CN114250514B - Flux for beta-gallium trioxide crystal growth and crystal growth method based on flux - Google Patents
Flux for beta-gallium trioxide crystal growth and crystal growth method based on flux Download PDFInfo
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- CN114250514B CN114250514B CN202111532634.8A CN202111532634A CN114250514B CN 114250514 B CN114250514 B CN 114250514B CN 202111532634 A CN202111532634 A CN 202111532634A CN 114250514 B CN114250514 B CN 114250514B
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- 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
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
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Abstract
The invention discloses a beta-Ga 2 O 3 A flux for crystal growth and a crystal growth method based on the flux. The invention adopts B 2 O 3 Alkali metal oxides as main component, with minor amounts of molybdenum oxides such as MoO 3 Molybdates such as K 2 Mo 2 O 7 、Na 2 Mo 2 O 7 Etc. as beta-Ga 2 O 3 A fluxing agent system for crystal growth, wherein the molar ratio of the fluxing agent system to the crystal growth is 0.8-1.5: 0.8 to 2.5:0 to 0.3. The flux system provided by the invention does not contain toxic and harmful components such as lead oxide, lead fluoride and the like commonly used in high-temperature fluxes, the crystal growth temperature range is 950-1080 ℃, the growth temperature of the crystal is effectively reduced, the solvent viscosity is low, the component volatilization is less, the high-temperature solution is clear and transparent, the crystal growth process is convenient to control in real time, the obtained crystal has good quality, no wrapping phenomenon and easy obtaining of high-quality beta-Ga 2 O 3 And (5) a crystal.
Description
Technical Field
The invention relates to a method for growing single crystals, in particular to beta-Ga 2 O 3 A flux for crystal growth and a crystal growth method based on the flux.
Background
β-Ga 2 O 3 The crystal is a direct band gap semiconductor material, the band gap width is 4.9eV, the crystal belongs to a fourth generation wide band gap semiconductor material, has wider band gap than the well-known third generation semiconductor materials such as SiC, gaN and the like, has an absorption cut-off edge of 250nm, can be used for optical communication and optoelectronic devices in the deep ultraviolet region, and is beta-Ga 2 O 3 The 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. Thus, beta-Ga with wide forbidden band 2 O 3 Semiconductor crystalline materials are the hottest of todayOne of the semiconductor materials of the gate has received a great deal of attention.
β-Ga 2 O 3 The crystal is a compound which melts consistently, the melting point is 1793 ℃, and a high-temperature melt method is generally adopted for preparing single crystals, and main growth methods comprise a guided mode method, a floating zone method, a pulling method, a descending method and the like. But under the high-temperature anoxic environment 2 O 3 The crystals undergo decomposition reactions, and when the temperature is higher than 1680 ℃, severe decomposition reactions occur, and the decomposition products are volatile elemental gallium metal and gallium oxides. Moreover, too high a growth temperature is effective for crucible materials, beta-Ga 2 O 3 The regulation of the properties of crystals presents a serious challenge. As early as 60 th century, it was proposed that beta-Ga be grown by flux method 2 O 3 The method effectively reduces the beta-Ga 2 O 3 The growth temperature of the crystal (generally lower than 1600 ℃ C.), but the flux method requires PbO and PbF 2 And toxic and harmful components, and the grown crystal has macroscopic defects such as encapsulation, cloud layer and the like, and the available parts in the crystal are limited. Some fluxing agent systems have overlarge viscosity, are not easy to transport solutes, and have overlong crystal growth period. In addition, because the temperature of the grown crystal is still higher, gallium oxide still has the problem of melt volatilization, the crystallization interval is narrower, the temperature fluctuation of the saturation point is larger, the stability of crystal growth is poorer, and the high-quality beta-Ga is not beneficial to 2 O 3 And (5) growing crystals.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: how to stably grow high-quality beta-Ga at a lower temperature 2 O 3 And (5) a crystal.
In order to solve the technical problems, the invention provides a beta-Ga 2 O 3 The fluxing agent for crystal growth comprises a boron source, an alkali metal source and a molybdenum-containing compound, wherein the molar ratio of the boron source to the alkali metal source to the molybdenum-containing compound is 0.8-1.5: 0.8 to 2.5:0 to 0.3, wherein the boron source is boron oxide and/or a boron-containing compound which can be decomposed into boron oxide under heating, and the alkali metal source is alkali metal oxide and/or alkali metal which can be decomposed into alkali metal oxide under heatingThe molybdenum-containing compound is molybdenum oxide and/or molybdate.
Preferably, the boron-containing compound capable of decomposing into boron oxide under heating comprises boric acid; the alkali metal compound capable of decomposing into an alkali metal oxide under heating includes an alkali metal carbonate.
Preferably, the alkali metal oxide is at least one of lithium oxide, sodium oxide and potassium oxide; the alkali metal carbonate is at least one of lithium carbonate, sodium carbonate and potassium carbonate; the oxide of molybdenum is MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The molybdate is K 2 Mo 2 O 7 、Na 2 Mo 2 O 7 、Li 2 Mo 2 O 7 、K 2 MoO 4 、Na 2 MoO 4 、Li 2 MoO 4 、K 2 Mo 3 O 10 、Na 2 Mo 3 O 10 And Li (lithium) 2 Mo 3 O 10 At least one of them.
The invention also provides a beta-Ga 2 O 3 The crystal growth method adopts the beta-Ga 2 O 3 The growth of the fluxing agent for crystal growth comprises the following steps:
step 1: according to the mol ratio of 1 to 1.5: 0.8-2 proportion of beta-Ga 2 O 3 The crystal and the fluxing agent are repeatedly mixed and stirred, uniformly mixed and kept at the constant temperature of more than 300 ℃ for 8-12 hours, and then cooled to room temperature;
step 2: transferring the mixed material obtained in the step 1 into a crystal growth furnace, heating until the mixed material is completely melted into a solution, then keeping the temperature for 18-36 hours to obtain a high-temperature melt, introducing seed crystals into the high-temperature melt at a temperature 0.5-5 ℃ higher than the saturation temperature, keeping the temperature for 5-30 minutes, and then reducing the temperature to the saturation point temperature;
step 3: taking the saturation point temperature as the initial temperature, reducing the temperature at the speed of 0.05-0.3 ℃/day, rotating the crystal at the same time, inducing nucleation on the seed crystal to grow the crystal, separating the crystal from the liquid surface after the crystal grows to the required size, and keeping the speed of 10-50 ℃/hThe temperature is reduced to room temperature, and the beta-Ga is obtained 2 O 3 And (5) a crystal.
Preferably, the temperature at which the mixture is completely melted into a solution in the step 2 is 900-1200 ℃.
Preferably, the saturation point temperature in the step 2 and the step 3 is 950-1280 ℃.
Preferably, the rotation speed of the crystals in the step 3 is 5-50rpm.
Compared with the prior art, the invention has the following beneficial effects:
1. the cosolvent system of the invention can grow beta-Ga at a lower temperature 2 O 3 The crystal effectively inhibits the component deviation of the crystal, and the system does not contain PbO and PbF 2 The system has the advantages that toxic and harmful components are removed, crystals grow in the system, the crystallization interval of the crystals is larger, the viscosity and volatility of a high-temperature solution are reduced, solute transmission in the crystal growth process is facilitated, inclusion generation can be effectively avoided, the stability of crystal growth is improved, the crystallization temperature interval of crystal growth is increased, large-size and high-quality single crystals are grown, high-temperature decomposition of the crystals is effectively inhibited, the component segregation of the crystals in the growth process is improved, and high-quality single crystals are obtained;
2. beta-Ga according to the invention 2 O 3 The crystal flux system and the growth method thereof can stably grow beta-Ga with the size of centimeter level and high quality and transparency 2 O 3 A crystal; if a crucible with larger size is used, the growth period is prolonged properly, and single crystals with correspondingly larger size can be obtained;
3. beta-Ga according to the invention 2 O 3 The fluxing agent system and the growth method of the crystal can effectively reduce the growth temperature of the crystal, the growth temperature range is approximately 950-1080 ℃, and compared with the growth of the crystal by the fluxing agent method reported in the literature, the growth temperature is reduced by 420-550 ℃, and the high-temperature solution is clear and transparent, thereby being convenient for clearly observing the growth condition of the crystal in real time.
Detailed Description
In order to make the present invention more comprehensible, preferred embodiments accompanied with the present invention are described in detail below.
Raw material Ga used in the following examples 2 O 3 、MoO 3 、Li 2 O、Na 2 O、K 2 O、B 2 O 3 And H 3 BO 3 The purity of (2) was 99.9%, which was purchased from Shanghai chemical reagent company, china medicine group.
Example 1: by B 2 O 3 –Li 2 O–MoO 3 Preparation of beta-Ga by flux system 2 O 3 Crystal body
By beta-Ga 2 O 3 Powder and analytically pure B 2 O 3 、Li 2 O and MoO 3 As raw material, beta-Ga according to mole ratio 2 O 3 ：B 2 O 3 ：Li 2 O：MoO 3 =1.1: 0.9:0.9:0.1 ingredient, 206.18 g of beta-Ga is weighed out 2 O 3 Powder, 62.66 g B 2 O 3 26.89 g Li 2 O, 14.39 g MoO 3 。
Grinding and mixing the weighed raw materials uniformly, and adding phi 100X 70mm in batches 3 In the platinum crucible, the temperature is firstly increased to 300 ℃ in a muffle furnace, the temperature is kept for 8 hours, the temperature is cooled to room temperature, then the temperature is increased to 950 ℃ in the muffle furnace, and the temperature is kept for 36 hours, so that the crystal growth raw material is obtained. Loading a crystal growth raw material into a fused salt single crystal growth furnace heated by a resistance wire, wherein a furnace tube of the single crystal growth furnace is a vertical hollow circular tube; the opening at the top of the furnace is sealed by a cover made of heat-insulating material, a small hole for the seed rod to go in and out is reserved at the position corresponding to the center of the crucible at the top of the furnace, the temperature is raised to 1000 ℃, the melt is completely melted to obtain clear high-temperature solution, a stirrer made of platinum sheet is used for continuously stirring for 36h at the temperature with the rotating speed of 20rpm, and after the high-temperature solution is fully homogenized, the stirrer is lifted.
Determining the saturation point temperature of crystal growth to 981 ℃ by using an attempted seed crystal method, then cooling the high-temperature solution to 981.5 ℃ (0.5 ℃ above the saturation point temperature), and finally obtaining the beta-Ga 2 O 3 Slowly feeding seed crystal from small hole at top of furnace until seed crystal contacts solution surface, bidirectionally rotating seed crystal at 18rpm, maintaining temperature for 60 min, cooling to 981 deg.C, and heating to high temperatureThe vertical temperature gradient of the solution is 0.1 ℃/cm, and then the temperature is reduced at the speed of 0.05-0.2 ℃/day, so as to carry out crystal growth.
In the growth process, the rotating speed is gradually reduced along with the growth of the crystal, and the rotating speed is controlled to be reduced to 15rpm by adjusting the motor. After 30 days, the crystal growth is finished, the crystal is pulled off the liquid level and cooled to room temperature at the speed of 5 ℃/h, and the beta-Ga is obtained 2 O 3 The crystal has regular appearance and no inclusion.
Example 2: by B 2 O 3 –Li 2 O–Li 2 Mo 2 O 7 Preparation of beta-Ga by flux system 2 O 3 Crystal body
By beta-Ga 2 O 3 Powder and analytically pure B 2 O 3 、Li 2 O and Li 2 Mo 2 O 7 As raw material, beta-Ga according to mole ratio 2 O 3 ：B 2 O 3 ：Li 2 O：Li 2 Mo 2 O 7 =1: 0.88:0.88:0.15 batch, 206.18 g of beta-Ga 2 O 3 Powder, 61.53 g B 2 O 3 26.29 g Li 2 O, 47.66 g Li 2 Mo 2 O 7 。
Grinding and mixing the weighed raw materials uniformly, and adding phi 100X 70mm in batches 3 In the platinum crucible, firstly
Heating to 300 ℃ in a muffle furnace, keeping the temperature for 8 hours, cooling to room temperature, heating to 1050 ℃ in the muffle furnace, and keeping the temperature for 24 hours to obtain the crystal growth raw material.
Loading a crystal growth raw material into a fused salt single crystal growth furnace heated by a resistance wire, wherein a furnace tube of the single crystal growth furnace is a vertical hollow circular tube; the opening at the top of the furnace is sealed by a cover made of heat-insulating material, a small hole for the seed rod to go in and out is reserved at the position corresponding to the center of the crucible at the top of the furnace, the temperature is raised to 1050 ℃, the melt is completely melted to obtain clear high-temperature solution, a stirrer made of platinum sheet is used for continuously stirring for 30 hours at the temperature at the rotating speed of 40rpm, and after the high-temperature solution is fully homogenized, the stirrer is lifted.
Determining the saturation point temperature of crystal growth to 1022 ℃ by using an attempted seed crystal method, then cooling the high-temperature solution to 1022.5 ℃ (0.5 ℃ above the saturation point temperature), slowly dropping the beta-Ga 2O3 seed crystal from a small hole at the top of the furnace until the seed crystal contacts the surface of the solution, bidirectionally rotating the seed crystal at a speed of 35rpm, cooling to 1022 ℃ after keeping the temperature for 45 minutes, cooling the high-temperature solution to a vertical temperature gradient of 0.5 ℃/cm, and then cooling at a speed of 0.02-0.15 ℃/day, thereby carrying out crystal growth.
In the growth process, the rotating speed is gradually reduced along with the growth of the crystal, and the rotating speed is controlled to be reduced to 20rpm by adjusting the motor. After 30 days, the crystal growth is finished, the crystal is pulled off the liquid surface and cooled to room temperature at the speed of 10 ℃/h, and the beta-Ga is obtained 2 O 3 And (5) a crystal.
Example 3: by B 2 O 3 –Na 2 O–Na 2 MoO 4 Preparation of beta-Ga by flux system 2 O 3 Crystal body
By beta-Ga 2 O 3 Powder and analytically pure B 2 O 3 、Na 2 O and Na 2 MoO 4 As raw material, beta-Ga according to mole ratio 2 O 3 ：B 2 O 3 ：Na 2 O：Na 2 MoO 4 =0.7: 0.44:0.22:0.15 batch, 131.21 g of beta-Ga 2 O 3 Powder, 30.76 g B 2 O 3 13.64 g of Na 2 O, 30.88 g Na 2 MoO 4 。
Grinding and mixing the weighed raw materials uniformly, and adding phi 100X 70mm in batches 3 In the platinum crucible, the temperature is firstly increased to 300 ℃ in a muffle furnace, the temperature is kept for 8 hours, the temperature is cooled to room temperature, then the temperature is increased to 1025 ℃ in the muffle furnace, and the temperature is kept for 32 hours, so that the crystal growth raw material is obtained.
Loading a crystal growth raw material into a fused salt single crystal growth furnace heated by a resistance wire, wherein a furnace tube of the single crystal growth furnace is a vertical hollow circular tube; the opening at the top of the furnace is sealed by a cover made of heat-insulating material, a small hole for the seed rod to go in and out is reserved at the position corresponding to the center of the crucible at the top of the furnace, the temperature is raised to 1025 ℃, the melt is completely melted to obtain clear high-temperature solution, a stirrer made of platinum sheet is used for continuously stirring for 35 hours at the temperature at the rotating speed of 50rpm, and after the high-temperature solution is fully homogenized, the stirrer is lifted.
Determining the saturation point temperature of crystal growth to 1018 deg.C by trial seed method, cooling the above high temperature solution to 1018 deg.C (0.5 deg.C above saturation point temperature), and mixing the beta-Ga 2 O 3 Slowly feeding the seed crystal from a small hole at the top of the furnace until the seed crystal contacts the surface of the solution, bidirectionally rotating the seed crystal at a speed of 45rpm, cooling to 1018 ℃ after keeping constant temperature for 45 minutes, cooling the high-temperature solution at a vertical temperature gradient of 0.85 ℃/cm, and then cooling at a speed of 0.08-0.25 ℃/day to perform crystal growth.
In the growth process, the rotating speed is gradually reduced along with the growth of the crystal, and the rotating speed is controlled to be reduced to 22rpm by adjusting the motor. After 30 days, the crystal growth is finished, the crystal is pulled off the liquid surface and cooled to room temperature at the speed of 3 ℃/h, and the beta-Ga is obtained 2 O 3 And (5) a crystal.
Example 4: by B 2 O 3 –Na 2 O–Na 2 Mo 3 O 10 Preparation of beta-Ga by flux system 2 O 3 Crystal body
By beta-Ga 2 O 3 Powder and analytically pure B 2 O 3 、Na 2 O and Na 2 MoO 4 As raw material, beta-Ga according to mole ratio 2 O 3 ：B 2 O 3 ：Na 2 O：Na 2 MoO 4 =1: 0.56:0.28:0.025 batch, 206.18 g of beta-Ga 2 O 3 Powder, 39.16 g B2O3, 17.35 g Na 2 O, 12.34 g Na 2 Mo 3 O 10 。
Grinding and mixing the weighed raw materials uniformly, and adding phi 100X 70mm in batches 3 In the platinum crucible, the material is firstly dried and crystallized in a muffle furnace at 300 ℃ for 8 hours, then cooled to room temperature, and then heated to 1150 ℃ in the muffle furnace, and the material is obtained after constant temperature for 28 hours, thus obtaining the crystal growth raw material.
Loading a crystal growth raw material into a fused salt single crystal growth furnace heated by a resistance wire, wherein a furnace tube of the single crystal growth furnace is a vertical hollow circular tube; the opening at the top of the furnace is sealed by a cover made of heat-insulating material, a small hole for the seed rod to go in and out is reserved at the position corresponding to the center of the crucible at the top of the furnace, the temperature is raised to 1150 ℃, the melt is completely melted to obtain clear high-temperature solution, a stirrer made of platinum sheet is used for continuously stirring for 48 hours at the temperature at the rotating speed of 45rpm, and after the high-temperature solution is fully homogenized, the stirrer is lifted.
Determining the saturation point temperature of crystal growth to 1138 ℃ by using an attempted seed crystal method, then cooling the high-temperature solution to 1138.5 ℃ (0.5 ℃ above the saturation point temperature), and finally obtaining the beta-Ga 2 O 3 Slowly feeding the seed crystal from a small hole at the top of the furnace until the seed crystal contacts the surface of the solution, bidirectionally rotating the seed crystal at a speed of 40rpm, cooling to 1138 ℃ after keeping constant temperature for 45 minutes, cooling the high-temperature solution at a vertical temperature gradient of 1 ℃/cm, and then cooling at a speed of 0.1-0.45 ℃/day to perform crystal growth.
In the growth process, the rotating speed is gradually reduced along with the growth of the crystal, and the rotating speed is controlled to be reduced to 25rpm by adjusting the motor. After 30 days, the crystal growth is finished, the crystal is pulled off the liquid surface and cooled to room temperature at the speed of 4.5 ℃/h, and the beta-Ga is obtained 2 O 3 And (5) a crystal.
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 (4)
1. beta-Ga 2 O 3 A method for growing crystals, comprising the steps of:
step 1: according to the molar ratio of 1-1.5: 0.8-2 proportion weighing beta-Ga 2 O 3 The crystal and the fluxing agent are repeatedly mixed and stirred, uniformly mixed and kept at the constant temperature of more than 300 ℃ for 8-12 hours, and then cooled to room temperature;
step 2: transferring the mixed material obtained in the step 1 into a crystal growth furnace, heating until the mixed material is completely melted into a solution, then keeping the temperature for 18-36 hours to obtain a high-temperature melt, introducing seed crystals into the high-temperature melt at a temperature 0.5-5 ℃ higher than the saturation temperature, keeping the temperature for 5-30 minutes, and then reducing the temperature to the saturation point temperature;
step 3: taking the saturation point temperature as the initial temperature, cooling at the speed of 0.05-0.3 ℃/day, rotating the crystal at the same time, inducing nucleation on the seed crystal to perform crystal growth, separating the crystal from the liquid surface after the crystal grows to the required size, and cooling to the room temperature at the speed of 10-50 ℃/h to obtain the beta-Ga 2 O 3 A crystal;
the cosolvent in the step 1 comprises a boron source, an alkali metal source and a molybdenum-containing compound, wherein the molar ratio of the boron source to the alkali metal source to the molybdenum-containing compound is 0.8-1.5: 0.8-2.5: 0-0.3, wherein the boron source is boron oxide and/or boric acid, the alkali metal source is alkali metal oxide and/or alkali metal carbonate, and the molybdenum-containing compound is molybdenum oxide and/or molybdate;
wherein the alkali metal oxide is at least one of lithium oxide, sodium oxide and potassium oxide; the alkali metal carbonate is at least one of lithium carbonate, sodium carbonate and potassium carbonate; the oxide of molybdenum is MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The molybdate is K 2 Mo 2 O 7 、Na 2 Mo 2 O 7 、Li 2 Mo 2 O 7 、K 2 MoO 4 、Na 2 MoO 4 、Li 2 MoO 4 、K 2 Mo 3 O 10 、 Na 2 Mo 3 O 10 And Li (lithium) 2 Mo 3 O 10 At least one of them.
2. beta-Ga according to claim 1 2 O 3 The crystal growing method is characterized in that the temperature of the mixed material in the step 2 which is completely melted into solution is 900-1200 ℃.
3. beta-Ga according to claim 1 2 O 3 The crystal growing method is characterized in that the saturation point temperature in the step 2 and the step 3 is 950-1280 ℃.
4. Such as weightbeta-Ga according to claim 1 2 O 3 A method for growing crystals, characterized in that the rate of rotation of the crystals in step 3 is 5-50rpm.
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