CN114836821B - Growth method of low dislocation density gallium oxide bulk single crystal - Google Patents
Growth method of low dislocation density gallium oxide bulk single crystal Download PDFInfo
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- CN114836821B CN114836821B CN202110136723.4A CN202110136723A CN114836821B CN 114836821 B CN114836821 B CN 114836821B CN 202110136723 A CN202110136723 A CN 202110136723A CN 114836821 B CN114836821 B CN 114836821B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
- C30B15/203—Controlling or regulating the relationship of pull rate (v) to axial thermal gradient (G)
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a growth method of a gallium oxide bulk single crystal with low dislocation density, which adopts a kyropoulos method to grow crystals and simultaneously pulls up seed crystals at a certain pulling speed, and the growth speed of the crystals is controlled by cooling a seed rod and adjusting a temperature step and adjusting a temperature gradient in a furnace. The invention controls the growth speed of the crystal by controlling the heating power and cooling the seed rod, thereby being beneficial to reducing the thermal stress of the crystal, reducing the cracking of the crystal, reducing the defect density in the crystal, effectively improving the quality of the crystal, increasing the temperature gradient by pulling at a certain speed in the whole crystal growth process and being beneficial to controlling the crystal growth.
Description
[ field of technology ]
The invention relates to the technical field of gallium oxide bulk single crystals, in particular to the technical field of a growth method of low dislocation density gallium oxide bulk single crystals.
[ background Art ]
With the rapid development of the fields of 5G mobile communication, photovoltaic power generation, high-voltage power transmission and transformation, electric automobiles, high-speed rail traffic and the like, wide-forbidden-band and ultra-wide-forbidden-band semiconductors become research hot spots of semiconductor materials and devices at present. Gallium oxide is used as a novel ultra-wide band gap semiconductor material, the band gap width of the novel ultra-wide band gap semiconductor material can reach 4.7-4.9 eV, and the novel ultra-wide band gap semiconductor material has the advantages of larger band gap width, higher breakdown field intensity, larger Baliga quality factor and the like compared with the third-generation wide band gap semiconductor, and is expected to be applied to the fields of ultraviolet detectors, high-power devices and the like. Ga 2 O 3 Six crystalline phases, multiple crystal structures, have been found, each of which is beta-Ga at high temperatures 2 O 3 The melting point is approximately 1820 ℃. That is to say beta-Ga 2 O 3 Single crystal growth can be performed by a melt method, and among wide band gap semiconductor materials, a few materials that can be used to prepare bulk single crystals by a melt method are available. Therefore, the production cost is lower, and the method has good development prospect in the aspect of industrial application.
The bubble growth method is a melt growth method with small temperature gradient, the bubble growth method is to utilize temperature to control the growth of crystals, only the head of the crystals is pulled out during growth, the crystal part is soaked in the melt, the crystal growth is realized by means of temperature change, and the melt is cooled mainly by reducing heating power, so that the temperature range most suitable for the crystal growth is reached, and the crystal growth is completed. The bubble growth method is always in a hot zone because the bubble growth method is not pulled in the crystal growth process, and the grown crystal has small thermal stress, few defects and low dislocation density.
The existing gallium oxide bulk single crystal growth methods reported in the gallium oxide industry mainly comprise a floating zone method, a guided mode method, a Czochralski method and the like. Among these growth methods, the floating zone method has a major advantage in that a crucible is not required, and thus heating is not limited by the melting point of the crucible and other impurities are not carried in, but during the growth, the melting zone is maintained mainly by surface tension and gravity, and the grown crystal has small component unevenness in the axial direction and is limited in size and single crystal quality. The Czochralski method is a common method for producing monocrystalline silicon wafers, and the technology is also mature, but the Czochralski method is adopted to prepare beta-Ga 2 O 3 The single crystal is difficult to control the constant diameter, and the single crystal is spirally grown, so that beta-Ga with higher quality can not be obtained 2 O 3 And (3) single crystals. The crystal growth method by the guided mode method utilizes the principle of liquid level rising in the capillary, and the crystal growth occurs on the upper surface of the capillary. beta-Ga prepared by the method 2 O 3 The quality of single crystal is improved, but the dislocation density is still as high as 10 5 ～10 6 Individual/cm 2 And the guided mode method needs a complete set of crucible, mold, crucible cover and the like to prepare the beta-Ga 2 O 3 The melting point of the alloy is higher, the noble metals such as iridium, platinum and rhodium are used, the production cost is higher, and the industrialization is not easy to realize. As a novel wide band gap semiconductor material, research on gallium oxide crystal materials is still in the primary stage, and development of a high-quality, large-size and low-cost gallium oxide single crystal growth method is the basis of later application and industrial production, so that a novel crystal growth process for improving the gallium oxide crystal quality with low cost is necessary to be researched.
[ invention ]
The invention aims to solve the problems in the prior art, and provides a growth method of a gallium oxide bulk single crystal with low dislocation density, which adopts a kyropoulos method to grow crystals and simultaneously pulls up seed crystals at a certain pulling speed, and by cooling a seed rod and adjusting a temperature step, high-quality crystals with few crystal defects, low dislocation density and large crystal size are grown.
In order to achieve the above object, the present invention provides a growth method of a low dislocation density gallium oxide bulk single crystal, comprising the steps of:
a. and (2) charging: loading a crucible filled with gallium oxide raw materials into a hearth, loading seed crystals on seed rods, vacuumizing the crystal growth furnace, and filling protective gas;
b. heating and melting: heating the crucible to raise the temperature, and keeping the melt state after the raw materials are completely melted;
c. firstly, descending seed crystal to be above the liquid level, keeping for a certain time, then controlling the seed crystal rod to start rotating clockwise or anticlockwise, wherein the rotating speed is 2-20 rad/min, descending seed crystal enters a seeding neck collecting stage, enters a shoulder expanding and equal diameter growing stage after seeding neck collecting, reduces heating power at a speed of 10-40W/h in the shoulder expanding and equal diameter growing stage, and lifts up at a speed of not more than 0.4mm/h when the equal crystal grows to 50-100 mm, and reduces the temperature of the seed crystal rod while lifting up to control uniform weight gain of the crystal;
d. after the crystal grows to a desired size, annealing is performed.
In step a, the purpose of the evacuation is to completely replace the furnace gas with the shielding gas, typically to reduce the vacuum level to 1X 10 -3 Pa or less, and more generally, the vacuum degree is reduced to 1X 10 -1 Pa or less, and the condition is satisfied, and the invention does not limit the vacuum degree.
In step c, the seed rod is cooled while the heating power is reduced to control the uniform weight gain of the crystal, and those skilled in the art should know that the uniform weight gain in the physical sense cannot be achieved in the actual operation, and generally, the weight gain needs to be recorded by periodically observing the weight curve of the crystal, and the difference between the two adjacent weight gains is controlled within an acceptable experience range.
The proposal adopts the kyropoulos method to grow gallium oxide crystal, gallium oxide beta-Ga 2 O 3 Is relatively low in [010 ]]The thermal conductivity at room temperature is the highest and is only 27.9W.m -1 ·K -1 And as the temperature increases, its thermal conductivity further decreases. Since the heat conduction mode during crystal growth at high temperature is mainly heat radiation, beta-Ga 2 O 3 The crystal is a semiconductor material, which is different from Al 2 O 3 Insulated oxide crystals such as YAG and the like have weak infrared radiation absorption, and beta-Ga 2 O 3 The crystal has strong absorption in the infrared band, and the heat transfer at the solid-liquid interface is affected, so that the internal temperature of the solid-liquid interface is higher, and the forward temperature gradient is weakened along with the growth of the crystal, so that the stable growth of the crystal is affected. If the gallium oxide monocrystal is grown by adopting the traditional kyropoulos method, the temperature gradient required by crystal growth is difficult to form, so that the crystal is pulled at a speed smaller than that of a pulling method in the whole crystal growth process, and meanwhile, the seed rod is cooled, and the temperature gradient of the crystal growth is regulated by the synergistic effect of the gallium oxide monocrystal and the seed rod, so that the growth speed of the crystal is controlled, the crystal is slowly and uniformly grown, the thermal stress of the crystal is reduced, the crystal cracking is reduced, the defect density in the crystal is reduced, and the crystal quality is effectively improved.
Preferably, the shielding gas in the step a is carbon dioxide with one atmosphere.
Carbon dioxide is selected as the protective gas, and has the function of inhibiting the pyrolysis of gallium oxide. Simultaneously selecting CO to be introduced 2 Either + inert gas (Ar gas, he gas, etc.) or gas (e.g., oxygen, air, etc.) having the function of suppressing the pyrolysis of gallium oxide and different gas pressure shielding gases can play a corresponding role. When the technology is applied to industrialization, the protection gas with lower price or the air pressure more suitable for working conditions are mixed in aiming at production cost.
Preferably, the seed crystal is beta-Ga 2 O 3 A crystal, the seed crystal is loaded on a seed crystal clamping head of the seed crystal rod, and the seed crystal is vertically upwardsThe direction is [010 ]]And (5) crystal orientation.
β-Ga 2 O 3 In [010 ]]The thermal conductivity at room temperature was 27.9W.m -1 ·K -1 Far greater than the crystal at room temperature [100 ]]And [001]Thermal conductivity in the direction is beneficial to control the temperature gradient.
Preferably, in the step c, the cooling mode of the seed rod is to introduce cooling water or cooling gas into the seed rod or outside the seed rod, and the uniform weight gain of the crystal is controlled by controlling the flow rate of the cooling water or the cooling gas.
The cooling of the seed rod is beneficial to improving the heat transfer at the solid-liquid interface, increasing the heat dissipation path and improving the crystal growth stability, thereby controlling the growth speed and quality of the crystal.
Preferably, the heating power is reduced in the step c at a rate of 20 to 30W/h.
If the heating power is reduced too fast, the internal thermal stress of the crystal is large, and the defect density is too high; if the heating power is reduced too slowly, the heat transfer becomes slow, a positive temperature gradient cannot be formed, and even a negative temperature gradient is generated, so that the crystal growth is affected.
Preferably, the speed of crystal pulling in step c is 0.1mm/h.
If the pulling rate is too high, the crystal grows by pulling the crystal out of the melt level as the driving force, because of the beta-Ga 2 O 3 The characteristics of serious infrared absorption and relatively low heat conductivity lead the solid-liquid interface to gradually become concave liquid level, and the crystal grows spirally and even breaks away from the liquid level.
Preferably, in the step c shoulder-expanding and constant diameter growth stage, the pulling is performed at a speed of 0.4 to 1mm/h before the crystal grows to 50 to 100 mm.
Preferably, in the step c, the seed crystal is firstly lowered to a position 5-10 mm above the liquid level and then is lowered to enter a seeding neck-collecting stage after being kept for 15-45 min.
Preferably, the step of seeding and neck collecting in the step c is as follows: when the seed crystal contacts the liquid level, the seed crystal is lowered to 10-30 mm below the liquid level at a speed of 20-40 mm/h, and the surface of the seed crystal is controlled to be melted off by 3-7 mm.
Preferably, in the step c, the seed crystal is firstly lowered to a position about 10mm above the liquid level, the seed crystal is kept for 20min, the rotating speed of the seed crystal rod is controlled to be 2rad/min, and the seed crystal is lowered to 20mm below the liquid level at a speed of 20mm/h after the seed crystal is contacted with the liquid level, and the surface of the seed crystal is controlled to be melted off by 3-7 mm.
Preferably, the annealing step in the step d is as follows: the state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the temperature is kept for 2-5 hours, the temperature enters a ending lifting and releasing stage, the heating power is increased by 1-2 kw, after the temperature is kept for 1-2 hours, the lifting speed is increased to 0.5-2 mm/h after the temperature is kept for 3-5 hours, the crystal is separated from the crucible, the lifting is stopped after the crystal weight is stable, the heating power is reduced at the speed of 30-60W/h until the working is stopped, and the temperature is naturally cooled to the room temperature.
Preferably, the annealing step in the step d is as follows: the state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the temperature is kept for 3 hours, the ending and lifting stages are carried out, the heating power is increased by 1-2 kw, after the temperature is kept for 2 hours, the lifting speed is increased to 1mm/h at first at a speed of 0.5mm/h, the crystal is separated from the crucible, the lifting is stopped after the crystal weight is stable, the heating power is reduced at a speed of 50W/h until the working is stopped, and the temperature is naturally cooled to the room temperature.
Preferably, in the step b, the time for maintaining the melt state is 3 to 5 hours.
The invention has the beneficial effects that:
1. according to the invention, the heating power is controlled, and the temperature gradient of crystal growth is controlled by cooling the seed rod, so that the growth speed of the crystal is controlled, the thermal stress of the crystal is reduced, the cracking of the crystal is reduced, the defect density in the crystal is reduced, and the crystal quality is effectively improved;
2. carbon dioxide is selected as a protective gas, so that the high-temperature decomposition of gallium oxide is reduced;
3. due to beta-Ga 2 O 3 The thermal conductivity of the crystal is lower, and the thermal conductivity of the crystal is reduced along with the increase of the temperature, and the crystal is pulled at a certain speed in the whole crystal growth process to increaseThe temperature gradient is favorable for controlling the growth of crystals;
4. the minimum dislocation density of the gallium oxide monocrystal obtained by growth of the invention reaches 3.5 multiplied by 10 4 Individual/cm 2 ；
5. The maximum size diameter of the gallium oxide monocrystal obtained by growth of the invention reaches 2 inches.
The invention provides a growth method of gallium oxide bulk single crystal, which mainly uses a mode of reducing heating power and small-speed pulling to control beta-Ga by matching with the regulation of the temperature of a seed rod 2 O 3 The crystal grows stably. beta-Ga obtained by growth of the invention 2 O 3 Bulk crystal has the characteristics of large size, few crystal defects, low dislocation density and the like. The invention overcomes the low heat conductivity and strong infrared absorption capability of gallium oxide at high temperature, solves the technical problems of difficult growth, uncontrollable constant diameter, low crystal quality and the like of the existing gallium oxide single crystal, and simultaneously has the advantages of simple operation, low equipment requirement, low production cost, i.e. saving accessories such as a die, a crucible cover and the like made of noble metal compared with the gallium oxide grown by a guided mode method, and provides a better scheme for industrialization of the gallium oxide single crystal.
The features and advantages of the present invention will be described in detail by way of example with reference to the accompanying drawings.
[ description of the drawings ]
FIG. 1 is a schematic view of a seed loading of the present invention;
figure 2 is an XRD pattern of the product prepared in example 1 of the present invention.
In the figure: 1-heat preservation layer, 2-induction coil, 3-crucible, 4-melt, 5-seed crystal and 6-seed crystal rod.
[ detailed description ] of the invention
Embodiment one:
referring to fig. 1 and 2, the method for growing a low dislocation density gallium oxide bulk single crystal according to the present invention comprises the steps of: firstly wiping with dust-free alcohol, cleaning a hearth, an insulating layer, a crucible and the like by using an industrial dust collector, then filling 5N-grade gallium oxide raw materials with purity of more than 99.99 percent into the crucible in a clean room, and placing the crucible in the hearth of a single crystal furnaceIn the process, [010 ]]Directional beta-Ga 2 O 3 Loading the crystal seed on the seed rod, centering the seed rod, and vacuumizing to 1×10 after final furnace closing -3 Under Pa, re-charging CO at 1 atmosphere 2 The method comprises the steps of taking gas as a protective gas, heating a crucible, heating the crucible, keeping a high-temperature melt state for 5 hours after gallium oxide raw materials are completely melted, lowering seed crystals to 10mm above a liquid level, keeping the temperature for 20 minutes, judging that the lowered seed crystals start seeding according to the temperature in a furnace, the liquid flow speed, the floating crystal size, the tail end of the seed crystals and the like, controlling the seed crystal rod to rotate clockwise at the rotating speed of 2rad/min, lowering the seed crystal rod to 20mm below the liquid level at the speed of 20mm/h after the seed crystals are contacted with the liquid level, controlling the surface of the seed crystals to melt off 3-7 mm, forming an arc surface, controlling the temperature of the melt to be close to the melting point after seeding and neck collecting, generally controlling the temperature to be 1780-1800 ℃, entering a shoulder expanding and equal diameter growth stage, and controlling the heating power to slowly reduce the heating power at the speed of 20-30W/h in the whole shoulder expanding and equal diameter growth stage to enable the crystals to grow slowly. In the shoulder expanding and constant diameter growth stage, the crystal is firstly pulled at the speed of 0.4mm/h, then pulled at the speed of 0.1mm/h after the crystal grows to 50 to 100mm, cooling gas is introduced into the seed rod while pulling, the weight curve of the crystal is observed, and the crystal is controlled to grow at a constant speed by controlling the flow rate of the cooling gas. In this example, the crystal weight gain is recorded once per hour, and the crystal weight gain value per hour is controlled by increasing or decreasing the flow rate or shutting down the cooling gas by not more than + -1% from the weight gain value recorded in the previous hour. The crystal weight gain may be different depending on the target crystal size and should not be taken as limiting the invention. The state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the crystal is indicated to touch the wall of the crucible or the bottom of the crucible, after the temperature is kept for 3 hours, the crystal enters a ending lifting and releasing stage, the heating power is increased by 1-2 kw, after the temperature is kept for 2 hours, the crystal is lifted at a speed of 0.5mm/h, after the temperature is kept for 3 hours, the lifting speed is increased to 1mm/h, the crystal is automatically separated from the crucible, cooling and annealing are carried out, the power is reduced to stop working at a speed of 50W/h, then the crystal is naturally cooled for 24 hours, and the gallium oxide crystal prepared by the method is beta-phase Ga 2 O 3 The diameter of the single crystal is 2 inches, and the dislocation of the single crystal is obtained by experimental testDensity of 3.5X10 4 Individual/cm 2 。
Embodiment two:
referring to fig. 1, the method for growing a low dislocation density gallium oxide bulk single crystal according to the invention comprises the following steps: firstly wiping with dust-free alcohol, cleaning a hearth, an insulating layer, a crucible and the like by using an industrial dust collector, then loading 5N-grade gallium oxide raw materials with purity of more than 99.99% into the crucible in a clean room, placing the crucible in the hearth of a single crystal furnace, and putting [010 ]]Directional beta-Ga 2 O 3 Loading the crystal seed on the seed rod, centering the seed rod, and vacuumizing to a vacuum degree of 1×10 after furnace closing -3 Under Pa, re-charging CO at 1 atmosphere 2 The method comprises the steps of taking gas as a protective gas, heating a crucible, heating the crucible, keeping a high-temperature melt state for 3 hours after gallium oxide raw materials are completely melted, lowering seed crystals to 10mm above a liquid level, keeping the temperature for 15 minutes, judging that the lowered seed crystals start seeding according to the temperature in a furnace, the liquid flow speed, the floating crystal size, the tail end of the seed crystals and the like, controlling the seed crystal rod to rotate clockwise at the rotating speed of 5rad/min, lowering the seed crystal rod to 30mm below the liquid level at the speed of 20mm/h after the seed crystals are contacted with the liquid level, controlling the surface of the seed crystals to melt off 3-7 mm and form an arc surface, controlling the temperature of the melt to be close to the melting point after seeding and neck collecting, generally controlling the temperature to be 1780-1800 ℃, entering a shoulder expanding and equal diameter growth stage, and controlling the heating power to slowly reduce the heating power at the speed of 10-20W/h in the whole shoulder expanding and equal diameter growth stage to enable the crystals to grow slowly. In the shoulder expanding and constant diameter growth stage, firstly, lifting at a speed of 1mm/h, then lifting at a speed of 0.4mm/h after crystals grow to 50-100 mm, introducing cooling gas into a seed rod while lifting, observing a crystal weight curve, and controlling the uniform growth of crystals by controlling the flow rate of the cooling gas. In this example, the crystal weight gain is recorded once per hour, and the crystal weight gain value per hour is controlled by increasing or decreasing the flow rate or shutting down the cooling gas by not more than + -1% from the weight gain value recorded in the previous hour. The crystal weight gain may be different depending on the target crystal size and should not be taken as limiting the invention. Monitoring the state of the crystal by a weight curve, indicating that the crystal is touching when the weight curve presents a wavy lineAfter the temperature of the crucible wall or the crucible bottom is kept for 2 hours, the temperature enters a ending lifting-falling stage, the heating power is increased by 1-2 kw, after the temperature is kept for 2 hours, the lifting speed is increased to 2mm/h after the temperature is kept for 3 hours, the crystal is automatically separated from the crucible, the cooling annealing is carried out, the power is reduced to stop working at the speed of 50W/h, and then the natural cooling is carried out for 24 hours, so that the gallium oxide crystal obtained by the method is beta-phase Ga 2 O 3 The dislocation density of the single crystal obtained by experimental test is 5.1 multiplied by 10 4 Individual/cm 2 。
Embodiment III:
referring to fig. 1, the method for growing a low dislocation density gallium oxide bulk single crystal according to the invention comprises the following steps: firstly wiping with dust-free alcohol, cleaning a hearth, an insulating layer, a crucible and the like by using an industrial dust collector, then loading 5N-grade gallium oxide raw materials with purity of more than 99.99% into the crucible in a clean room, placing the crucible in the hearth of a single crystal furnace, and putting [010 ]]Directional beta-Ga 2 O 3 Loading the crystal seed on the seed rod, centering the seed rod, and vacuumizing to 1×10 after final furnace closing -3 Under Pa, re-charging CO at 1 atmosphere 2 The method comprises the steps of taking gas as a protective gas, heating a crucible, heating the crucible, keeping a high-temperature melt state for 3 hours after gallium oxide raw materials are completely melted, lowering seed crystals to 10mm above a liquid level, keeping the temperature for 45 minutes, judging that the lowered seed crystals start seeding according to the temperature in a furnace, the liquid flow speed, the floating crystal size, the tail end of the seed crystals and the like, controlling the seed crystal rod to rotate clockwise at the rotating speed of 10rad/min, lowering the seed crystal rod to 10mm below the liquid level at the speed of 20mm/h after the seed crystals are contacted with the liquid level, controlling the surface of the seed crystals to melt off 3-7 mm, forming an arc surface, controlling the temperature of the melt to be close to the melting point after seeding and neck collecting, generally controlling the temperature to be 1780-1800 ℃, entering a shoulder expanding and equal diameter growth stage, and controlling the heating power to slowly reduce the heating power at the speed of 30-40W/h in the whole shoulder expanding and equal diameter growth stage to enable the crystals to grow slowly. In the shoulder expansion and equal diameter growth stage, the crystal is not pulled first, the crystal is pulled at the speed of 0.1mm/h after the crystal grows to 50 to 100mm, cooling gas is introduced into the seed rod while the crystal is pulled, the weight curve of the crystal is observed, and the uniform speed of the crystal is controlled by controlling the flow rate of the cooling gasAnd (5) growing. In this example, the crystal weight gain is recorded once per hour, and the crystal weight gain value per hour is controlled by increasing or decreasing the flow rate or shutting down the cooling gas by not more than + -1% from the weight gain value recorded in the previous hour. The crystal weight gain may be different depending on the target crystal size and should not be taken as limiting the invention. The state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the crystal is indicated to touch the wall of the crucible or the bottom of the crucible, after the temperature is kept for 2 hours, the crystal enters a ending lifting and releasing stage, the heating power is increased by 1-2 kw, after the temperature is kept for 3 hours, the crystal is lifted at a speed of 1mm/h, after the temperature is kept for 3 hours, the lifting speed is increased to 2mm/h, the crystal is automatically separated from the crucible, the crystal is cooled and annealed, the power is reduced to stop working at a speed of 50W/h, and then the crystal is naturally cooled for 24 hours, and the gallium oxide crystal prepared by the method is beta-phase Ga 2 O 3 The dislocation density of the single crystal obtained by experimental test is 4.2 multiplied by 10 4 Individual/cm 2 。
Example IV
Referring to fig. 1, the method for growing a low dislocation density gallium oxide bulk single crystal according to the invention comprises the following steps: firstly wiping with dust-free alcohol, cleaning a hearth, an insulating layer, a crucible and the like by using an industrial dust collector, then loading 5N-grade gallium oxide raw materials with purity of more than 99.99% into the crucible in a clean room, placing the crucible in the hearth of a single crystal furnace, and putting [010 ]]Directional beta-Ga 2 O 3 Loading the crystal seed on the seed rod, centering the seed rod, and vacuumizing to a vacuum degree of 1×10 after furnace closing -3 Under Pa, re-charging CO at 1 atmosphere 2 The gas is used as protective gas to heat the crucible, after the gallium oxide raw material is completely melted, the high-temperature melt state is kept for 3 hours, the seed crystal is lowered to 5mm above the liquid level, the lowering speed is kept for 15 minutes, the lowering speed is 120mm/h, the seed crystal is judged to be lowered according to the temperature in the furnace, the liquid flow speed, the size of floating crystals, the tail end of the seed crystal and the like, the seed crystal rod is controlled to rotate clockwise, the rotating speed is 2rad/min, the seed crystal is lowered to 10mm below the liquid level at the speed of 20mm/h after contacting the liquid level, the surface of the seed crystal is controlled to be melted off for 3-7 mm, the arc surface is formed, the temperature of the melt is controlled to be near the melting point after seeding and neck collecting, the temperature of the melt is generally controlled to be near the melting point after the seedingThe temperature is 1780-1800 ℃, the crystal enters into a shoulder expansion and equal diameter growth stage, and the heating power is controlled to be slowly reduced at the speed of 10W/h in the whole shoulder expansion and equal diameter growth stage so as to enable the crystal to slowly grow. In the shoulder expanding and constant diameter growth stage, the crystal is firstly pulled at the speed of 0.6mm/h, then pulled at the speed of 0.2mm/h after the crystal grows to 50 to 100mm, cooling gas is introduced into the seed rod while pulling, the weight curve of the crystal is observed, and the crystal is controlled to grow at a constant speed by controlling the flow rate of the cooling gas. In this example, the crystal weight gain is recorded once per hour, and the crystal weight gain value per hour is controlled by increasing or decreasing the flow rate or shutting down the cooling gas by not more than + -1% from the weight gain value recorded in the previous hour. The crystal weight gain may be different depending on the target crystal size and should not be taken as limiting the invention. The state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the crystal is indicated to touch the wall of the crucible or the bottom of the crucible, after the temperature is kept for 2 hours, the crystal enters a ending lifting and removing stage, the heating power is increased by 1-2 kw, after the temperature is kept for 1 hour, the crystal is lifted at a speed of 0.3mm/h, after the temperature is kept for 3 hours, the lifting speed is increased to 0.5mm/h, the crystal is automatically separated from the crucible, the crystal is cooled and annealed, the power is reduced to stop working at a speed of 30W/h, and then the crystal is naturally cooled for 24 hours, and the gallium oxide crystal prepared by the method is beta-phase Ga 2 O 3 And (3) single crystals.
Fifth embodiment:
referring to fig. 1, the method for growing a low dislocation density gallium oxide bulk single crystal according to the invention comprises the following steps: firstly wiping with dust-free alcohol, cleaning a hearth, an insulating layer, a crucible and the like by using an industrial dust collector, then loading 5N-grade gallium oxide raw materials with purity of more than 99.99% into the crucible in a clean room, placing the crucible in the hearth of a single crystal furnace, and putting [010 ]]Directional beta-Ga 2 O 3 Loading the crystal seed on the seed rod, centering the seed rod, and vacuumizing to a vacuum degree of 1×10 after furnace closing -3 Under Pa, re-charging CO at 1 atmosphere 2 The gas is used as protective gas, the crucible is heated, after the gallium oxide raw material is completely melted, the high-temperature melt state is kept for 3 hours, the seed crystal is lowered to 7mm above the liquid level, the temperature is kept for 30 minutes, and the lowering speed is 120And judging that the descending seed crystal starts seeding according to the temperature in the furnace, the liquid flow speed thickness, the floating crystal size, the tail end of the seed crystal and the like, controlling the seed crystal rod to rotate clockwise at the rotating speed of 10rad/min, reducing the seed crystal to 15mm below the liquid level at the speed of 25mm/h after the seed crystal contacts the liquid level, controlling the surface of the seed crystal to melt off by 3-7 mm to form an arc surface, controlling the temperature of the melt to be near the melting point after seeding and neck collecting, generally at the temperature of 1780-1800 ℃, entering a shoulder expanding and constant diameter growth stage, and controlling the heating power in the whole shoulder expanding and constant diameter growth stage to slowly reduce the heating power at the speed of 20W/h so as to enable the crystal to grow slowly. In the shoulder expanding and constant diameter growth stage, the crystal is firstly pulled at the speed of 0.8mm/h, then pulled at the speed of 0.3mm/h after the crystal grows to 50 to 100mm, cooling gas is introduced into the seed rod while pulling, the weight curve of the crystal is observed, and the crystal is controlled to grow at a constant speed by controlling the flow rate of the cooling gas. In this example, the crystal weight gain is recorded once per hour, and the crystal weight gain value per hour is controlled by increasing or decreasing the flow rate or shutting down the cooling gas by not more than + -1% from the weight gain value recorded in the previous hour. The crystal weight gain may be different depending on the target crystal size and should not be taken as limiting the invention. The state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the crystal is indicated to touch the wall of the crucible or the bottom of the crucible, after the temperature is kept for 3 hours, the crystal enters a ending lifting-falling stage, the heating power is increased by 1-2 kw, after the temperature is kept for 1.5 hours, the crystal is lifted at a speed of 0.6mm/h, after the temperature is kept for 4 hours, the lifting speed is increased to 1.5mm/h, the crystal is automatically separated from the crucible, the crystal is cooled and annealed, the power is reduced to stop working at a speed of 40W/h, and then the crystal is naturally cooled for 24 hours, and the gallium oxide crystal prepared by the method is beta-phase Ga 2 O 3 And (3) single crystals.
Example six:
referring to fig. 1, the method for growing a low dislocation density gallium oxide bulk single crystal according to the invention comprises the following steps: firstly wiping with dust-free alcohol, cleaning a hearth, an insulating layer, a crucible and the like by using an industrial dust collector, then loading 5N-grade gallium oxide raw materials with purity of more than 99.99% into the crucible in a clean room, placing the crucible in the hearth of a single crystal furnace, and putting [010 ]]Directional beta-Ga 2 O 3 Crystal seedLoading the crystal on seed rod, centering the seed rod, and vacuumizing to vacuum degree of 1×10 -3 Under Pa, re-charging CO at 1 atmosphere 2 The method comprises the steps of taking gas as a protective gas, heating a crucible, heating the crucible, keeping a high-temperature melt state for 3 hours after gallium oxide raw materials are completely melted, lowering seed crystals to 8mm above a liquid level, keeping the temperature for 25 minutes, judging that the lowered seed crystals start seeding according to the temperature in a furnace, the liquid flow speed, the floating crystal size, the tail end of the seed crystals and the like, controlling the seed crystal rod to rotate clockwise, controlling the rotating speed to be 15rad/min, lowering the seed crystal to 20mm below the liquid level at the speed of 30mm/h after the seed crystals are contacted with the liquid level, controlling the surface of the seed crystals to melt off 3-7 mm, forming an arc surface, controlling the temperature of the melt to be close to the melting point after seeding and neck collecting, generally controlling the temperature to be 1780-1800 ℃, entering a shoulder expanding and equal diameter growth stage, and controlling the heating power to be slowly lowered at the speed of 30W/h for enabling the crystals to grow slowly in the whole shoulder expanding and equal diameter growth stage. In the shoulder expanding and constant diameter growth stage, the crystal is firstly pulled at the speed of 0.4mm/h, then pulled at the speed of 0.05mm/h after the crystal grows to 50 to 100mm, cooling gas is introduced into the seed rod while pulling, the weight curve of the crystal is observed, and the crystal is controlled to grow at a constant speed by controlling the flow rate of the cooling gas. In this example, the crystal weight gain is recorded once per hour, and the crystal weight gain value per hour is controlled by increasing or decreasing the flow rate or shutting down the cooling gas by not more than + -1% from the weight gain value recorded in the previous hour. The crystal weight gain may be different depending on the target crystal size and should not be taken as limiting the invention. The state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the crystal is indicated to touch the wall of the crucible or the bottom of the crucible, after the temperature is kept for 4 hours, the crystal enters a ending lifting and releasing stage, the heating power is increased by 1-2 kw, after the temperature is kept for 2 hours, the crystal is lifted at a speed of 1mm/h, after the temperature is kept for 5 hours, the lifting speed is increased to 1mm/h, the crystal is automatically separated from the crucible, the crystal is cooled and annealed, the power is reduced to stop working at a speed of 50W/h, and then the crystal is naturally cooled for 24 hours, and the gallium oxide crystal prepared by the method is beta-phase Ga 2 O 3 And (3) single crystals.
Embodiment seven:
referring to FIG. 1, a method of the present inventionA method for growing a low dislocation density gallium oxide bulk single crystal comprising the steps of: firstly wiping with dust-free alcohol, cleaning a hearth, an insulating layer, a crucible and the like by using an industrial dust collector, then loading 5N-grade gallium oxide raw materials with purity of more than 99.99% into the crucible in a clean room, placing the crucible in the hearth of a single crystal furnace, and putting [010 ]]Directional beta-Ga 2 O 3 Loading the crystal seed on the seed rod, centering the seed rod, and vacuumizing to a vacuum degree of 1×10 after furnace closing -3 Under Pa, re-charging CO at 1 atmosphere 2 The method comprises the steps of taking gas as a protective gas, heating a crucible, heating the crucible, keeping a high-temperature melt state for 3 hours after gallium oxide raw materials are completely melted, lowering seed crystals to 10mm above a liquid level, keeping the temperature for 45 minutes, judging that the lowered seed crystals start seeding according to the temperature in a furnace, the liquid flow speed, the floating crystal size, the tail end of the seed crystals and the like, controlling the seed crystal rod to rotate clockwise at 20rad/min, lowering the speed to 30mm below the liquid level at the speed of 40mm/h after the seed crystals are contacted with the liquid level, controlling the surface of the seed crystals to melt off 3-7 mm, forming an arc surface, controlling the temperature of the melt to be near the melting point after seeding and neck collecting, generally controlling the temperature to be 1780-1800 ℃, entering a shoulder expansion and equal diameter growth stage, and controlling the heating power to slowly reduce the heating power at the speed of 40W/h in the whole shoulder expansion and equal diameter growth stage to enable the crystals to grow slowly. In the shoulder expansion and constant diameter growth stage, firstly, lifting at a speed of 1mm/h, then lifting at a speed of 0.02mm/h after crystals grow to 50-100 mm, introducing cooling gas into a seed rod while lifting, observing a crystal weight curve, and controlling the uniform growth of crystals by controlling the flow rate of the cooling gas. In this example, the crystal weight gain is recorded once per hour, and the crystal weight gain value per hour is controlled by increasing or decreasing the flow rate or shutting down the cooling gas by not more than + -1% from the weight gain value recorded in the previous hour. The crystal weight gain may be different depending on the target crystal size and should not be taken as limiting the invention. The state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the crystal is indicated to touch the wall of the crucible or the bottom of the crucible, after the temperature is kept for 5 hours, the crystal enters a ending lifting-off stage, the heating power is increased by 1-2 kw, after the temperature is kept for 2 hours, the crystal is lifted at a speed of 1.5mm/h, and after the temperature is kept for 5 hours, the crystal is liftedThe speed is increased to 2mm/h, the crystal is automatically separated from the crucible, the cooling annealing is carried out, the power is reduced to stop working at the speed of 60W/h, then the natural cooling is carried out for 24h, the gallium oxide crystal prepared by the method is beta-phase Ga 2 O 3 And (3) single crystals.
According to the invention, the heating power is controlled, and the temperature gradient of crystal growth is controlled by cooling the seed rod, so that the growth speed of the crystal is controlled, the thermal stress of the crystal is reduced, the cracking of the crystal is reduced, the defect density in the crystal is reduced, the crystal quality is effectively improved, and the gallium oxide bulk single crystal with low single crystal dislocation density is obtained; carbon dioxide is selected as a protective gas, so that the high-temperature decomposition of gallium oxide is reduced; the crystal orientation is selected to be [010 ]]Directional beta-Ga 2 O 3 As seed crystal, its heat conductivity is far greater than that of crystal orientation [100 ]]And [001]The directional crystals are beneficial to controlling the temperature gradient; due to beta-Ga 2 O 3 Is relatively low in [010 ]]The thermal conductivity at room temperature was 27.9W.m -1 ·K -1 And as the temperature increases, the thermal conductivity of the crystal is reduced, and the crystal is pulled at a certain speed in the whole crystal growth process to increase the temperature gradient, thereby being beneficial to controlling the crystal growth.
The above embodiments are illustrative of the present invention, and not limiting, and any simple modifications of the present invention fall within the scope of the present invention.
Claims (13)
1. A method for growing a low dislocation density gallium oxide bulk single crystal, comprising the steps of:
a. and (2) charging: loading a crucible filled with gallium oxide raw materials into a hearth, loading seed crystals on seed rods, vacuumizing the crystal growth furnace, and filling protective gas;
b. heating and melting: heating the crucible to raise the temperature, and keeping the melt state after the raw materials are completely melted;
c. crystal growth: firstly, descending seed crystal to be above the liquid level, keeping for a certain time, then controlling the seed crystal rod to start rotating clockwise or anticlockwise, wherein the rotating speed is 2-20 rad/min, descending seed crystal enters a seeding neck collecting stage, enters a shoulder expanding and equal diameter growing stage after seeding neck collecting, reduces heating power at a speed of 10-40W/h in the shoulder expanding and equal diameter growing stage, and lifts up at a speed of not more than 0.4mm/h when the equal crystal grows to 50-100 mm, and reduces the temperature of the seed crystal rod while lifting up to control uniform weight gain of the crystal;
d. after the crystal grows to a desired size, annealing is performed.
2. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: the shielding gas in the step a is carbon dioxide with one atmosphere.
3. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: the seed crystal is beta-Ga 2 O 3 A crystal, wherein the seed crystal is loaded on a seed crystal clamping head of a seed crystal rod, and the vertical upward direction of the seed crystal is [010 ]]And (5) crystal orientation.
4. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: and c, cooling the seed rod in the step, namely introducing cooling water or cooling gas into the seed rod or outside the seed rod, and controlling the uniform weight gain of the crystal by controlling the flow rate of the cooling water or the cooling gas.
5. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: the heating power is reduced at a speed of 20-30W/h in the step c.
6. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: the speed of crystal pulling in the step c is 0.1mm/h.
7. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: in the step c shoulder expanding and constant diameter growth stage, the crystal is pulled at a speed of 0.4-1 mm/h before growing to 50-100 mm.
8. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: in the step c, the seed crystal is firstly lowered to a position 5-10 mm above the liquid level and is maintained for 15-45 min, and then the seed crystal is lowered to enter a seeding neck collecting stage.
9. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 8, wherein: the step of seeding and neck collecting in the step c is as follows: when the seed crystal contacts the liquid level, the seed crystal is lowered to 10-30 mm below the liquid level at a speed of 20-40 mm/h, and the surface of the seed crystal is controlled to be melted off by 3-7 mm.
10. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 9, wherein: in the step c, the seed crystal is firstly lowered to the position about 10mm above the liquid level, the temperature is kept for 20min, the rotating speed of the seed crystal rod is controlled to be 2rad/min, the seed crystal is lowered to 20mm below the liquid level at the speed of 20mm/h after contacting with the liquid level, and the surface of the seed crystal is controlled to be melted off by 3-7 mm.
11. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: the annealing step in the step d is as follows: the state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the temperature is kept for 2-5 hours, the temperature enters a ending lifting and releasing stage, the heating power is increased by 1-2 kw, after the temperature is kept for 1-2 hours, the lifting speed is increased to 0.5-2 mm/h after the temperature is kept for 3-5 hours, the crystal is separated from the crucible, the lifting is stopped after the crystal weight is stable, the heating power is reduced at the speed of 30-60W/h until the working is stopped, and the temperature is naturally cooled to the room temperature.
12. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 11, wherein: the annealing step in the step d is as follows: the state of the crystal is monitored through a weight curve, when the weight curve shows a wavy line, the temperature is kept for 3 hours, the ending and lifting stages are carried out, the heating power is increased by 1-2 kw, after the temperature is kept for 2 hours, the lifting speed is increased to 1mm/h at first at a speed of 0.5mm/h, the crystal is separated from the crucible, the lifting is stopped after the crystal weight is stable, the heating power is reduced at a speed of 50W/h until the working is stopped, and the temperature is naturally cooled to the room temperature.
13. A method for growing a low dislocation density gallium oxide bulk single crystal as defined in claim 1, wherein: in the step b, the time for maintaining the melt state is 3-5 hours.
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| CN103147121A (en) * | 2013-04-03 | 2013-06-12 | 中国科学院上海硅酸盐研究所 | Device for growing crystals by using lifting and Kyropoulos method |
| CN104357899A (en) * | 2014-11-21 | 2015-02-18 | 中国电子科技集团公司第二十六研究所 | Kyropoulos method-based preparation method of large-size Yb-YAG laser crystals |
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