CN111020689A - Crystal growth apparatus and method - Google Patents
Crystal growth apparatus and method Download PDFInfo
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- CN111020689A CN111020689A CN201911282500.8A CN201911282500A CN111020689A CN 111020689 A CN111020689 A CN 111020689A CN 201911282500 A CN201911282500 A CN 201911282500A CN 111020689 A CN111020689 A CN 111020689A
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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
- C30B11/002—Crucibles or containers for supporting the melt
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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
- C30B11/003—Heating or cooling of the melt or the crystallised material
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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
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/42—Gallium arsenide
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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
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/04—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion materials in the liquid state
Abstract
The invention provides a crystal growth device, which comprises an outer crucible, a PBN crucible, seed crystals and a PBN plug, wherein the PBN crucible is arranged in the outer crucible, the PBN crucible comprises a crystal growth part, a shouldering part and a seed crystal well from top to bottom, the lower end of the seed crystal well is closed, the crystal growth part, the shouldering part and the seed crystal well form an accommodating space together, the seed crystals are positioned in the accommodating space corresponding to the seed crystal well and the shouldering part in the crystal growth process, polycrystalline materials and covering agents are positioned in the accommodating space corresponding to the upper part of the seed crystals, the PBN plug is positioned in the seed crystal well, the lower end of the PBN plug is abutted against the inner bottom surface of the seed crystal well, and the upper end of the PBN plug is abutted against. The invention also provides a crystal growth method. The crystal growth device and the method can improve the welding quality of seed crystals in the crystal growth process, ensure the stoichiometric ratio, control the impurity level in the crystal growth process and finally realize high-quality crystal growth with low cost.
Description
Technical Field
The invention relates to the field of semiconductor crystal preparation, in particular to a crystal growth device and a crystal growth method.
Background
Gallium arsenide single crystals are widely applied to the fields of microelectronics and photoelectrons, the demand for gallium arsenide single crystals develops towards the direction of large size, high precision and low dislocation density, and the growth methods of the gallium arsenide single crystals at present comprise LEC, HB, VB, VGF and the like. Growing large size and low dislocation density (EPD) crystals at low cost is an important prerequisite for large-scale application of gallium arsenide. The thermal conductivity of gallium arsenide is 0.58W/M.K, and the dislocation generation critical stress is about 0.5 MPa. The low EPD single crystal is grown by a vertical Bridgman method (VB method) and a vertical gradient freeze method (VGF method). The VGF method is further divided into a resistance wire heating quartz tube sealing growth method and a graphite heater high-pressure cold wall furnace growth method.
US8231727B2 discloses systems and methods for producing crystal growth using VGF and VB growth processes that reduce dendrites, improve the utilization of crystal growth, and thereby reduce costs. However, the quartz tube is used in the growth process, the mechanical property of the quartz tube is obviously reduced near 1255 ℃, the reaction activity of impurities in the quartz tube is high, and the impurities are easy to enter gallium arsenide crystals, so that the growth of large-size high-purity gallium arsenide crystals is not facilitated.
Chinese patent application CN106400101A provides a method for growing gallium arsenide single crystal by VB method, but the apparatus of this method has the following disadvantages: (1) the energy consumption of equipment operation is too high; (2) the equipment adopts a descending device, and the mechanical vibration of the descending device is not beneficial to obtaining crystals with low dislocation density; (3) the sealing of the descending shaft is easy to damage, and the replacement procedure of the sealing ring is complicated; after the gas leaks slightly, the pressure fluctuation in the furnace causes the temperature change.
Still another crystal growth apparatus used in the prior art is shown in fig. 1 and 2, the crystal growth apparatus 100 includes a graphite crucible 110, a PBN crucible 120, a seed crystal 130, and a PBN plug 140, the PBN crucible 120 is disposed in the graphite crucible 110, the PBN crucible 120 includes a crystal growth portion 121, a shoulder portion 122, and a seed well 123 from top to bottom, the lower end of the seed well 123 is open, the crystal growth portion 121, the shoulder portion 122, and the seed well 123 together form a receiving space 124, during the crystal growth process, the seed crystal 130 is located in the receiving space 124 corresponding to the seed well 123 and the shoulder portion 122, while the polycrystalline material and the covering agent are both located in the receiving space 124 corresponding to the upper portion of the seed crystal 130, the PBN plug 140 protrudes from the inside of the seed well 123, and the lower end of the PBN plug 140 abuts against the inner bottom surface of the graphite crucible 110.
The disadvantages of the above-mentioned devices are: because of seed crystal well 123 lower extreme opening, be difficult to avoid revealing of sealant, lead to the seed crystal well 123 and the graphite crucible 110 crucible of PBN crucible 120 to bond, difficult separation, and in PBN stopper 140 need rely on the manual work to fill in seed crystal well 123, relapse many times, fragile seed crystal well 123 for whole PBN crucible 120 is scrapped, improves the long brilliant cost.
In view of the above technical problems, it is desirable to provide an improved crystal growth apparatus and method.
Disclosure of Invention
The invention aims to provide an improved crystal growing device and method.
In order to achieve the purpose, the invention adopts the following technical scheme: the utility model provides a crystal growth device, this crystal growth device includes outer crucible, the PBN crucible, the seed crystal, the PBN stopper, the PBN crucible is arranged in outer crucible, the PBN crucible includes top-down crystal growth portion, put the shoulder, the seed crystal well, seed crystal well lower extreme is sealed, crystal growth portion, put the shoulder, the seed crystal well forms an accommodation space jointly, in crystal growth process, the seed crystal is located the seed crystal well and puts the accommodation space that the shoulder corresponds, and polycrystal material and covering agent all are located the accommodation space that the seed crystal top corresponds, the PBN stopper is located the seed crystal well, and PBN stopper lower extreme butt seed crystal well inner bottom surface, PBN stopper upper end butt seed crystal lower bottom surface.
As a further improvement of the invention, the crystal growth device also comprises a heat preservation device, a furnace body and a crucible support, wherein the outer crucible is erected above the crucible support, the heat preservation device comprises a heat preservation layer and a plurality of annular heaters arranged around the outer crucible, the central axes of the annular heaters are superposed with the central axis of the outer crucible, the outer crucible and the crucible support are both positioned in the heat preservation layer, and the heat preservation layer is positioned in the furnace body.
A crystal growth method adopts the crystal growth device, and the method comprises the following steps:
s1, charging: cleaning the PBN crucible, putting the PBN crucible into an outer crucible, putting a PBN plug and seed crystals into a seed crystal well, putting a polycrystalline material into the PBN crucible, putting a dopant and a covering agent into the PBN crucible, and then packaging the outer crucible;
s2, charging and ventilating: placing the outer crucible on a crucible support, closing the furnace body, and carrying out air exchange for 2-3 times; filling protective gas with the purity of 4-5N into the furnace body to enable the absolute pressure in the furnace body at room temperature to be P0, wherein the range of P0 is 300-500 KPa;
s3, heating and melting: forming a first temperature zone and a second temperature zone in the furnace body, and starting a heater to ensure that the first temperature zone and the second temperature zone are uniformly heated to the temperature of T1 at a constant speed within T1 time from room temperature at a heating rate of V1; then preserving the heat for 2-4 h; then continuing heating, so that the first temperature zone is heated to 1240-1270 ℃ within t2 time at the temperature raising rate of V2, and simultaneously the second temperature zone is heated to 1150-1200 ℃ within t2 time at the temperature raising rate of V3, and the temperature is kept for t3 time, so that the polycrystalline material is fully melted, and the doping agent is uniformly distributed in the melt;
s4, seed crystal fusion: then, the first temperature zone and the second temperature zone are lifted by 5-10 ℃, and then the temperature is kept for t4 time, so that the seed crystals are partially melted;
s5, crystal growth: adjusting the temperature control temperature of each heater to enable the isothermal surface to move upwards and the crystal to grow upwards, wherein the moving speed of the isothermal surface is 0.5-5 mm/h;
s6, cooling and discharging: after the temperature of each area of crystal growth is reduced to the freezing point of the crystal, adjusting the temperature of the heater to ensure that the temperature of the first temperature area and the second temperature area is adjusted to 1180-1220 ℃ to form constant temperature areas; and then, continuously reducing the temperature of the constant-temperature area at a constant speed at a V4 temperature reduction rate until the temperature reaches T4, then reducing the temperature to room temperature at a V5 temperature reduction rate, and finishing the crystal growth process to obtain the single crystal.
As a further improvement of the invention, t1 is 1.5-2 h; t1 is 500-650 ℃.
As a further improvement of the invention, t2 is 2-4 h.
As a further improvement of the invention, t3 is 5-20 h.
As a further improvement of the invention, t4 is 5-48 h.
As a further improvement of the invention, T4 is 800-950 ℃; v4 is 10-20 ℃/h.
As a further improvement of the invention, V5 is 20-40 ℃/h.
As a further improvement of the invention, the moving speed of the isothermal surface is 0.5-2 mm/h.
Compared with the seed crystal well with an opening, the crystal growth device can avoid the leakage of the sealant, reduce the damage of taking and placing the PBN plug to the seed crystal well and increase the use times of the PBN crucible; the crystal growth method can reduce the decomposition and energy consumption of gallium arsenide, obtain stable growth atmosphere and temperature conditions, control the impurity level in the crystal growth process and finally realize high-quality crystal growth at low cost.
Drawings
Fig. 1 is a first structural diagram in the prior art.
Fig. 2 is a schematic structural diagram of the prior art.
FIG. 3 is a schematic view of the overall structure of an embodiment of the crystal growth apparatus of the present invention.
FIG. 4 is a schematic view of a portion of a crystal growth apparatus according to an embodiment of the present invention.
FIG. 5 is a schematic diagram of a second partial structure of the crystal growth apparatus according to the embodiment of the present invention.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a crystal growth device 200, please refer to fig. 3-5, the crystal growth device 200 comprises an outer crucible 210, a PBN crucible 220, a seed crystal 230, and a PBN plug 240, the PBN crucible 220 is disposed in the outer crucible 210, the PBN crucible 220 comprises a crystal growth part 221, a shoulder 222, and a seed well 223 from top to bottom, the lower end of the seed well 223 is closed, the crystal growth part 221, the shoulder 222, and the seed well 223 together form a receiving space 224, during the crystal growth process, the seed crystal 230 is disposed in the receiving space 224 corresponding to the seed well 223 and the shoulder 222, while the polycrystalline material and the covering agent are both disposed in the receiving space 224 corresponding to the upper part of the seed crystal 230, the PBN plug 240 is disposed in the seed well 223, and the seed crystal at the lower end of the PBN plug 240 abuts against the inner bottom surface of the well 223, and the upper end of the PBN plug 240 abuts against the lower bottom surface of the seed.
In certain embodiments of the present invention, the outer crucible 210 is a graphite crucible. The device adopts the graphite outer crucible to replace a disposable quartz ampoule in the prior art, and can save the cost.
This crystal growth device 200 still includes heat preservation device 250, furnace body 260 and crucible support 270, and heat preservation device 250 includes that heat preservation 251 and symmetry locate a plurality of circular heater 252 of outer crucible 210 both sides, and outer crucible 210 erects in the crucible support 270 top, and outer crucible 210 and crucible support 270 all are located heat preservation 251, and heat preservation 251 is located furnace body 260. The crystal growing apparatus 200 is controlled by a central controller (not shown).
This crystal growth device 200 still includes heat preservation device 250, furnace body 260 and crucible support 270, and outer crucible 210 erects in the crucible support 270 top, and heat preservation device 250 includes heat preservation 251 and a plurality of ring heater 252 that set up around outer crucible 210, and the central axis coincidence of a plurality of ring heater 252 central axes and outer crucible 210, and outer crucible 210 and crucible support 270 all are located heat preservation 251, and heat preservation 251 is located furnace body 260, and crystal growth device 200 receives central controller (not shown on the figure) control.
This crystal growth device changes to seal lengthened seed crystal well to increase the PBN stopper, have two benefits: on one hand, compared with a short seed crystal well, the length of the seed crystal can be reduced by adding the PBN plug, the heat conduction of the seed crystal is increased, and the crystallization heat is ensured to be transferred along the seed crystal; on the other hand, compared with the seed crystal well with an opening, the leakage of the sealant can be avoided, the damage of taking and placing the PBN plug to the seed crystal well is reduced, and the use times of the PBN crucible is increased.
The invention provides a crystal growth method, which adopts the crystal growth device and comprises the following steps:
s1, charging: cleaning the PBN crucible, putting the PBN crucible into an outer crucible, putting a PBN plug and seed crystals into a seed crystal well, putting a polycrystalline material into the PBN crucible, putting a dopant and a covering agent into the PBN crucible, and then packaging the outer crucible;
s2, charging and ventilating: placing the outer crucible on a crucible support, closing the furnace body, and carrying out air exchange for 2-3 times; filling protective gas with the purity of 4-5N into the furnace body to enable the absolute pressure in the furnace body at room temperature to be P0, wherein the range of P0 is 300-500 KPa;
s3, heating and melting: forming a first temperature zone and a second temperature zone in the furnace body, and starting a heater to ensure that the first temperature zone and the second temperature zone are uniformly heated to the temperature of T1 at a constant speed within T1 time from room temperature at a heating rate of V1; then preserving the heat for 2-4 h; then continuing heating, so that the first temperature zone is heated to 1240-1270 ℃ within t2 time at the temperature raising rate of V2, and simultaneously the second temperature zone is heated to 1150-1200 ℃ within t2 time at the temperature raising rate of V3, and the temperature is kept for t3 time, so that the polycrystalline material is fully melted, and the doping agent is uniformly distributed in the melt;
s4, seed crystal fusion: then, the first temperature zone and the second temperature zone are lifted by 5-10 ℃, and then the temperature is kept for t4 time, so that the seed crystals are partially melted;
s5, crystal growth: adjusting the temperature control temperature of each heater to enable the isothermal surface to move upwards and the crystal to grow upwards, wherein the moving speed of the isothermal surface is 0.5-5 mm/h;
s6, cooling and discharging: after the temperature of each area of crystal growth is reduced to the freezing point of the crystal, adjusting the temperature of the heater to ensure that the temperature of the first temperature area and the second temperature area is adjusted to 1180-1220 ℃ to form constant temperature areas; and then, continuously reducing the temperature of the constant-temperature area at a constant speed at a V4 temperature reduction rate until the temperature reaches T4, then reducing the temperature to room temperature at a V5 temperature reduction rate, and finishing the crystal growth process to obtain the single crystal.
In some embodiments of the present invention, t1 is 1.5-2 h; t1 is 500-650 ℃.
In some embodiments of the present invention, t2 is 2-4 h.
In some embodiments of the present invention, t3 is 5-20 h.
In some embodiments of the present invention, t4 is 5-48 h.
In some embodiments of the present invention, T4 is 800-950 ℃ and V4 is 10-20 ℃/h.
In some embodiments of the present invention, V5 is 20-40 ℃/h.
In some embodiments of the present invention, the moving speed of the isothermal surface is 0.5 to 5 mm/h. Preferably, the moving speed of the isothermal surface is 0.5-2 mm/h.
In certain embodiments of the invention, the shielding gas is nitrogen or an inert gas.
The crystal growth method divides the temperature rise and material melting stage into three stages: a) heating to melt the covering agent, b) heating to melt the material, and c) heating to melt the seed crystal. The temperature rise process is adjusted, so that the polycrystalline materials can be fully covered by the covering agent, and the decomposition of the polycrystalline materials is reduced. Meanwhile, the temperature is raised in a stepped mode, materials are melted and seed crystals are welded in a staged mode, the welding length of the seed crystals is controlled, and excessive melting is prevented.
Based on the improved crystal growth method, the decomposition and energy consumption of gallium arsenide can be reduced, stable growth atmosphere and temperature conditions can be obtained, the welding quality of seed crystals in the crystal growth process is improved, the stoichiometric ratio is ensured, the impurity level in the crystal growth process can be controlled, and finally high-quality crystal growth is realized at low cost.
Example 1.
In this example, the above-mentioned crystal growth apparatus and method were used to prepare a 10Kg weight of 4 inch GaAs single crystal. The method comprises the following steps.
Charging: the 4 inch PBN crucible was cleaned for use. Preparing gallium arsenide seed crystal with the (100) 15-degree deviation direction, the diameter of 8mm and the length of 35 mm. PBN plugs, seed crystals, 10Kg of gallium arsenide polycrystalline material, 2.4g of dopant silicon and 100g of sealant boron oxide are sequentially placed in a PBN crucible from bottom to top, wherein the PBN plugs and the seed crystals are placed in seed crystal wells. The PBN crucible was placed in the outer crucible, which was then sealed.
Charging and ventilating: and (3) connecting the outer crucible on a crucible support, and adjusting the position of the crucible to ensure that the crucible and the crucible support are coaxial. Closing the furnace body, and introducing high-purity N2Ventilation was performed 3 times. And at room temperature, filling argon with the purity of 5N into the furnace body to ensure that the air pressure in the furnace body is 300 KPa.
Heating and material melting: forming a first temperature zone and a second temperature zone in the furnace body, and starting a heater to ensure that the first temperature zone and the second temperature zone are heated to 500 ℃ from room temperature for 1.5 h; then preserving the heat for 2 h; and then continuing heating, so that the temperature of the first temperature zone is raised to 1240 ℃ for 2h, simultaneously the temperature of the second temperature zone is raised to 1180 ℃ for 4h, and the temperature is maintained for 12h, so that the polycrystalline material is fully melted, and the dopant is uniformly distributed in the solution.
Seed crystal welding: the temperature of the first temperature zone is raised by 10 ℃, the temperature of the second temperature zone is raised by 5 ℃, and the temperature is kept for 12 hours, so that partial melting of the seed crystals is ensured.
Crystal growth: and regulating the temperature control temperature of each heater to ensure that the isothermal surface moves upwards and the crystal grows upwards, wherein the moving speed of the isothermal surface is 2.0 mm/h.
Cooling and discharging: after the temperature of each area of crystal growth is reduced to the freezing point of the crystal, the temperature of the heater is adjusted, so that the temperature of the first temperature area and the second temperature area is adjusted to 1180 ℃ to form a constant temperature area; then the constant temperature area is continuously cooled at a constant speed at a cooling rate of 10 ℃/h until reaching 800 ℃, and then is cooled to room temperature at a cooling rate of 40 ℃/h, and the crystal growth process is finished to obtain the single crystal.
Through detection, the obtained gallium arsenide monocrystal is 4 inches, and the length is 180 mm.
Example 2.
In this example, the above-mentioned crystal growth apparatus and method were used to prepare a 10Kg gallium arsenide single crystal of 6 inches. The method comprises the following steps.
Charging: the 6 inch PBN crucible was cleaned for use. Preparing gallium arsenide seed crystal with (100) deviation in the (111) 6-degree direction, the diameter of 8mm and the length of 30 mm. PBN plugs, seed crystals, 12Kg of gallium arsenide polycrystalline material, 2.8g of dopant silicon and 250g of sealant boron oxide are sequentially placed in a PBN crucible from bottom to top, wherein the PBN plugs and the seed crystals are placed in seed crystal wells. The PBN crucible was placed in the outer crucible, which was then sealed.
Charging and ventilating: and (3) connecting the outer crucible on a crucible support, and adjusting the position of the crucible to ensure that the crucible and the crucible support are coaxial. Closing the furnace body, and introducing high-purity N2Ventilation was performed 3 times. And at room temperature, filling argon with the purity of 5N into the furnace body to ensure that the air pressure in the furnace body is 400 KPa.
Heating and material melting: forming a first temperature zone and a second temperature zone in the furnace body, and starting a heater to ensure that the first temperature zone and the second temperature zone are both heated to 550 ℃ from the room temperature of 100 Min; then preserving the heat for 4 hours; and then heating is continued, so that the temperature of the first temperature zone is raised to 1260 ℃ for 3h, the temperature of the second temperature zone is raised to 1180 ℃ for 4h, and the temperature is maintained for 20h, so that the polycrystalline material is fully melted, and the dopant is uniformly distributed in the solution.
Seed crystal welding: and raising the temperature of the first temperature zone by 8 ℃, raising the temperature of the second temperature zone by 8 ℃, and preserving the heat for 5 hours to ensure that the seed crystal is partially melted.
Crystal growth: and regulating the temperature control temperature of each heater to ensure that the isothermal surface moves upwards and the crystal grows upwards, wherein the moving speed of the isothermal surface is 1.0 mm/h.
Cooling and discharging: after the temperature of each area of crystal growth is reduced to the freezing point of the crystal, the temperature of the heater is adjusted, so that the temperature of the first temperature area and the second temperature area is adjusted to 1220 ℃ to form a constant temperature area; then the constant temperature area is continuously cooled at a constant speed at a cooling rate of 10 ℃/h until the temperature reaches 850 ℃, then the temperature is reduced to the room temperature at a cooling rate of 30 ℃/h, and the crystal growth process is finished to obtain the single crystal.
The detection shows that the obtained gallium arsenide monocrystal is 4 inches and the length is 90 mm.
Example 3.
In this example, the above-mentioned crystal growth apparatus and method were used to prepare a 10Kg gallium arsenide single crystal of 6 inches. The method comprises the following steps.
Charging: the 6 inch PBN crucible was cleaned for use. Preparing gallium arsenide seed crystal with (100) 2-degree deviation direction, diameter of 8mm and length of 40 mm. PBN plugs, seed crystals, 15Kg of gallium arsenide polycrystalline material, 3.6g of dopant silicon and 250g of sealant boron oxide are sequentially placed in a PBN crucible from bottom to top, wherein the PBN plugs and the seed crystals are placed in seed crystal wells. The PBN crucible was placed in the outer crucible, which was then sealed.
Charging and ventilating: and (3) connecting the outer crucible on a crucible support, and adjusting the position of the crucible to ensure that the crucible and the crucible support are coaxial. Closing the furnace body, and introducing high-purity N2Ventilation was performed 3 times. And at room temperature, filling argon with the purity of 5N into the furnace body to ensure that the air pressure in the furnace body is 500 KPa.
Heating and material melting: forming a first temperature zone and a second temperature zone in the furnace body, and starting a heater to ensure that the first temperature zone and the second temperature zone are heated to 650 ℃ from room temperature for 2 h; then preserving the heat for 3 h; and then heating is continued, so that the temperature of the first temperature zone is raised to 1270 ℃ for 4h, the temperature of the second temperature zone is raised to 1200 ℃ for 4h, and the temperature is maintained for 5h, so that the polycrystalline material is fully melted, and the dopant is uniformly distributed in the solution.
Seed crystal welding: and raising the temperature of the first temperature zone by 5 ℃, raising the temperature of the second temperature zone by 10 ℃, and preserving the heat for 48 hours to ensure that the seed crystal is partially melted.
Crystal growth: and regulating the temperature control temperature of each heater to ensure that the isothermal surface moves upwards and the crystal grows upwards, wherein the moving speed of the isothermal surface is 0.5 mm/h.
Cooling and discharging: after the temperature of each area of crystal growth is reduced to the freezing point of the crystal, the temperature of the heater is adjusted, so that the temperature of the first temperature area and the second temperature area is adjusted to 1200 ℃ to form a constant temperature area; then the constant temperature area is continuously cooled at a constant speed at a cooling rate of 10 ℃/h until the temperature reaches 950 ℃, then the temperature is reduced to the room temperature at a cooling rate of 20 ℃/h, and the crystal growth process is finished to obtain the single crystal.
The detection shows that the obtained gallium arsenide monocrystal is 6 inches and 120mm in length.
Compared with the seed crystal well with an opening, the crystal growth device can avoid the leakage of the sealant, reduce the damage of taking and placing the PBN plug to the seed crystal well and increase the use times of the PBN crucible; the crystal growth method can reduce the decomposition and energy consumption of gallium arsenide, obtain stable growth atmosphere and temperature conditions, improve the welding quality of seed crystals in the crystal growth process, ensure the stoichiometric ratio, control the impurity level in the crystal growth process, and finally realize high-quality crystal growth with low cost.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (10)
1. The utility model provides a crystal growth device, this crystal growth device includes outer crucible, PBN crucible, seed crystal, PBN stopper, and in the outer crucible was arranged in to the PBN crucible, the PBN crucible included top-down crystal growth portion, put shoulder, seed crystal well, its characterized in that: the underground end of the seed crystal is closed, the crystal growth part, the placing shoulder part and the seed crystal well form an accommodating space together, in the crystal growth process, the seed crystal is positioned in the accommodating space corresponding to the seed crystal well and the placing shoulder part, the polycrystalline material and the covering agent are both positioned in the accommodating space corresponding to the upper part of the seed crystal, the PBN plug is positioned in the seed crystal well, the lower end of the PBN plug is abutted to the inner bottom surface of the seed crystal well, and the upper end of the PBN plug is abutted to the lower bottom surface of the seed crystal.
2. The crystal growth apparatus of claim 1, wherein: this crystal growth device still includes heat preservation device, furnace body and crucible and holds in the palm, and outer crucible erects in crucible holds in the palm the top, and the heat preservation device includes the heat preservation and around a plurality of cyclic annular heaters of outer crucible setting, the coincidence of the central axis of a plurality of cyclic annular heater central axes and outer crucible, and outer crucible and crucible hold in the palm and all be located the heat preservation in situ, and the heat preservation is located the furnace body.
3. A crystal growth method using the furnace body of claim 2, characterized in that: the method comprises the following steps:
s1, charging: cleaning the PBN crucible, putting the PBN crucible into an outer crucible, putting a PBN plug and seed crystals into a seed crystal well, putting a polycrystalline material into the PBN crucible, putting a dopant and a covering agent into the PBN crucible, and then packaging the outer crucible;
s2, charging and ventilating: placing the outer crucible on a crucible support, closing the furnace body, and carrying out air exchange for 2-3 times; filling protective gas with the purity of 4-5N into the furnace body to enable the absolute pressure in the furnace body at room temperature to be P0, wherein the range of P0 is 300-500 KPa;
s3, heating and melting: forming a first temperature zone and a second temperature zone in the furnace body, and starting a heater to ensure that the first temperature zone and the second temperature zone are uniformly heated to the temperature of T1 at a constant speed within T1 time from room temperature at a heating rate of V1; then preserving the heat for 2-4 h; then continuing heating, so that the first temperature zone is heated to 1240-1270 ℃ within t2 time at the temperature raising rate of V2, and simultaneously the second temperature zone is heated to 1150-1200 ℃ within t2 time at the temperature raising rate of V3, and the temperature is kept for t3 time, so that the polycrystalline material is fully melted, and the doping agent is uniformly distributed in the melt;
s4, seed crystal fusion: then, the first temperature zone and the second temperature zone are lifted by 5-10 ℃, and then the temperature is kept for t4 time, so that the seed crystals are partially melted;
s5, crystal growth: adjusting the temperature control temperature of each heater to enable the isothermal surface to move upwards and the crystal to grow upwards, wherein the moving speed of the isothermal surface is 0.5-5 mm/h;
s6, cooling and discharging: after the temperature of each area of crystal growth is reduced to the freezing point of the crystal, adjusting the temperature of the heater to ensure that the temperature of the first temperature area and the second temperature area is adjusted to 1180-1220 ℃ to form constant temperature areas; and then, continuously reducing the temperature of the constant-temperature area at a constant speed at a V4 temperature reduction rate until the temperature reaches T4, then reducing the temperature to room temperature at a V5 temperature reduction rate, and finishing the crystal growth process to obtain the single crystal.
4. A crystal growth method according to claim 3, characterized in that: t1 is 1.5-2 h; t1 is 500-650 ℃.
5. A crystal growth method according to claim 3, characterized in that: t2 is 2-4 h.
6. A crystal growth method according to claim 3, characterized in that: t3 is 5-20 h.
7. A crystal growth method according to claim 3, characterized in that: t4 is 5-48 h.
8. A crystal growth method according to claim 3, characterized in that: t4 is 800-950 ℃; v4 is 10-20 ℃/h.
9. A crystal growth method according to claim 3, characterized in that: v5 is 20-40 ℃/h.
10. A crystal growth method according to claim 3, characterized in that: the moving speed of the isothermal surface is 0.5-2 mm/h.
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| CN113213970A (en) * | 2021-04-20 | 2021-08-06 | 广东先导微电子科技有限公司 | PBN crucible boron oxide wetting device, method and application thereof |
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Application publication date: 20200417 |