CN113512754A - Alumina ceramic crucible, use structure thereof and method for growing single crystal - Google Patents
Alumina ceramic crucible, use structure thereof and method for growing single crystal Download PDFInfo
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- CN113512754A CN113512754A CN202110576484.4A CN202110576484A CN113512754A CN 113512754 A CN113512754 A CN 113512754A CN 202110576484 A CN202110576484 A CN 202110576484A CN 113512754 A CN113512754 A CN 113512754A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000013078 crystal Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000007789 sealing Methods 0.000 claims abstract description 78
- 239000000919 ceramic Substances 0.000 claims abstract description 74
- 239000000835 fiber Substances 0.000 claims abstract description 59
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims abstract description 51
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 36
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 17
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052582 BN Inorganic materials 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 229910052810 boron oxide Inorganic materials 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 6
- 239000011224 oxide ceramic Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 11
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 238000003466 welding Methods 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- JPYPZXAFEOFGSM-UHFFFAOYSA-N O.[B]=O Chemical compound O.[B]=O JPYPZXAFEOFGSM-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
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Classifications
-
- 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
-
- 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
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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 invention discloses an alumina ceramic crucible, a use structure thereof and a method for growing single crystals, wherein the alumina ceramic crucible comprises an alumina ceramic crucible, an alumina ceramic sealing cap, an aluminum silicate ceramic fiber sealing gasket and an aluminum silicate ceramic fiber paper layer; the alumina ceramic crucible comprises a seed crystal cavity, a pyramid part and a body part which are sequentially connected from bottom to top, the top of the body part is of an open structure, an alumina ceramic sealing cap is in threaded connection with the top of the body part, and a ceramic fiber sealing gasket is arranged between the alumina ceramic sealing cap and the top of the body part; the alumina silicate ceramic fiber paper layer is movably paved on the inner side of the alumina ceramic crucible. When the single crystal is grown, the alumina ceramic crucible is used for replacing a quartz crucible, quartz oxyhydrogen flame welding seal is not needed, and nitrogen is not needed to be filled into a VGF single crystal furnace for balancing pressure, so that the production cost is reduced; through the arrangement of the aluminum silicate ceramic fiber paper, the stability of the temperature field of the single crystal furnace is greatly improved, the dislocation density of the indium phosphide single crystal is reduced, and the crystallization rate is improved.
Description
Technical Field
The invention relates to an alumina ceramic crucible, a using structure thereof and a method for growing single crystals, belonging to the technical field of InP single crystal growth.
Background
Indium phosphide (InP) is one of important group iii-v compound semiconductor materials, and is a new-generation electronic functional material following Si and GaAs. GaAs, InP and the like have superior characteristics (such as high electron mobility, large forbidden band width and the like) which Ge and Si do not have, and can be widely applied to the fields of microwave and photoelectric devices. The InP material is suitable for manufacturing millimeter wave frequency conversion devices, can be widely applied to radar communication and accurate guidance, and InP-based microwave devices are key components of new-generation satellite communication and accurate guidance and directly determine the quick response capability of weapon equipment systems.
The method for obtaining InP single crystal material at present is mainly a vertical temperature gradient freezing (VGF) method, firstly, indium phosphide polycrystal material is cleaned and then mixed with dopant and B2O3Filling a liquid sealing agent, high-purity red phosphorus, seed crystals and the like into a cleaned PBN crucible, then putting the PBN crucible and the seed crystals into a quartz crucible together, vacuumizing the interior of the quartz crucible to vacuum by using a molecular vacuum pump, and sealing the vacuumized quartz crucible by using oxyhydrogen flame; a heater with a multi-section heating structure is adopted to establish a temperature gradient in the vertical direction, the indium phosphide polycrystal material is melted, the cooling speed of each temperature zone is controlled, the growth interface is slowly moved upwards, and the directional solidification growth of the indium phosphide is realized. When the indium phosphide single crystal growth is carried out, along with the temperature rise, the high-purity red phosphorus charged during the batching is sublimated into red phosphorus steam, the pressure of 2.75MPa is generated inside the quartz crucible, and the pressure vessel is required to be filled with nitrogen or argon slightly higher than 2.75MPa for balancing the pressure.
The nitrogen gas filled in the single crystal furnace generates violent gas convection under the conditions of high temperature and high pressure, so that the temperature of a temperature field generates larger fluctuation, the obtained single crystal has high dislocation density, fine twin crystals are easy to grow in the crystal, the crystallization rate is not high, and a quartz tube, a quartz cap and the like after use are immediately scrapped, so that the price of a large-size high-quality substrate in the market is always high. And the welding path position of the quartz tube is stressed after being sealed by oxyhydrogen flame welding, the quartz tube is easy to generate cracks under the conditions of high temperature and high pressure to cause tube breakage, so that the indium phosphide polycrystal material is dissociated, a large amount of red phosphorus is burnt to damage a single crystal furnace, and the production is delayed.
Disclosure of Invention
The invention provides an alumina ceramic crucible, a using structure thereof and a method for growing a single crystal, which can effectively overcome the defects of high dislocation density, low crystallization rate, high cost and the like in the existing indium phosphide single crystal growth process.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an alumina ceramic crucible comprises an alumina ceramic crucible, an alumina ceramic sealing cap, an aluminum silicate ceramic fiber sealing gasket and an aluminum silicate ceramic fiber paper layer; the alumina ceramic crucible comprises a seed crystal cavity, a pyramid part and a body part which are sequentially connected from bottom to top, the top of the body part is of an open structure, an alumina ceramic sealing cap is in threaded connection with the top of the body part, and a ceramic fiber sealing gasket is arranged between the alumina ceramic sealing cap and the top of the body part; the alumina silicate ceramic fiber paper layer is movably paved on the inner side of the alumina ceramic crucible.
According to the aluminum oxide ceramic crucible, the aluminum oxide ceramic sealing cap is in threaded connection with the aluminum ceramic crucible, the aluminum oxide ceramic sealing cap can be repeatedly used, the preparation cost is obviously reduced, meanwhile, a welding line is not needed, the loss of raw and auxiliary materials and equipment caused by cracking of a quartz tube in the prior art is avoided, and the service life of the equipment is prolonged; the sealing performance between the alumina ceramic crucible and the alumina ceramic sealing cap is ensured by the arrangement of the alumina silicate ceramic fiber sealing gasket; the bonding state of the PBN crucible and the outer crucible can be effectively improved through the arrangement of the aluminum silicate ceramic fiber paper layer, the stability of a temperature field of a single crystal furnace is greatly improved, nitrogen or argon is not required to be filled in the single crystal preparation process to balance the pressure, the dislocation density of the indium phosphide single crystal is reduced, the crystallization rate is improved, and the large-size high-quality indium phosphide substrate is obtained.
In order to improve the connection stability and the sealing performance of the alumina ceramic sealing cap and the aluminum ceramic crucible, external threads are arranged on the periphery of the top of the body part, and internal threads matched with the external threads on the body part are arranged at the bottom of the alumina ceramic sealing cap; the aluminum silicate ceramic fiber sealing gasket comprises a first sealing gasket and a second sealing gasket, the first sealing gasket is sleeved at the bottom of the external thread of the body, and the second sealing gasket is arranged at the top of the internal thread of the aluminum oxide ceramic sealing cap.
In order to further increase the crystallization rate, the taper angle is 90 °. I.e. the angle of inclination of the taper to the axial direction is 45 deg..
The using structure of the alumina ceramic crucible also comprises a PBN crucible, wherein the PBN crucible is positioned at the inner side of the alumina silicate ceramic fiber paper layer, and the PBN crucible is tightly attached to the alumina silicate ceramic fiber paper layer and the alumina ceramic crucible; the bottom of the PBN crucible seed crystal cavity is sealed by a boron nitride ceramic rod.
PBN is an abbreviation for pyrolytic boron nitride.
In order to ensure the smooth production, the aluminum silicate ceramic fiber paper layer completely covers the outer side wall of the PBN crucible, namely, no gap exists.
The method for growing the single crystal by using the alumina ceramic crucible comprises the following steps:
1) cleaning raw materials and auxiliary materials:
1.1) soaking the indium phosphide polycrystal material in a mixed solution of ammonium hydroxide and hydrogen peroxide for 2-4 h, ultrasonically cleaning the material for 2-4 h by using pure water, replacing the pure water every hour during ultrasonic cleaning, and drying the material;
1.2) carrying out ultrasonic treatment on an alumina ceramic crucible, an alumina ceramic sealing cap, an aluminum silicate ceramic fiber sealing gasket and a boron nitride ceramic rod for 2-4 h by pure water, replacing the pure water every hour during ultrasonic cleaning, and then drying; drying for 2h at 120 ℃ by using a vacuum drying oven after the ultrasonic treatment is finished;
1.3) soaking the indium phosphide seed crystals in a mixed solution of bromine and absolute ethyl alcohol for 1-5 min, ultrasonically cleaning the seed crystals for 2-4 h by using pure water, replacing the pure water every hour during ultrasonic cleaning, and then drying the seed crystals;
1.4) soaking the PBN crucible in aqua regia for 2-4 h, ultrasonically cleaning the PBN crucible for 2-4 h by pure water, replacing the pure water every hour during ultrasonic cleaning, airing the PBN crucible under natural conditions, and oxidizing the PBN crucible for 3-4 h at the temperature of 1000 +/-100 ℃ under pure oxygen atmosphere;
2) charging:
2.1) putting indium phosphide polycrystal, indium phosphide seed crystal, anhydrous boron oxide, a doping agent, an alumina ceramic crucible, an alumina ceramic sealing cap, an alumina silicate ceramic fiber sealing gasket, alumina silicate ceramic fiber paper, a boron nitride ceramic rod and other raw and auxiliary materials into a vacuum glove box, and vacuumizing to below 1.0E-2 Pa;
2.2) putting indium phosphide seed crystals into a PBN crucible seed crystal cavity, sealing the lower end of the PBN crucible seed crystal cavity by using a boron nitride ceramic rod, and putting indium phosphide polycrystal, anhydrous boron oxide, 6N red phosphorus and a doping agent into a PBN crucible;
2.3) paving a layer of aluminum silicate ceramic fiber paper on the inner wall of the alumina ceramic crucible, putting the PBN crucible containing the raw and auxiliary materials into the alumina ceramic crucible, wherein the aluminum silicate ceramic fiber paper has certain plasticity, and the PBN crucible containing the raw and auxiliary materials presses the aluminum silicate ceramic fiber paper to ensure that the alumina ceramic crucible, the aluminum silicate ceramic fiber paper and the PBN crucible are tightly attached to each other;
2.4) placing an aluminum silicate ceramic fiber sealing gasket on the sealing surface of the alumina ceramic crucible, and screwing the alumina ceramic sealing cap and the alumina ceramic crucible tightly;
3) growing a single crystal:
3.1) taking the alumina ceramic crucible filled with the materials out of the vacuum glove box, placing the alumina ceramic crucible in a VGF single crystal furnace, heating to 350 +/-10 ℃ within 30-45 min, and vacuumizing the furnace to-0.1 +/-0.01 MPa;
3.2) controlling the heating rate to be 3-5 ℃/min, heating for 3-5 h to 1070-1090 ℃ of the melting point of the indium phosphide polycrystal material, melting the indium phosphide polycrystal material in the furnace, and melting 5-15 mm of indium phosphide seed crystals;
3.3) keeping the temperature for 22-24 h, controlling the temperature to slowly decrease to ensure that the temperature gradient of a growth interface is 5-6 ℃/cm, the temperature decrease rate is 0-5 ℃/h, carrying out stepped temperature decrease growth, and starting a single crystal furnace when the temperature is decreased to below 150 ℃ to obtain the indium phosphide single crystal.
The sealing surface of the alumina ceramic crucible, namely the surface of the alumina ceramic sealing cap contacting with the alumina ceramic crucible.
And in the step 3.3), when the growth interface is reduced to the temperature (1062 +/-7 ℃) below the crystallization point, the growth is started, after the growth is finished, the temperature is about 900 ℃, the temperature is reduced, and when the temperature is reduced to below 150 ℃, the ingot is discharged.
In order to improve the cleaning effect and further improve the product quality, in the step 1.1), the volume ratio of ammonium hydroxide (EL grade), hydrogen peroxide (EL grade) and pure water in the mixed solution of ammonium hydroxide and hydrogen peroxide is (1.5-2.5) to 1: 1; the drying is carried out in a vacuum drying oven at the temperature of 115-125 ℃ for 1.5-2 h. In the step 1.2), the drying is carried out in a vacuum drying oven at the temperature of 115-125 ℃ for 1.5-2 h.
In order to further improve the cleaning effect and further improve the product quality, in the step 1.3), the mass ratio of bromine to absolute ethyl alcohol is 1 (2.5-3.5); the drying is carried out in a vacuum drying oven at the temperature of 115-125 ℃ for 1.5-2 h.
In order to avoid pollution, in the step 1.4), after ultrasonic cleaning is finished, the ultrasonic cleaning solution is placed on a hundred-grade clean workbench to be dried.
In order to further improve the product quality, in the step 2.2), the mass ratio of the indium phosphide polycrystal, the anhydrous boron oxide, the 6N red phosphorus and the dopant is as follows: (3500-4000): (36-48): (30-60): (0 to 1).
The prior art is referred to in the art for techniques not mentioned in the present invention.
When the single crystal grows, the alumina ceramic crucible is used for replacing the quartz crucible, quartz oxyhydrogen flame welding seal is not needed, nitrogen is not needed to be filled into the VGF single crystal furnace for balancing pressure, the inside of the single crystal furnace is kept in a vacuum state, meanwhile, a layer of plastic aluminum silicate ceramic fiber paper is added between the PBN crucible and the outer crucible, the joint state of the PBN crucible and the outer crucible is improved, the stability of a temperature field of the single crystal furnace is greatly improved, the dislocation density of an indium phosphide single crystal can be reduced, the crystallization rate is improved, and a large-size high-quality indium phosphide substrate is obtained; meanwhile, the loss of raw and auxiliary materials and equipment caused by cracking of the quartz tube in the prior art is avoided, the service life of the equipment is prolonged, and the method is different from the disposable use of the quartz tube.
Drawings
FIG. 1 is a schematic view of the structure of the alumina ceramic crucible of the present invention;
in the figure, 1 is a boron nitride ceramic rod; 2 is seed crystal; 3 is an alumina ceramic crucible; 31 is a seed crystal cavity of an alumina ceramic crucible; 32 is the cone part (angle 90 degree) of the alumina ceramic crucible; 4 is an aluminum silicate ceramic fiber paper layer; 5 is indium phosphide polycrystal material; PBN crucible 6; 61 is a PBN crucible seed crystal cavity; PBN crucible taper (angle 90 °) 62; 7 is an aluminum silicate ceramic fiber sealing gasket; and 8 is an alumina ceramic sealing cap.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used herein in an orientation that is based on the orientation or positional relationship shown in the drawings or in use, and are used for convenience in describing the present application, but do not indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present application.
Example 1
As shown in figure 1, the alumina ceramic crucible comprises an alumina ceramic crucible, an alumina ceramic sealing cap, an alumina silicate ceramic fiber sealing gasket and an alumina silicate ceramic fiber paper layer; the alumina ceramic crucible comprises a seed crystal cavity, a cone part and a body part which are sequentially connected from bottom to top, wherein the angle of the cone part is 90 degrees, the top of the body part is of an open structure, external threads are arranged on the periphery of the top of the body part, and internal threads matched with the external threads on the body part are arranged at the bottom of the alumina ceramic sealing cap; the aluminum silicate ceramic fiber sealing gasket comprises a first sealing gasket and a second sealing gasket, the first sealing gasket is sleeved at the bottom of the external thread of the body part, the second sealing gasket is arranged at the top of the internal thread of the alumina ceramic sealing cap, the alumina ceramic sealing cap is in threaded connection with the top of the body part, and the ceramic fiber sealing gasket is sealed between the alumina ceramic sealing cap and the top of the body part; the alumina silicate ceramic fiber paper layer is movably paved on the inner side of the alumina ceramic crucible.
Example 2
The using structure of the alumina ceramic crucible in the previous embodiment further comprises a PBN crucible, wherein the PBN crucible is positioned on the inner side of the alumina silicate ceramic fiber paper layer, the angle of a cone part of the PBN crucible is the same as that of the cone part of the alumina ceramic crucible, the PBN crucible and the alumina silicate ceramic fiber paper layer are tightly attached, the alumina silicate ceramic fiber paper layer and the alumina ceramic crucible are tightly attached, and the alumina silicate ceramic fiber paper layer completely covers the outer side wall of the PBN crucible; the bottom of the PBN crucible seed crystal cavity is sealed by a boron nitride ceramic rod.
The method for growing single crystal by using the alumina ceramic crucible in the above example comprises the following steps:
firstly, cleaning raw and auxiliary materials:
1. preparing a solution by using ammonium hydroxide (containing 25 wt% of ammonia), hydrogen peroxide (the mass concentration is 35%) and pure water according to the volume ratio of 2:1:1, soaking 4000g of indium phosphide polycrystal material in the solution for 4 hours, ultrasonically cleaning the indium phosphide polycrystal material for 4 hours by using the pure water, replacing the pure water every hour during ultrasonic treatment, and drying the indium phosphide polycrystal material for 2 hours at 120 ℃ by using a vacuum drying oven after the ultrasonic treatment;
2. performing ultrasonic treatment on an alumina ceramic crucible, an alumina ceramic sealing cap, an aluminum silicate ceramic fiber sealing gasket and a boron nitride ceramic rod for 4 hours by pure water, replacing the pure water once per hour, and drying for 2 hours at 120 ℃ by using a vacuum drying oven after the ultrasonic treatment is completed;
3. preparing a solution by using bromine and absolute ethyl alcohol according to the ratio of 1:3, soaking indium phosphide seed crystals in the solution for about 3min, performing ultrasonic treatment for 4h by using pure water, replacing the pure water every hour during ultrasonic treatment, and drying for 2h at 120 ℃ by using a vacuum drying oven after the ultrasonic treatment;
4. soaking the PBN crucible in aqua regia for 4h, ultrasonically cleaning with pure water for 4h, replacing the pure water every hour during the ultrasonic treatment, airing on a hundred-grade clean workbench after the ultrasonic treatment is finished, and oxidizing for 4h at 1000 ℃ under the pure oxygen atmosphere;
secondly, charging:
1. putting indium phosphide polycrystal, seed crystal, anhydrous boron oxide, dopant, alumina ceramic crucible, alumina ceramic sealing cap, alumina silicate ceramic fiber sealing gasket, alumina silicate ceramic fiber paper, boron nitride ceramic rod and other raw and auxiliary materials into a vacuum glove box, and vacuumizing to below 1.0E-2 Pa;
2. putting seed crystal into a PBN crucible seed crystal cavity, sealing the lower end of the PBN crucible seed crystal cavity by using a boron nitride ceramic rod, and then carrying out 4000g indium phosphide polycrystal without crystal48g of boron oxide hydrate, 60g of 6N red phosphorus and In as dopant2S30.5g of the mixture is put into a PBN crucible;
3. paving a layer of aluminum silicate ceramic fiber paper on the inner wall of the alumina ceramic crucible, putting the PBN crucible filled with the raw and auxiliary materials into the alumina ceramic crucible, wherein the aluminum silicate ceramic fiber paper has certain plasticity, and the PBN crucible filled with the raw and auxiliary materials presses the aluminum silicate ceramic fiber paper to enable the alumina ceramic crucible, the aluminum silicate ceramic fiber paper and the PBN crucible to be tightly attached to each other;
4. placing an aluminum silicate ceramic fiber sealing gasket on the sealing surface of the alumina ceramic crucible, and screwing the alumina ceramic sealing cap and the alumina ceramic crucible tightly;
III, single crystal growth
1. Taking out the loaded materials, placing the materials in a VGF single crystal furnace, heating to 350 ℃ within 30-45 min, and vacuumizing the furnace to-0.1 MPa;
2. controlling the heating rate to be 4 ℃/min, heating to the melting point of the indium phosphide polycrystal material of 1070-1090 ℃, melting the indium phosphide polycrystal material in the furnace, and melting the seed crystal by 5-15 mm;
3. and (3) keeping the temperature for 24h, controlling the temperature to slowly decrease to ensure that the temperature gradient of a growth interface is 5 ℃/cm, the temperature decrease rate is 2 ℃/h, carrying out stepped temperature decrease growth, and starting a single crystal furnace to take out the obtained indium phosphide single crystal when the temperature is decreased to be below 150 ℃.
4. The obtained indium phosphide single crystal head and tail cutting sampling piece is subjected to Hall test and dislocation corrosion, and the performances of the indium phosphide single crystal obtained by the existing VGF process (a quartz crucible is adopted, and nitrogen or argon is used for balancing pressure during preparation) are compared as follows:
TABLE 1
TABLE 2
As can be seen from the table above, the single crystal yield of the produced single crystal is obviously improved, the dislocation density of the product is obviously reduced, the uniformity of the performance of the product is improved, the product quality is stable after multiple tests and pilot tests, and the requirement of expanding production is met.
Claims (10)
1. An alumina ceramic crucible, characterized in that: comprises an alumina ceramic crucible, an alumina ceramic sealing cap, an aluminum silicate ceramic fiber sealing gasket and an aluminum silicate ceramic fiber paper layer; the alumina ceramic crucible comprises a seed crystal cavity, a pyramid part and a body part which are sequentially connected from bottom to top, the top of the body part is of an open structure, an alumina ceramic sealing cap is in threaded connection with the top of the body part, and a ceramic fiber sealing gasket is arranged between the alumina ceramic sealing cap and the top of the body part; the alumina silicate ceramic fiber paper layer is movably paved on the inner side of the alumina ceramic crucible.
2. The alumina ceramic crucible of claim 1, wherein: the periphery of the top of the body part is provided with an external thread, and the bottom of the alumina ceramic sealing cap is provided with an internal thread matched with the external thread on the body part; the aluminum silicate ceramic fiber sealing gasket comprises a first sealing gasket and a second sealing gasket, the first sealing gasket is sleeved at the bottom of the external thread of the body, and the second sealing gasket is arranged at the top of the internal thread of the aluminum oxide ceramic sealing cap.
3. The alumina ceramic crucible of claim 1 or 2, wherein: the taper angle is 90 deg..
4. The use structure of the alumina ceramic crucible as set forth in any one of claims 1 to 3, wherein: the PBN crucible is positioned on the inner side of the aluminum silicate ceramic fiber paper layer, the PBN crucible and the aluminum silicate ceramic fiber paper layer are tightly attached, and the aluminum silicate ceramic fiber paper layer and the aluminum oxide ceramic crucible are tightly attached; the bottom of the PBN crucible seed crystal cavity is sealed by a boron nitride ceramic rod.
5. A method of growing a single crystal using the alumina ceramic crucible of any one of claims 1 to 3, wherein: the method comprises the following steps:
1) cleaning raw materials and auxiliary materials:
1.1) soaking the indium phosphide polycrystal material in a mixed solution of ammonium hydroxide and hydrogen peroxide for 2-4 h, ultrasonically cleaning the material for 2-4 h by using pure water, replacing the pure water every hour during ultrasonic cleaning, and drying the material;
1.2) carrying out ultrasonic treatment on an alumina ceramic crucible, an alumina ceramic sealing cap, an aluminum silicate ceramic fiber sealing gasket and a boron nitride ceramic rod for 2-4 h by pure water, replacing the pure water every hour during ultrasonic cleaning, and then drying; drying for 2h at 120 ℃ by using a vacuum drying oven after the ultrasonic treatment is finished;
1.3) soaking the indium phosphide seed crystals in a mixed solution of bromine and absolute ethyl alcohol for 1-5 min, ultrasonically cleaning the seed crystals for 2-4 h by using pure water, replacing the pure water every hour during ultrasonic cleaning, and then drying the seed crystals;
1.4) soaking the PBN crucible in aqua regia for 2-4 h, ultrasonically cleaning the PBN crucible for 2-4 h by pure water, replacing the pure water every hour during ultrasonic cleaning, airing the PBN crucible under natural conditions, and oxidizing the PBN crucible for 3-4 h at the temperature of 1000 +/-100 ℃ under pure oxygen atmosphere;
2) charging:
2.1) putting the indium phosphide polycrystal, the indium phosphide seed crystal, the anhydrous boron oxide, the doping agent, the alumina ceramic crucible, the alumina ceramic sealing cap, the alumina silicate ceramic fiber sealing gasket, the alumina silicate ceramic fiber paper and the boron nitride ceramic rod into a vacuum glove box, and vacuumizing to below 1.0E-2 Pa;
2.2) putting indium phosphide seed crystals into a PBN crucible seed crystal cavity, sealing the lower end of the PBN crucible seed crystal cavity by using a boron nitride ceramic rod, and putting indium phosphide polycrystal, anhydrous boron oxide, 6N red phosphorus and a doping agent into a PBN crucible;
2.3) paving a layer of aluminum silicate ceramic fiber paper on the inner wall of the alumina ceramic crucible, putting the PBN crucible containing the raw and auxiliary materials into the alumina ceramic crucible, wherein the aluminum silicate ceramic fiber paper has certain plasticity, and the PBN crucible containing the raw and auxiliary materials presses the aluminum silicate ceramic fiber paper to ensure that the alumina ceramic crucible, the aluminum silicate ceramic fiber paper and the PBN crucible are tightly attached to each other;
2.4) placing an aluminum silicate ceramic fiber sealing gasket on the sealing surface of the alumina ceramic crucible, and screwing the alumina ceramic sealing cap and the alumina ceramic crucible tightly;
3) growing a single crystal:
3.1) taking the alumina ceramic crucible filled with the materials out of the vacuum glove box, placing the alumina ceramic crucible in a VGF single crystal furnace, heating to 350 +/-10 ℃ within 30-45 min, and vacuumizing the furnace to-0.1 +/-0.01 MPa;
3.2) controlling the heating rate to be 3-5 ℃/min, heating for 3-5 h to 1070-1090 ℃ of the melting point of the indium phosphide polycrystal material, melting the indium phosphide polycrystal material in the furnace, and melting 5-15 mm of indium phosphide seed crystals;
3.3) keeping the temperature for 22-24 h, controlling the temperature to slowly decrease to ensure that the temperature gradient of a growth interface is 5-6 ℃/cm, the temperature decrease rate is 0-5 ℃/h, carrying out stepped temperature decrease growth, and starting a single crystal furnace when the temperature is decreased to below 150 ℃ to obtain the indium phosphide single crystal.
6. The method of claim 5, wherein: in the step 1.1), the volume ratio of ammonium hydroxide, hydrogen peroxide and pure water in the mixed solution of ammonium hydroxide and hydrogen peroxide is (1.5-2.5) to 1: 1; the drying is carried out in a vacuum drying oven at the temperature of 115-125 ℃ for 1.5-2 h.
7. The method of claim 5 or 6, wherein: in the step 1.2), the drying is carried out in a vacuum drying oven at the temperature of 115-125 ℃ for 1.5-2 h.
8. The method of claim 5 or 6, wherein: in the step 1.3), the mass ratio of bromine to absolute ethyl alcohol is 1 (2.5-3.5); the drying is carried out in a vacuum drying oven at the temperature of 115-125 ℃ for 1.5-2 h.
9. The method of claim 5 or 6, wherein: and step 1.4), after ultrasonic cleaning, putting the ultrasonic cleaning machine on a hundred-grade clean workbench for airing.
10. The method of claim 5 or 6, wherein: in the step 2.2), the mass ratio of the indium phosphide polycrystal, the anhydrous boron oxide, the 6N red phosphorus and the dopant is as follows: (3500-4000): (36-48): (30-60): (0 to 1).
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| JP2014139120A (en) * | 2012-12-19 | 2014-07-31 | Sumitomo Electric Ind Ltd | Crucible for crystal growth and production method of single crystal using the same |
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| CN214830774U (en) * | 2021-05-26 | 2021-11-23 | 中锗科技有限公司 | Alumina ceramic crucible and use structure thereof |
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| JP2014139120A (en) * | 2012-12-19 | 2014-07-31 | Sumitomo Electric Ind Ltd | Crucible for crystal growth and production method of single crystal using the same |
| CN106400101A (en) * | 2016-10-11 | 2017-02-15 | 广东先导先进材料股份有限公司 | Compound semiconductor monocrystal growing device and method |
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