials for the subsequent single crystal growth, and the process can cause raw material pollution, so that the purity of the subsequent single crystal growth is reduced. Therefore, the current method has low crystallization rate and causes material waste, resulting in high production cost.
Disclosure of Invention
In order to solve the technical problem of raw material waste after single crystal growth, the invention designs a single crystal regrowth method, which mainly selects single crystal growth which is not crystallized after primary single crystal growth before cutting, and carries out a series of pretreatment and then feeds the single crystal growth into a furnace for growth again, thereby saving the raw material for single crystal growth and improving the crystallization rate.
In order to achieve the above object, the technical scheme of the present invention is as follows.
A single crystal regrowth method comprising the steps of:
s1, packaging seed crystals and materials required by single crystal growth in a quartz tube, putting the quartz tube into a single crystal furnace, and discharging the quartz tube after the single crystal growth is completed once;
s2, checking whether the tightness of the quartz tube after the single crystal growth is finished is good, if so, entering a step S3, otherwise, entering a step S9;
s3, heating the quartz cap at the top of the quartz tube to gasify and transfer materials attached to the inner wall of the quartz cap until the quartz cap is in a transparent state;
s4, observing whether defects exist at the tail of the crystal after one-time monocrystal growth through the quartz cap, if so, entering a step S5, otherwise, entering a step S9;
s5, putting the quartz tube into the single crystal furnace again, and increasing the temperature in the single crystal furnace to fuse the crystal into a required material;
s6, changing the growth parameters of the regrowth of the single crystal according to the result of the primary single crystal growth;
s7, controlling the melting depth of seed crystals during the regrowth of single crystals;
s8, discharging the single crystal from the furnace after the single crystal regrowth is completed according to the setting of the growth parameters;
s9, demolding the quartz tube which is discharged from the furnace, and performing subsequent crystal processing treatment.
By adopting the scheme, in order to improve the utilization rate of raw materials, the tightness of the quartz tube is judged after the primary monocrystal growth is finished, if the tightness of the quartz tube is poor, the quartz tube is directly cut to take out crystals no matter whether the monocrystal grows or not; the quartz tube with perfect sealing performance is used for observing whether the crystal has bad phenomenon or not, judging that the conditions that the quartz tube with perfect sealing performance and the tail end of the crystal have bad phenomenon and products cannot be grown out are met at the same time, and feeding the quartz tube into a furnace for single crystal regrowth; by analyzing the cause of the defect, the growth parameters of the regrowth are reset on the basis of the primary growth, thereby increasing the crystal formation rate of the regrowth.
Further, the materials in the step S1 comprise polycrystal materials, seed crystals, boron oxide, red phosphorus and doping agents, and the seed crystals are vertically arranged at the bottom of the quartz tube.
In the scheme, the seed crystal is a raw material for single crystal growth, the seed crystal is vertically placed at the bottom of the quartz tube through the boron nitride crucible, and the crystal grows along a model of the boron nitride crucible from the top of the seed crystal during single crystal growth. In the process of single crystal growth, red phosphorus is gasified at high temperature and fully runs into the space of the quartz tube. When the quartz tube is taken out from the single crystal furnace and then cooled, red phosphorus can be attached to the inner wall of the quartz tube, so that the originally transparent quartz tube is red, and the inside of the quartz tube is inconvenient to observe. In step S3, the top of the quartz tube is heated to gasify red phosphorus and then the red phosphorus is moved to other places, and the quartz tube is in a transparent state.
Further, the defects in step S4 include disordered polycrystalline, dendrite, and non-parallel twinning lines.
Further, the single crystal furnace is provided with a first temperature zone, a second temperature zone, a third temperature zone and a fourth temperature zone from bottom to top, and the method for controlling the melting depth of the seed crystal in the step S5 comprises the following steps:
s51, adjusting the temperatures of the first temperature region and the second temperature region to be lower than the crystal melting point, and adjusting the temperatures of the third temperature region and the fourth temperature region to be the melting point;
s52, keeping the temperatures of the first temperature area and the second temperature area constant, and gradually increasing the temperatures of the third temperature area and the fourth temperature area according to a gradient to gradually melt the crystal from top to bottom until the crystal is completely melted;
and S53, after the crystal is melted, keeping the first temperature zone, the second temperature zone, the third temperature zone and the fourth temperature zone at constant temperature for 5-8 hours.
By adopting the scheme, the unqualified crystal which grows is required to be melted in the regrowth process, and is directly melted in the airtight quartz tube, so that the materials in the quartz tube after the melting is complete are the same as those in the process of primary growth. The temperature of the first temperature area and the second temperature area is set to be far lower than that of the third temperature area and the fourth temperature area, the effect that seed crystals are not melted in the crystal melting process is achieved, the temperature of the third temperature area and the temperature of the fourth temperature area are gradually increased according to the gradient, and crystals can be slowly and fully melted.
Further, the gradient of the gradual heating of the third temperature zone and the fourth temperature zone of the single crystal furnace is 2 ℃ per ten minutes.
Further, the judgment basis of the complete melting of the crystal is as follows: after the temperature is adjusted up, the temperatures of the third temperature zone and the fourth temperature zone of the single crystal furnace are stable within ten minutes, and the temperature value is increased by 1.9-2.1 ℃.
By adopting the scheme, the crystal is solid, heat is absorbed when the crystal is melted into liquid, and when the crystal is not completely melted, the temperature can fluctuate and cannot be stabilized in a short time. So when the temperature stabilized within ten minutes, it was indicative of complete crystal melting.
Further, in step S7, the method for controlling the melting depth of the seed crystal includes:
s71, keeping the temperatures of the third temperature zone and the fourth temperature zone of the single crystal furnace unchanged after the step S53;
s72, synchronously and repeatedly adjusting the temperatures of the first temperature area and the second temperature area to be 20-40 ℃ in total, so that the seed crystal is melted to the target length;
and S73, after the seed crystal is melted to the target length, keeping the temperatures of the first temperature zone, the second temperature zone, the third temperature zone and the fourth temperature zone constant for 8-12 hours.
By adopting the scheme, the melt adjusting seed crystal in the single crystal regrowth process is used for melting the upper part of the seed crystal to a proper position, so that the top of the seed crystal is ensured to have no disordered crystal, and the purity and quality of single crystal regrowth are ensured.
Further, the target length of the seed crystal melting in step S72 is 10-25mm.
Still further, the single crystal has a melting point of 1064 ℃.
Still further, the procedure for single crystal regrowth is regulated as follows: the growth temperature field and the growth rate of the regrowth are adjusted by analyzing the reasons of the adverse phenomena after the primary growth.
By adopting the scheme, according to the result of single crystal one-time growth, if the tail end of the crystal generates twin crystals, the reason is that the growth speed is too high, and the growth step time is increased to reduce the growth speed when the single crystal is re-grown; if the tail end of the crystal is provided with disordered polycrystal or dendrite crystal, the reason is that the temperature gradient in the primary growth process is insufficient, namely, the temperature is required to be increased to speed up the growth rate during the regrowth, so that the temperature field of single crystal growth is controlled; if the tail end of the crystal is rugged or even cracked, the temperature setting values of the first, second, third and fourth temperature areas need to be adjusted when the single crystal grows, but the temperature should be kept within the range of 1065-1085 ℃ to ensure the normal growth of the single crystal.
The beneficial effects are that: on the basis of finishing one single crystal growth, the invention judges that the condition of re-growth is reached, and then the furnace is charged again to carry out the process of re-growth of the single crystal. The method avoids the damage of the boron nitride crucible caused by factors such as red phosphorus combustion, quartz tube collision, demoulding, external force and the like in the tube opening process, avoids the pollution and waste of raw materials in the repeated charging process, improves the purity of single crystals, and improves the utilization rate of the raw materials.
Drawings
Fig. 1 is a flow chart of the method of the present invention.
Fig. 2 is a schematic structural diagram of a single crystal furnace.
In the figure, a 1-single crystal furnace, a 2-seed crystal, a 3-crystal, a 4-quartz tube and a 5-quartz cap.
Detailed Description
The invention will be described in detail below with reference to fig. 1-2 and examples.
The single crystal regrowth method of the invention is mainly used for growing indium phosphide single crystal by a vertical temperature gradient method, and is also suitable for growing gallium arsenide single crystal by a vertical temperature gradient method.
Examples: as shown in fig. 1, a single crystal regrowth method includes the steps of:
s1, packaging seed crystals 2 and materials required by single crystal growth in a quartz tube 4, putting the quartz tube into a single crystal furnace 1, and discharging the quartz tube after the single crystal growth is finished once.
The primary single crystal growth process comprises the following steps:
s11, as shown in FIG. 2, vertically placing a raw material seed crystal 2 at the bottom of a boron nitride crucible, loading materials such as polycrystal materials, boron oxide, red phosphorus, doping agents and the like into the boron nitride crucible, vertically placing the boron nitride crucible into a quartz tube 4, welding a quartz cap 55 on the top of the quartz tube 4 for sealing after vacuum extraction, cooling to room temperature after welding sealing, detecting the vacuum degree of the quartz tube 4, and putting the quartz tube 1 into a single crystal furnace for heating after the vacuum degree is qualified.
In this embodiment, the temperature rise in the single crystal furnace 1 is divided into three stages, wherein the first stage is vacuum pumping, so that the interior of the single crystal furnace 1 is kept in a vacuum state, and in this stage, the temperatures in the single crystal furnace 1 and the quartz tube 4 are lower, and the red phosphorus in the quartz tube 4 is not gasified yet; the second stage is an air inlet stage, namely, inert protective gas is fed into the single crystal furnace 1, the air pressure in the single crystal furnace 1 is increased, the temperature in the single crystal furnace 1 is gradually increased in the process, red phosphorus begins to be gasified slowly, and the air pressure in the quartz tube 4 is slowly increased, so that the air pressure in the single crystal furnace 1 is basically level with the red phosphorus gasification air pressure in the quartz tube 4; and stopping air intake in the third stage, and heating up the single crystal furnace 1 normally.
S12, carrying out local temperature control on the quartz tube 4 to melt the polycrystalline material: as shown in fig. 2, the single crystal furnace 1 is provided with four temperature areas from bottom to top, and the temperatures of the third temperature area and the fourth temperature area are raised first to make the temperatures of the third temperature area and the fourth temperature area equal to or higher than the melting point of the polycrystalline material, so that the polycrystalline material at the upper part of the boron nitride crucible is melted, and the melted polycrystalline material flows to the position of the seed crystal 2 along the gap. At this time, the polycrystalline material contacts with the seed crystal 2, so that the temperature of the seed crystal 2 can be quickly raised by 5-15 ℃, and in order to ensure that the seed crystal 2 is not melted, the temperatures of the first temperature region and the second temperature region should be set to be far less than the melting point of the seed crystal 2.
S13, controlling the seed crystal 22 to melt: after the polycrystal material is completely melted, the temperatures of a third temperature area and a fourth temperature area of the single crystal furnace 1 are kept unchanged, the temperatures of the first temperature area and the second temperature area are slowly increased to reach 1064 ℃ of the melting point of the seed crystal 2, the top of the seed crystal 2 is melted, the melting depth is 1-10mm, and after the seed crystal 2 is melted to a proper position, the temperatures of the first temperature area, the second temperature area, the third temperature area and the fourth temperature area are kept unchanged for 8-12 hours, so that the thermal field in the single crystal furnace 1 is uniform.
S14, setting single crystal growth parameters, and carrying out single crystal growth according to the set growth rate and temperature field.
S2, checking whether the tightness of the quartz tube 4 after the single crystal growth is finished is good, if so, entering a step S3, otherwise, entering a step S9.
And S3, heating the quartz cap 5 at the top of the quartz tube 4 to gasify and transfer materials attached to the inner wall of the quartz cap 5 until the quartz cap 5 is in a transparent state.
S4, observing whether defects exist at the tail of the crystal 3 after one-time single crystal growth through the quartz cap 5, if so, entering a step S5, otherwise, entering a step S9.
S5, putting the quartz tube 4 into the single crystal furnace 1 again, and increasing the temperature in the single crystal furnace 1 to enable the crystal 3 to be melted to become an original material.
The method for controlling the melting of the crystal 3 comprises the following steps:
s51, the temperatures of the first temperature area and the second temperature area are adjusted to be lower than the melting point of the crystal 3, and the temperatures of the third temperature area and the fourth temperature area are adjusted to be the melting point.
S52, keeping the temperatures of the first temperature area and the second temperature area constant, and gradually increasing the temperatures of the third temperature area and the fourth temperature area according to a gradient to gradually melt the crystal 3 from top to bottom until the crystal 3 is completely melted.
And S53, after the crystal 3 is melted, keeping the first temperature zone, the second temperature zone, the third temperature zone and the fourth temperature zone at constant temperature for 5-8 hours.
S6, changing the growth parameters of the regrowth of the single crystal according to the result of the single crystal growth.
In this embodiment, the procedure for single crystal regrowth is regulated as follows: the growth temperature field and the growth rate of the regrowth are adjusted by analyzing the reasons of the adverse phenomena after the primary growth. The regulation and control method of the regrowth program comprises the following steps: compared with the primary single crystal growth, if the tail end of the crystal 3 is twined, the reason is that the growth speed is too high, and the growth step time is increased to reduce the growth speed when the single crystal is re-grown; if the tail end of the crystal 3 is provided with disordered polycrystal or dendrite, the reason is that the temperature gradient in the primary growth process is insufficient, namely, the temperature is required to be increased to speed up the growth rate during the regrowth, so that the temperature field of single crystal growth is controlled; if the tail end of the crystal 3 is rugged or even cracked, the temperature setting values of the first, second, third and fourth temperature areas need to be adjusted when the single crystal grows, and the temperature is adjusted up or down according to specific conditions, but the temperature is kept within the range of 1065-1085 ℃ to ensure the normal growth of the single crystal.
S7, controlling the melting depth of the seed crystal 2 during the regrowth of the single crystal.
The method for controlling the melting depth of the seed crystal 2 comprises the following steps:
and S71, keeping the temperatures of the third temperature zone and the fourth temperature zone of the single crystal furnace 1 unchanged after the step S53.
S72, synchronously and gradually adjusting the temperatures of the first temperature area and the second temperature area, and adjusting the temperature to 20-40 ℃ so as to melt the seed crystal 2 to the target length.
In this embodiment, the depth of fusion of the seed crystal at the time of the first single crystal growth is 1-10mm, and the target depth of fusion of the seed crystal 2 at the time of the regrowth should be greater than that of the first single crystal growth and about 10-25mm in order to ensure the purity of the crystal regrown by the single crystal.
And S73, after the seed crystal 2 is melted to the target length, keeping the temperatures of the first temperature zone, the second temperature zone, the third temperature zone and the fourth temperature zone constant for 8-12 hours.
S8, discharging the single crystal from the furnace after the single crystal regrowth is completed according to the setting of the growth parameters.
S9, opening the quartz tube 4 which is discharged from the furnace, demolding, and carrying out subsequent processing treatment on the crystal 3.
In this embodiment, the original total length of the seed crystal 2 is 30-45mm. The above-described single crystal regrowth method can be repeated to increase the crystallization rate of single crystal growth when the length of the seed crystal 2 and the lifetime of the quartz tube 4 are satisfied.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (4)
1. A single crystal regrowth method comprising the steps of:
s1, packaging seed crystals and materials required by single crystal growth in a quartz tube, putting the quartz tube into a single crystal furnace, and discharging the quartz tube after the single crystal growth is completed once;
s2, checking whether the tightness of the quartz tube after the single crystal growth is finished is good, if so, entering a step S3, otherwise, entering a step S9;
s3, heating the quartz cap at the top of the quartz tube to gasify and transfer materials attached to the inner wall of the quartz cap until the quartz cap is in a transparent state;
s4, observing whether defects exist at the tail of the crystal after one-time monocrystal growth through the quartz cap, if so, entering a step S5, otherwise, entering a step S9;
the defects include disordered polycrystalline, dendrite and non-parallel twin lines;
s5, putting the quartz tube into the single crystal furnace again, and increasing the temperature in the single crystal furnace to enable the crystal to be melted to become an original material;
the single crystal furnace is provided with a first temperature zone, a second temperature zone, a third temperature zone and a fourth temperature zone from bottom to top, and the crystal melting method comprises the following steps:
s51, adjusting the temperatures of the first temperature region and the second temperature region to be lower than the crystal melting point, and adjusting the temperatures of the third temperature region and the fourth temperature region to be the melting point;
s52, keeping the temperatures of the first temperature area and the second temperature area constant, and gradually increasing the temperatures of the third temperature area and the fourth temperature area according to a gradient to gradually melt the crystal from top to bottom until the crystal is completely melted; the gradient of gradually heating up in the third temperature zone and the fourth temperature zone of the single crystal furnace is 2 ℃ rising every ten minutes;
the judgment basis of the complete melting of the crystal is as follows: after the temperature is adjusted up, the temperatures of the third temperature zone and the fourth temperature zone of the single crystal furnace are stable within ten minutes, and the temperature value is increased by 1.9-2.1 ℃;
s53, after the crystal is melted, keeping the first temperature zone, the second temperature zone, the third temperature zone and the fourth temperature zone at constant temperature for 5-8 hours;
s6, changing the growth parameters of the regrowth of the single crystal according to the result of the primary single crystal growth;
the growth parameters of the single crystal regrowth comprise a growth temperature field and a growth rate, and the growth parameter regulation method of the regrowth comprises the following steps: compared with primary single crystal growth, if the tail end of the crystal has twin crystals, the growth step time is increased to reduce the growth rate; if the tail end of the crystal is in disorder polycrystal or dendrite crystal, the temperature is increased to accelerate the growth rate during regrowth, and if the tail end of the crystal 3 is uneven, the temperature setting values of the first, second, third and fourth temperature areas during single crystal growth are adjusted;
s7, controlling the melting depth of seed crystals during the regrowth of single crystals;
the control method of the seed crystal melting depth comprises the following steps:
s71, keeping the temperatures of the third temperature zone and the fourth temperature zone of the single crystal furnace unchanged after the step S53;
s72, synchronously and repeatedly adjusting the temperatures of the first temperature area and the second temperature area to be 20-40 ℃ in total, so that the seed crystal is melted to the target length;
s73, after the seed crystal is melted to the target length, keeping the temperatures of the first temperature zone, the second temperature zone, the third temperature zone and the fourth temperature zone constant for 8-12 hours;
s8, discharging the single crystal from the furnace after the single crystal regrowth is completed according to the setting of the growth parameters;
s9, demolding the quartz tube which is discharged from the furnace, and performing subsequent crystal processing treatment.
2. The method of claim 1, wherein the material in step S1 includes a polycrystalline material, boron oxide, red phosphorus, and a dopant, and the seed crystal is vertically placed at the bottom of the quartz tube.
3. A single crystal regrowth method as claimed in claim 1, wherein said target length of seed crystal melting in step S72 is 10mm to 25mm.
4. A method of regrowth of single crystal according to claim 1, wherein the single crystal has a melting point of 1064 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110793429.0A CN113668044B (en) | 2021-07-14 | 2021-07-14 | Single crystal regeneration method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110793429.0A CN113668044B (en) | 2021-07-14 | 2021-07-14 | Single crystal regeneration method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113668044A CN113668044A (en) | 2021-11-19 |
| CN113668044B true CN113668044B (en) | 2024-03-15 |
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