CN118516740A - Beta-Ga based on fluxing agent2O3Crystal growth method - Google Patents
Beta-Ga based on fluxing agent2O3Crystal growth method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 125
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002109 crystal growth method Methods 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 9
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 9
- 239000006184 cosolvent Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 66
- 238000001816 cooling Methods 0.000 claims description 35
- 229910052697 platinum Inorganic materials 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 28
- 230000004907 flux Effects 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 229910003069 TeO2 Inorganic materials 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001195 gallium oxide Inorganic materials 0.000 abstract description 14
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 229910052741 iridium Inorganic materials 0.000 abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 5
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- 239000012856 weighed raw material Substances 0.000 description 4
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- 238000004364 calculation method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007716 flux method Methods 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
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- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a beta-Ga 2O3 crystal growth method based on a fluxing agent. The invention adopts nontoxic fluxing agent tellurium dioxide (TeO 2) and alkali metal carbonate to grow beta-Ga 2O3 monocrystal, which can avoid using expensive iridium, reduce energy consumption and greatly reduce crystal growth cost. Tellurium dioxide in the cosolvent can reduce the high melting point of gallium oxide due to the characteristic of low melting point, so that the method can grow beta-Ga 2O3 crystals in a low-temperature environment, and the volatilization and decomposition problems of gallium oxide in the crystal growth can be effectively solved; and the melting point of gallium oxide can be further reduced by introducing alkali carbonate, and the solution viscosity is reduced, so that the solution obtained by melting has lower viscosity, is beneficial to solute transmission in the crystal growth process, can effectively avoid inclusion generation, and is beneficial to growth of large-size high-quality beta-Ga 2O3 single crystals.
Description
Technical Field
The invention relates to a beta-Ga 2O3 crystal growth method based on a fluxing agent, and belongs to the technical field of crystal material growth.
Background
The semiconductor material is used as a core material for promoting the development of the semiconductor industry, and plays an irreplaceable role in the national defense and civil fields. With the rapid development of technology, higher requirements are being placed on the power and device performance of semiconductor materials, and electronic devices with high voltage resistance, low loss and high power have become the trend of the future electronic industry. Thus, there is a need to explore and develop new semiconductor materials to better advance the corresponding technological field.
The beta-Ga 2O3 crystal is a novel ultra-wide band gap semiconductor material, and compared with a third-generation semiconductor such as SiC, gaN and the like, the beta-Ga 2O3 crystal has the advantages of wider band gap, shorter absorption cut-off edge and the like, and is a preferable material applied to optical communication, photoelectric detection and power devices in the deep ultraviolet region. In addition, the beta-Ga 2O3 crystal also has higher breakdown voltage and lower loss, is an ideal material inferior to diamond in pressure resistance and power, and can be used for preparing high-pressure-resistance, high-power and low-loss power devices. Therefore, the beta-Ga 2O3 crystal material is one of the most popular semiconductor materials in the field of semiconductor material research at present, and is widely paid attention at home and abroad.
Beta-Ga 2O3 crystal is a consistent molten compound, but the melting point is up to 1800 ℃, and large-size beta-Ga 2O3 single crystal is generally grown by adopting a high-temperature melt method such as a Czochralski method, a Bridgman method, a guided mode method, a light floating zone method and the like. But the problems of volatilization of high-temperature raw materials, corrosion of an iridium noble metal crucible, unstable crystal growth, spiral crystal growth, serious coloring and the like still exist in the aspect of crystal growth. In the last 60 th century, it was proposed to grow β -Ga 2O3 crystals by the flux method, which can effectively reduce the growth temperature of the crystals. However, the fluxing agent mainly comprises toxic raw materials such as PbO, pbF 2 and the like, and has certain potential safety hazard. In addition, the solution viscosity of the flux systems is too high, solute transport is not easy, and grown crystals have macroscopic defects such as wrapping, cloud layers and the like. Although the growth temperature of beta-Ga 2O3 crystals grown by the flux method reported in the literature is generally lower than 1600 ℃, the problem of volatilization of the high-temperature gallium oxide melt still exists. For example, patent document CN114250514a discloses a flux for beta-gallium trioxide crystal growth and a crystal growth method based on the flux, the invention uses B 2O3 -alkali metal oxide as main material, and small amount of molybdenum oxide such as MoO 3, molybdate such as K 2Mo2O7、Na2Mo2O7, etc. as a flux system for beta-Ga 2O3 crystal growth. The crystal growth temperature range of the invention is 950-1080 ℃, and the use of the cosolvent reduces the growth temperature of the crystal. However, the problems of high growth temperature and volatilization of the high-temperature gallium oxide melt still exist, and the preparation method is complicated. Therefore, further exploration of suitable flux systems is urgent for growing high quality β -Ga 2O3 crystals.
Disclosure of Invention
Aiming at the technical problems of the existing high-quality beta-Ga 2O3 crystal growth, the invention provides a beta-Ga 2O3 crystal growth method based on a fluxing agent. The invention adopts nontoxic fluxing agent tellurium dioxide (TeO 2) and alkali metal carbonate to grow beta-Ga 2O3 monocrystal, which can avoid using expensive iridium, reduce energy consumption and greatly reduce crystal growth cost. Tellurium dioxide in the cosolvent can reduce the high melting point of gallium oxide due to the characteristic of low melting point, so that the method can grow beta-Ga 2O3 crystals in a low-temperature environment, and the volatilization and decomposition problems of gallium oxide in the crystal growth can be effectively solved; and the melting point of gallium oxide can be further reduced by introducing alkali carbonate, and the solution viscosity is reduced, so that the solution obtained by melting has lower viscosity, is beneficial to solute transmission in the crystal growth process, can effectively avoid inclusion generation, and is beneficial to growth of large-size high-quality beta-Ga 2O3 single crystals.
The technical scheme of the invention is as follows:
A flux-based beta-Ga 2O3 crystal growth method comprising the steps of:
(1) The beta-Ga 2O3 and the fluxing agent are ground and mixed uniformly, the temperature is raised to enable the materials to be completely melted, and then the materials are stirred at constant temperature to obtain uniform molten liquid; the cosolvent is TeO 2 and alkali metal carbonate; the mol ratio of the beta-Ga 2O3、TeO2 to the alkali metal carbonate is 1:4.1-7.9:0.5-1.5;
(2) The temperature of the molten liquid is reduced to be higher than the temperature of the saturation point, and a platinum rod or beta-Ga 2O3 seed crystal is put in and rotated; then cooling to the saturation point temperature, cooling and growing, and cooling to room temperature after the crystal growth is finished to obtain the beta-Ga 2O3 crystal.
According to a preferred embodiment of the present invention, in step (1), the mixture of β -Ga 2O3 and the flux is placed in a platinum crucible, and then melted and crystal grown in a crystal growth furnace.
According to a preferred embodiment of the present invention, in the step (1), the alkali metal carbonate is one or a combination of two or more of lithium carbonate, sodium carbonate and potassium carbonate.
According to a preferred embodiment of the present invention, in the step (1), the molar ratio of β -Ga 2O3、TeO2 to alkali metal carbonate is 1:7.9:1.5.
According to the invention, in the step (1), the melting temperature is 830-920 ℃, and the heating rate is 0.5-2 ℃ per minute.
According to the invention, in the step (1), the constant temperature stirring is performed by using a platinum stirring paddle, the stirring temperature is 830-920 ℃, and the stirring time is 18-24 hours.
According to the invention, in the step (2), the saturation point temperature is 720-770 ℃; the temperature above the saturation point is the saturation point temperature plus 2-5 ℃.
According to the invention, in the step (2), the cooling rate in the process of cooling to the saturation point temperature is 0.01-5 ℃/h; the cooling rate of the cooling growth is 0.05-5 ℃/d, preferably 0.05-0.2 ℃/d, if the rate is too fast or too slow, polycrystal is easy to appear, the temperature is reduced to 700-750 ℃, and the crystal growth is finished.
According to the invention, in the step (2), the rotation parameters of the platinum rod or the beta-Ga 2O3 seed crystal are as follows: the rotation speed is 5-50rd, and the stop time is 5-50s when the motor runs for 30-180 s.
According to the invention, the preferred unit cell parameters of the beta-Ga 2O3 crystals are Α=γ=90°, β= 103.866 (4) °, z=2, belonging to the monoclinic system, the space group being C2/m.
The invention has the technical characteristics and beneficial effects that:
1. The fluxing agent does not contain toxic raw materials such as lead oxide, lead fluoride and the like, and avoids potential safety hazards existing in crystal growth. Tellurium dioxide in the cosolvent can reduce the high melting point of gallium oxide due to the characteristic of low melting point, and the introduction of alkali carbonate can further reduce the melting point of gallium oxide and reduce the solution viscosity. The cosolvent is suitable for the melt method growth of the beta-Ga 2O3 crystal, so that the beta-Ga 2O3 crystal can grow in a lower temperature range, the crystal growth temperature range is approximately 700-800 ℃, and compared with the melt method growth of the beta-Ga 2O3 crystal reported in the literature, the growth temperature is approximately reduced by 400-800 ℃, and volatilization and decomposition of high-temperature crystal components are effectively inhibited. The cosolvent ensures that the solution obtained by melting the invention is clear and transparent, and is favorable for observing the growth condition of crystals; has lower viscosity, is beneficial to solute transmission in the crystal growth process, can effectively avoid inclusion generation, and is beneficial to growth of large-size high-quality beta-Ga 2O3 single crystals. Meanwhile, the fluxing agent can avoid using expensive iridium, reduce energy consumption and reduce crystal growth cost.
2. The beta-Ga 2O3 crystal growth method provided by the invention has the advantages of simple method, rapid growth and more simplified flux proportion, and can grow the centimeter-level high-quality beta-Ga 2O3 crystal, if a platinum crucible with larger size is used, the cooling interval of the crystal is increased, the growth period of the crystal is prolonged, and the larger-size beta-Ga 2O3 single crystal can be obtained. The single crystal analysis to obtain monoclinic system with space group C2/m and unit cell parameters of α＝γ＝90°,β＝103.866(4)°,Z＝2。
Drawings
FIG. 1 is an external view of a β -Ga 2O3 single crystal grown in example 1-3.
FIG. 2 is an X-ray diffraction pattern and theoretical calculation result of the beta-Ga 2O3 single crystal powder grown in example 3.
FIG. 3 is a diagram showing the structure of the β -Ga 2O3 crystal of the present invention.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials, or apparatus, unless otherwise specified, are all commercially available.
Example 1
A flux-based beta-Ga 2O3 crystal growth method comprising the steps of:
(1) Gallium oxide powder with the purity of 99.999%, tellurium dioxide powder with the purity of 99.99%, lithium carbonate powder with the purity of 99.99% and potassium carbonate powder with the purity of 99.99% are used as experimental raw materials, and are weighed according to the mol ratio of beta-Ga 2O3:TeO2:K2CO3:Li2CO3 =1:4.1:0.5:0.5.
The weighed raw materials are put into an agate mortar to be fully ground and uniformly mixed, the agate mortar is put into a platinum crucible with the volume of phi 50mm multiplied by 50mm, the platinum crucible with the mixture is placed at the central position of a fused salt single crystal growth furnace heated by a resistance wire and then heated to 870 ℃ at 1 ℃/min, the mixture is completely melted, the platinum stirring paddle is put into the temperature, the stirring is continued for 24 hours, and the platinum stirring paddle is taken out after uniform high-temperature molten liquid is obtained.
(2) Determining the saturation temperature of the solution by adopting a seed crystal test contact method, preparing high-temperature molten liquid according to the method, putting the seed crystal into the high-temperature molten liquid for about 0.5mm at a certain temperature, and observing the state of the seed crystal, wherein if the seed crystal is molten, the solution is in an unsaturated state; if the seed crystal grows up, the solution is in a supersaturated state, and if the seed crystal has no obvious change, the solution is saturated at the moment, and the determination of the saturation point is repeatedly performed for a plurality of times, so that the accuracy is less than 1 ℃. The saturation point temperature was measured to be 770 ℃.
(3) And (3) cooling the high-temperature molten liquid obtained in the step (1) to a temperature 2 ℃ higher than the saturation point, putting the overheated platinum rod into the high-temperature molten liquid and rotating (the rotating speed is 30rd, the stop is 30s when the operation is 60 s), cooling the growth solution to the saturation point temperature at a cooling rate of 1 ℃/h, cooling to 750 ℃ at a cooling rate of 5 ℃/d, and after the crystal growth is finished, lifting the platinum rod to the liquid level, and naturally cooling to the room temperature to finally obtain the beta-Ga 2O3 crystal.
As shown in FIG. 1 (a), the beta-Ga 2O3 crystal obtained in this example has poor crystal quality overall at a cooling rate of 5 ℃/d, a large amount of floccules exist in the crystal, and the transparent part is less.
Example 2
A flux-based beta-Ga 2O3 crystal growth method comprising the steps of:
(1) Gallium oxide powder with the purity of 99.999 percent, tellurium dioxide powder with the purity of 99.99 percent and potassium carbonate powder with the purity of 99.99 percent are used as experimental raw materials and are weighed according to the mol ratio of beta-Ga 2O3:TeO2:K2CO3 =1:6.1:0.5.
The weighed raw materials are put into an agate mortar to be fully ground and uniformly mixed, the agate mortar is put into a platinum crucible with the volume of phi 50mm multiplied by 50mm, the platinum crucible with the mixture is placed at the central position of a fused salt single crystal growth furnace heated by a resistance wire and then heated to 900 ℃ at the speed of 1 ℃/min, the mixture is completely melted, the platinum stirring paddles are put into the mixture at the temperature, the mixture is continuously stirred for 24 hours, and the platinum stirring paddles are taken out after uniform high-temperature molten liquid is obtained.
(2) Determining the saturation temperature of the solution by adopting a seed crystal test contact method, preparing high-temperature molten liquid according to the method, putting the seed crystal into the high-temperature molten liquid for about 0.5mm at a certain temperature, and observing the state of the seed crystal, wherein if the seed crystal is molten, the solution is in an unsaturated state; if the seed crystal grows up, the solution is in a supersaturated state, and if the seed crystal has no obvious change, the solution is saturated at the moment, and the determination of the saturation point is repeatedly performed for a plurality of times, so that the accuracy is less than 1 ℃. The saturation point temperature was measured to be 760 ℃.
(3) And (3) cooling the high-temperature molten liquid obtained in the step (1) to a temperature 2 ℃ higher than the saturation point, putting the overheated platinum rod into the high-temperature molten liquid and rotating (the rotating speed is 30rd, the stop is 30s when the operation is 60 s), cooling the growth solution to the saturation point temperature at a cooling rate of 1 ℃/h, cooling to 750 ℃ at a cooling rate of 5 ℃/d, and after the crystal growth is finished, lifting the platinum rod to the liquid level, and naturally cooling to the room temperature to finally obtain the beta-Ga 2O3 crystal.
The beta-Ga 2O3 crystal obtained in this example is shown in FIG. 1 (b). The crystal is transparent and has a natural growth surface.
Example 3
A flux-based beta-Ga 2O3 crystal growth method comprising the steps of:
(1) Gallium oxide powder with the purity of 99.999 percent, tellurium dioxide powder with the purity of 99.99 percent and lithium carbonate powder with the purity of 99.99 percent are used as experimental raw materials and are weighed according to the mol ratio of beta-Ga 2O3:TeO2:Li2CO3 =1:7.9:1.5.
The weighed raw materials are put into an agate mortar to be fully ground and uniformly mixed, the agate mortar is put into a platinum crucible with the volume of phi 50mm multiplied by 50mm, the platinum crucible with the mixture is placed at the central position of a fused salt single crystal growth furnace heated by a resistance wire and then heated to 850 ℃ at the speed of 1 ℃/min, the mixture is completely melted, the platinum stirring paddles are put into the fused salt single crystal growth furnace at the temperature, the fused salt single crystal growth furnace is continuously stirred for 24 hours, and the platinum stirring paddles are taken out after uniform high-temperature fused liquid is obtained.
(2) Determining the saturation temperature of the solution by adopting a seed crystal test contact method, preparing high-temperature molten liquid according to the method, putting the seed crystal into the high-temperature molten liquid for about 0.5mm at a certain temperature, and observing the state of the seed crystal, wherein if the seed crystal is molten, the solution is in an unsaturated state; if the seed crystal grows up, the solution is in a supersaturated state, and if the seed crystal has no obvious change, the solution is saturated at the moment, and the determination of the saturation point is repeatedly performed for a plurality of times, so that the accuracy is less than 1 ℃. The saturation point temperature was measured to be 740 ℃.
(3) And (3) reducing the high-temperature molten liquid obtained in the step (1) to a temperature 2 ℃ higher than the saturation point, putting a overheated platinum rod into the high-temperature molten liquid and rotating (the rotating speed is 30rd, the stop is 30s when the operation is 60 s), reducing the temperature of the growth solution to the saturation point temperature at a cooling rate of 1 ℃/h, then reducing the temperature to 720 ℃ at a cooling rate of 0.2 ℃/d, and after the crystal growth is finished, extracting the liquid level of the crystal by the platinum rod, and naturally cooling to the room temperature to finally obtain the beta-Ga 2O3 crystal.
The beta-Ga 2O3 crystal obtained in the embodiment is as shown in fig. 1 (c), and has good crystal quality, transparency and regular shape.
Example 4
A flux-based beta-Ga 2O3 crystal growth method comprising the steps of:
(1) Gallium oxide powder with the purity of 99.999 percent, tellurium dioxide powder with the purity of 99.99 percent and lithium carbonate powder with the purity of 99.99 percent are used as experimental raw materials and are weighed according to the mol ratio of beta-Ga 2O3:TeO2:Li2CO3 =1:7.9:1.5.
The weighed raw materials are put into an agate mortar to be fully ground and uniformly mixed, the agate mortar is put into a platinum crucible with the volume of phi 50mm multiplied by 50mm, the platinum crucible with the mixture is placed at the central position of a fused salt single crystal growth furnace heated by a resistance wire and then heated to 850 ℃ at the speed of 1 ℃/min, the mixture is completely melted, the platinum stirring paddles are put into the fused salt single crystal growth furnace at the temperature, the fused salt single crystal growth furnace is continuously stirred for 24 hours, and the platinum stirring paddles are taken out after uniform high-temperature fused liquid is obtained.
(2) Determining the saturation temperature of the solution by adopting a seed crystal test contact method, preparing high-temperature molten liquid according to the method, putting the seed crystal into the high-temperature molten liquid for about 0.5mm at a certain temperature, and observing the state of the seed crystal, wherein if the seed crystal is molten, the solution is in an unsaturated state; if the seed crystal grows up, the solution is in a supersaturated state, and if the seed crystal has no obvious change, the solution is saturated at the moment, and the determination of the saturation point is repeatedly performed for a plurality of times, so that the accuracy is less than 1 ℃. The saturation point temperature was measured to be 740 ℃.
(3) And (3) reducing the high-temperature molten liquid obtained in the step (1) to a temperature 2 ℃ higher than the saturation point, putting a overheated platinum rod into the high-temperature molten liquid and rotating (the rotating speed is 30rd, the stop is 30s when the operation is 60 s), reducing the temperature of the growth solution to the saturation point temperature at a cooling rate of 1 ℃/h, then reducing the temperature to 720 ℃ at a cooling rate of 0.05 ℃/d, and after the crystal growth is finished, extracting the liquid level of the crystal by the platinum rod, and naturally cooling to the room temperature to finally obtain the beta-Ga 2O3 crystal.
The β -Ga 2O3 crystal obtained in this example is shown in fig. 1 (d), and on the basis of example 3, a slower cooling rate is set, so that the quality and size of the crystal are further improved, and the crystal has a good natural growth surface, is transparent and has a regular shape.
The X-ray diffraction pattern of the beta-Ga 2O3 crystal prepared in this example was tested to be consistent with the theoretical calculation result of the beta-Ga 2O3 crystal (FIG. 2), and single crystal X-ray diffraction test and structural analysis were performed, with unit cell parameters of Α=γ=90°, β= 103.866 (4) °, z=2, belonging to the monoclinic system, the space group being C2/m. It was confirmed that β -Ga 2O3 crystals were obtained. The crystal structure of beta-Ga 2O3 is shown in figure 3. Wherein FIG. 3 (a) represents an atomic coordination sphere model of β -Ga 2O3 single crystal in one unit cell, and FIG. 3 (b) is a polyhedral model of β -Ga 2O3.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A flux-based beta-Ga 2O3 crystal growth method comprising the steps of:
(1) The beta-Ga 2O3 and the fluxing agent are ground and mixed uniformly, the temperature is raised to enable the materials to be completely melted, and then the materials are stirred at constant temperature to obtain uniform molten liquid; the cosolvent is TeO 2 and alkali metal carbonate; the mol ratio of the beta-Ga 2O3、TeO2 to the alkali metal carbonate is 1:4.1-7.9:0.5-1.5;
(2) The temperature of the molten liquid is reduced to be higher than the temperature of the saturation point, and a platinum rod or beta-Ga 2O3 seed crystal is put in and rotated; then cooling to the saturation point temperature, cooling and growing, and cooling to room temperature after the crystal growth is finished to obtain the beta-Ga 2O3 crystal.
2. The flux-based β -Ga 2O3 crystal growth method according to claim 1, wherein in step (1), the β -Ga 2O3 and flux mixture is placed in a platinum crucible, and then melted and crystal grown in a crystal growth furnace.
3. The flux-based β -Ga 2O3 crystal growth process according to claim 1, wherein in step (1), the alkali metal carbonate is one or a combination of two or more of lithium carbonate, sodium carbonate or potassium carbonate.
4. The flux-based β -Ga 2O3 crystal growth process according to claim 1, wherein in step (1), the molar ratio of β -Ga 2O3、TeO2 to alkali carbonate is 1:7.9:1.5.
5. The flux-based β -Ga 2O3 crystal growth process according to claim 1, wherein in step (1), the melting temperature is 830-920 ℃ and the temperature rise rate is 0.5 ℃/min-2 ℃/min.
6. The flux-based β -Ga 2O3 crystal growth method according to claim 1, wherein in step (1), the constant temperature stirring is performed using a platinum stirrer, the stirring temperature is 830-920 ℃, and the stirring time is 18-24 hours.
7. The flux-based β -Ga 2O3 crystal growth process according to claim 1, wherein in step (2), the saturation point temperature is 720-770 ℃; the temperature above the saturation point is the saturation point temperature plus 2-5 ℃.
8. The flux-based β -Ga 2O3 crystal growth method according to claim 1, wherein in step (2), the cooling rate during cooling to the saturation point temperature is 0.01-5 ℃/h; the cooling rate of the cooling growth is 0.05-5 ℃/d, preferably 0.05-0.2 ℃/d, the temperature is reduced to 700-750 ℃, and the crystal growth is finished.
9. The flux-based β -Ga 2O3 crystal growth method according to claim 1, wherein in step (2), the rotation parameters of the platinum rod or β -Ga 2O3 seed crystal are: the rotation speed is 5-50rd, and the stop time is 5-50s when the motor runs for 30-180 s.
10. The method for growing a β -Ga 2O3 crystal based on a flux according to claim 1, wherein the unit cell parameters of the β -Ga 2O3 crystal areΑ=γ=90°, β= 103.866 (4) °, z=2, belonging to the monoclinic system, the space group being C2/m.
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