CN115198370B - Device and method for preparing indium phosphide crystal through vertical temperature gradient solidification - Google Patents
Device and method for preparing indium phosphide crystal through vertical temperature gradient solidification Download PDFInfo
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- CN115198370B CN115198370B CN202210829230.3A CN202210829230A CN115198370B CN 115198370 B CN115198370 B CN 115198370B CN 202210829230 A CN202210829230 A CN 202210829230A CN 115198370 B CN115198370 B CN 115198370B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/003—Heating or cooling of the melt or the crystallised material
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/006—Controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/008—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method using centrifugal force to the charge
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/04—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt
- C30B11/06—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt at least one but not all components of the crystal composition being added
- C30B11/065—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt at least one but not all components of the crystal composition being added before crystallising, e.g. synthesis
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A device and a method for preparing indium phosphide crystals by vertical temperature gradient solidification relate to the preparation of semiconductor materials. The device comprises a furnace body, a crucible, a centrifugal motor and an injection system, and the method is characterized in that in the synthesis process, the crucible is rotated to ensure that the melt in the crucible is attached to the side wall of the crucible under the action of centrifugal force; injecting bubbles into the position of the metal melt close to the side wall of the crucible; after the synthesis is finished, controlling the vertical temperature gradient to finish the growth of the single crystal. Under the action of centrifugal force, the indium atoms with heavier density can move towards the edge of the crucible, the phosphorus atoms with lighter density can move towards the center of the crucible, the synthesis speed is higher, the whole synthesis process is accelerated, and meanwhile, the melt pollution is reduced.
Description
Technical Field
The invention relates to preparation of semiconductor materials, in particular to a device and a method for preparing an indium phosphide crystal by vertical temperature gradient solidification.
Background
InP (indium phosphide) is an important compound semiconductor material following silicon (Si), germanium (Ge) and gallium arsenide (GaAs), is one of the first choice materials for preparing high-frequency and high-speed devices, and InP-based microelectronic devices have the characteristics of high frequency, low noise, high efficiency, radiation resistance and the like, and are widely applied to the fields of 5G networks, space solar cells, terahertz communication, millimeter wave communication and detection and the like. The faster the synthesis of InP, the less contamination from the outside world and the easier it is to prepare high performance InP crystals.
The main synthesis method of InP comprises: solute diffusion synthesis (SSD), horizontal Bridgeman (HB)/Horizontal Gradient Freezing (HGF), infusion synthesis. Among them, the injection synthesis method has the highest efficiency, and is a method for realizing low-cost and high-quality polycrystal industrialization, and for example, chinese issued patents having application numbers of 202010487276.2, 202110618242.7, 201911155615.0, 202110145424.7, respectively, disclose technical schemes for synthesizing compound semiconductor materials using a gas injection device: after the volatile gas source material is heated and gasified, the gasified element is injected into the melt which is static or rotates slowly through the injection pipe to complete the synthesis.
Pure indium begins in the melt and as phosphorus atoms enter the indium melt, an indium-phosphorus melt is formed. When the temperature is reduced to the crystallization temperature (lower than the melting point of indium phosphide), the solidified melt becomes indium phosphide when the phosphorus content reaches or exceeds 50 atomic percent, and excessive phosphorus can overflow; when the composition of phosphorus is less than 50 atomic%, the melt solidifies into indium phosphide and indium.
The time for indium phosphide synthesis depends mainly on the rate of phosphorus uptake by the melt. At a constant temperature, the greater the difference between the saturated phosphorus concentration of the melt and the phosphorus concentration in the melt, the faster the melt can absorb phosphorus.
At the initial stage of phosphorus entering the melt, the concentration of phosphorus in the melt is very low, and the speed of phosphorus element absorption of the melt is very high; as the synthesis is carried out, the concentration of phosphorus in the melt is higher and higher, the phosphorus absorption capacity of the melt is poorer and poorer, and the phosphorus absorption speed of the melt is slower and slower.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method which accelerates the synthesis speed and realizes the in-situ growth of single crystals.
In order to realize the purpose, the invention adopts the following technical scheme:
the utility model provides a device of perpendicular temperature gradient solidification preparation indium phosphide crystal, includes the furnace body, places the crucible that holds in the palm in the support, sets up the seed crystal groove in the crucible bottom, the peripheral multistage heater of crucible, motor, the bracing piece, the injection system, the thermocouple that connect support hold in the palm and the motor, and the key is: the device comprises a crucible, a motor, an injection system and an auxiliary heating system, wherein the motor is a centrifugal motor, the device also comprises an isolation cover covering a central opening of the crucible, the injection system comprises an injection tank, an injection pipe arranged transversely, a transmission pipe connecting the injection tank and the injection pipe, and the auxiliary heating system is arranged on the periphery of the injection tank, the transmission pipe penetrates through the isolation cover, and the injection pipe is arranged in the crucible.
The injection system is connected at the top with a detachable moving rod which is connected with a driving device.
The bottom of the injection system and the top of the isolation cover are provided with mutually matched limiting devices.
Further, the outlet of the injection pipe is close to the side wall of the crucible.
Based on the device, the invention also provides a method for preparing the indium phosphide crystal by vertical temperature gradient solidification, which comprises the following steps:
step 1, placing seed crystals into a seed crystal groove of a crucible, and placing metal indium and boron oxide into the crucible; the red phosphorus was placed in an injection tank and the apparatus was assembled.
And 2, charging 4.0-8.0MPa of pressure protection into the furnace body.
And 4, starting the centrifugal motor to drive the supporting rod crucible to rotate, wherein the rotation speed of the centrifugal motor is 500-5000 r/min.
And 6, after the synthesis is finished, adjusting the power of each sectional heater of the multi-sectional heaters to ensure that the temperature of the thermocouple E, the thermocouple A and the thermocouple D is 500-800 ℃, solidifying the synthesized indium phosphide into a cylindrical solid, and enabling boron oxide to be in a liquid state.
Gradually reducing the rotating speed of the centrifugal motor until the rotating speed is stopped, and completely flowing boron oxide to the bottom of the crucible.
And 7, inserting a thermocouple B and a thermocouple C, adjusting the power of each segmented heater of the multi-segment heaters, enabling the thermocouple E to be 20-50 ℃ lower than the melting point of the indium phosphide, enabling the thermocouple A and the thermocouple D to be 50-200 ℃ higher than the melting point of the indium phosphide, enabling the cylindrical solid indium phosphide to be melted again and liquid to flow to the bottom of the crucible, and lifting the injection system.
The temperature gradient of 5-50 cm/DEG C is established by the indium phosphide fusant in the crucible, and the temperature close to the direction of the seed crystal is the low temperature direction.
And 8, adjusting the power of each sectional heater of the multi-sectional heaters to realize the growth of the indium phosphide single crystal, cooling the system to room temperature after the growth is finished, and taking out the single crystal.
Density of indium in the melt during polycrystalline synthesis (7.3 g/cm) 3 ) Greater than the combined phosphorus and indium atoms (approximately 4.787 g/cm in indium phosphide density) 3 Calculated), boron oxide density (1.8 g/cm) as a covering agent 3 ) And the lowest. The change of the spatial distribution concentration in the indium-phosphorus melt can be changed by centrifugal force: in the crucible, pure indium is at the outermost periphery,the phosphorus and indium atoms bonded together will move together, with the innermost being boron oxide, on the inside of pure indium. The outlet of the injection tube is arranged at the edge of the crucible, pure indium without bonded phosphorus atoms is distributed in the melt around the injection area, the content of phosphorus is always the minimum in all the melt, and the phosphorus can be rapidly absorbed.
And after the synthesis is finished, stopping rotating the crucible, and contacting the melt with the seed crystal to grow the crystal.
Has the beneficial effects that: under the action of centrifugal force, the indium atoms with higher density move towards the edge of the crucible, and the phosphorus atoms with lower density move towards the center of the crucible, so that more indium atoms are arranged on the side wall of the crucible. The concentration of phosphorus atoms around the injection region is low, so that the synthesis rate is high, and the whole synthesis process is accelerated; the centrifugal rapid synthesis and the crystal growth are combined, and the temperature gradient in the vertical direction is accurately controlled during the growth of the single crystal, so that the crystal growth efficiency after injection synthesis is further improved.
Drawings
Figure 1 is a schematic view of the assembled device,
FIG. 2 is a view showing the state of the apparatus in centrifugal synthesis,
figure 3 is a state diagram of the apparatus at the completion of synthesis,
FIG. 4 is a state diagram of the apparatus at the start of single crystal growth,
FIG. 5 is a state diagram of the apparatus in the course of starting the growth of a single crystal,
figure 6 is a diagram of an embodiment of an implantation system.
Wherein, 1: a crucible; 1-1: an isolation cover; 2: a supporting bracket; 3: a multi-stage heater; 4: a metal melt; 5: boron oxide; 6: a support bar; 7: a centrifugal motor; 8: an auxiliary heating system; 9: red phosphorus; 10: an injection system; 10-1: injecting into a tank; 10-2: a conveying pipe; 10-3: an injection pipe; 11, bubbles; 14-1: a bump; 14-2: a groove; 15: a detachable travel bar; 16: indium; 17: a drive device; 18-1, 18-2, 18-3, 18-4, 18-5: a thermocouple; 19: seed crystal; 20: an indium phosphide single crystal.
Detailed Description
A device for preparing indium phosphide crystals by vertical temperature gradient solidification, which is shown in figure 1.
The device comprises a furnace body, a crucible 1 arranged in the furnace body and placed on a support holder 2, a seed crystal groove 1-2 arranged at the bottom of the crucible 1, a multi-section heater 3 at the periphery of the crucible 1, a centrifugal motor 7, a support rod 6 connected with the support holder 2 and the centrifugal motor 7, an injection system 10 and a thermocouple.
The apparatus further comprises an isolation cover 1-1 covering the central opening of the crucible 1; the injection system 10 comprises an injection tank 10-1, an injection pipe 10-3 arranged transversely, a transfer pipe 10-2 connecting the injection tank 10-1 and the injection pipe 10-3, and an auxiliary heating system 8 arranged on the periphery of the injection tank 10-1, wherein the transfer pipe 10-2 penetrates through an isolation cover 1-1, and the injection pipe 10-3 is arranged inside a crucible 1.
The injection system 10 is connected at the top with a detachable moving rod 15, and the moving rod 15 is connected with a driving device 17.
The bottom of the injection system 10 and the top of the isolation cover 1-1 are provided with mutually matched limiting devices.
In the present invention, the injection system 10 rotates synchronously with the crucible 1, remains relatively stationary, and prevents the injection tube 10-3 from stirring the melt in the crucible 1.
The injection system 10 can be independently provided with a driving system to rotate synchronously with the crucible 1, and the injection system 10 can also be limited on the isolating cover 1-1.
In the invention, a limiting device consisting of a groove 14-2 arranged at the top of an isolation cover 1-1 and a bump 14-1 arranged at the corresponding position at the bottom of an injection tank 10-1 is adopted.
The injection system 10 is limited together with the isolation cover 1-1 by the matching of the groove and the bump. The isolating cover 1-1 is firmly connected (e.g. welded) with the crucible 1, and the injection system 10 and the crucible 1 can rotate synchronously.
Due to the centrifugal force, the pure indium in the crucible 1 is distributed on the side wall of the crucible 1, the outlet of the injection pipe 10-3 is close to the side wall of the crucible 1, and the position near the outlet, namely the periphery of the injection area is always in an indium-rich state. In this embodiment, the distance between the outlet of the injection tube 10-3 and the side wall of the crucible 1 is 1-5mm.
Because the injection system 10 needs to lift out the melt after the synthesis is finished, in the embodiment, the injection pipe 10-3 is horizontally arranged or the included angle of 1-5 degrees is formed between the two ends of the injection pipe and the horizontal direction, in the synthesis process, if the injection pipe is horizontally arranged, after all phosphorus is gasified, the melt can enter the injection pipe 10-3 and be solidified in the injection pipe 10-3 after being cooled, so that raw materials are wasted, and the injection pipe 10-3 cannot be reused. In this embodiment, the two ends of the injection pipe 10-3 form downward included angles of 1-5 degrees with the horizontal direction, as shown in fig. 6, when the injection system 10 lifts the melt, a small amount of melt in the injection pipe 10-3 flows out, and the above problem is not caused.
Based on the device for preparing the indium phosphide crystal by vertical temperature gradient solidification, the invention also provides an embodiment of a method for preparing the indium phosphide crystal by vertical temperature gradient solidification, which comprises the following steps:
step 1, placing a metal material required for synthesis in a crucible, and placing a non-metal volatile material required for synthesis in an injection device.
Step 1, placing a seed crystal 19 into a seed crystal groove 1-2 of a crucible 1, and placing metal indium 16 and boron oxide 5 into the crucible 1; placing red phosphorus 9 in an injection tank 10-1, assembling the apparatus: the cover plate on the upper part of the injection tank 10-1 can be separated, and the red phosphorus 9 is placed and then welded; the injection pipe 10-3 is inserted into the central air of the isolation cover 1-1, the injection pipe 10-3 and the transmission pipe 10-2 are welded together, and the upper edge of the crucible 1 and the isolation cover 1-1 are welded together after the welding seam is cooled.
Placing the crucible 1 into a crucible support holder 2; the auxiliary heating system 8 is arranged outside the injection tank 10-1, and the injection system 10 and the detachable movable rod 15 are connected in a manner of adopting a mechanical arm. And (5) sealing the furnace body.
And 2, filling 4.0-8.0MPa of inert gas into the furnace body to play a pressure protection role, as shown in figure 1.
The robot is released and the disengageable transfer bar 15 is disengaged from the implantation system 10.
The crucible 1 is now heated to a lower temperature in order to prevent loss of phosphorus from the injection system 10 prior to injection synthesis.
And 4, starting the centrifugal motor 7 to drive the supporting rod 6 and the crucible 1 to rotate, wherein the rotation speed of the centrifugal motor 7 is 500-5000 r/l. Since the disengageable movable rod 15 is disengaged from the injection system 10 and the thermocouples B18-2 and C18-3 are disengaged, the rotation of the crucible 1 is not affected by the outside.
The indium metal melt is distributed on the inner wall of the crucible 1 and separated from the seed crystal 19, and the boron oxide 5 is distributed on the inner side surface of the indium metal melt.
the auxiliary heating system 8 is started to make the injection tank 10-1 reach 600-900 ℃, the red phosphorus 9 in the injection tank 10-1 is sublimated, and the gas bubbles 11 discharged by the injection pipe 10-3 enter the metal melt 4 for centrifugal injection synthesis, as shown in figure 2.
The power of the auxiliary heating system 8 is gradually increased to ensure that the air bubbles 11 discharged by the injection pipe 10-3 are stable; meanwhile, in order to ensure that the injection system 10 is not separated from the isolation cover 1-1, inert gas can be injected again, and the gas pressure in the furnace body and outside the crucible 1 is increased, so that the external pressure of the crucible 1 is greater than or equal to the internal pressure.
The reason why the temperature inside the crucible 1 is lowered to solidify indium phosphide is that the temperature of the melt is high after the synthesis is completed, and if the rotation of the centrifugal motor 7 is stopped at this time, the high-temperature melt flows toward the bottom of the crucible 1 to melt the seed crystal 19.
The temperature gradient of 5-50 cm/DEG C is established by the indium phosphide melt in the crucible 1, and the temperature close to the seed crystal 19 is in the low temperature direction.
Due to the low temperature at the bottom of the seed crystal 19 and the melting point of indium phosphide, the synthesized indium phosphide melt is higher than the melting point, and eventually a part of the seed crystal 19 will melt and establish an equilibrium state of the seed crystal 19 and the indium phosphide melt.
In the above step, the injection system (10) may solidify into the indium phosphide solid at step 6, possibly damaging the injection tube (10-3). For this purpose, the improvement is as follows:
The speed of the centrifugal motor 7 is reduced by 10-100 revolutions per minute. When the rotation speed of the centrifugal motor 7 is reduced to 0, the disengageable movable rod 15 and the injection system 10 are connected, and the injection system 10 is lifted off the liquid surface in the crucible 1, as shown in FIG. 4.
And 7, inserting a thermocouple B18-2 and a thermocouple C18-3, adjusting the power of each segmented heater of the segmented heaters 3, establishing a temperature gradient of 5-50 cm/DEG C for the indium phosphide melt in the crucible 1, and setting the temperature close to the seed crystal 19 to be in a low-temperature direction.
In the invention, two keys are as follows: 1. in the indium phosphide synthesis stage, the crucible rotates, the melt is separated by centrifugal force, and gaseous phosphorus is injected to the side of the crucible; 2. during the single crystal growth phase, a temperature gradient in the vertical direction is established.
Experiments show that the synthesis speed is improved by 20-30% compared with the traditional injection method in the indium phosphide synthesis stage by adopting the device and the method provided by the invention, and the single crystal production process is accelerated. Because the synthesis speed is accelerated, the melt pollution is reduced, and the carrier concentration of the indium phosphide is less than or equal to 2 multiplied by 10 15 cm -3 Mobility of>4500 cm 2 ·V -1 ·s -1 (ii) a The degree of carrier concentration of the conventional synthetic polycrystal in the case of using the same raw material>5×10 15 cm -3 Mobility of about 3000-4000 cm 2 •V -1 •s -1 。
Claims (6)
1. A device for preparing indium phosphide crystals by vertical temperature gradient solidification comprises a furnace body, a crucible (1) arranged on a support holder (2), a seed crystal groove (1-2) arranged at the bottom of the crucible (1), a multi-section heater (3) arranged at the periphery of the crucible (1), a motor, a support rod (6) connecting the support holder (2) and the motor, an injection system (10) and a thermocouple,
the method is characterized in that: the device comprises a crucible (1), a motor, an injection system (10), an auxiliary heating system (8), a centrifugal motor (7), an isolation cover (1-1) and an isolation cover, wherein the isolation cover covers the central opening of the crucible (1), the injection system (10) comprises an injection tank (10-1), an injection pipe (10-3) which is transversely arranged, a transmission pipe (10-2) which connects the injection tank (10-1) and the injection pipe (10-3), the auxiliary heating system (8) is arranged on the periphery of the injection tank (10-1), the transmission pipe (10-2) penetrates through the isolation cover (1-1), and the injection pipe (10-3) is arranged inside the crucible (1);
the top of the injection system (10) is connected with a detachable moving rod (15), and the moving rod (15) is connected with a driving device (17);
the bottom of the injection system (10) and the top of the isolation cover (1-1) are provided with mutually matched limiting devices.
2. The apparatus according to claim 1, characterized in that the outlet of the injection pipe (10-3) is close to the crucible (1) side wall.
3. Device according to claim 1, characterized in that the number of injection pipes (10-3) is 2-8, horizontally arranged or at an angle of 1-5 ° to the horizontal.
4. The device according to claim 1, characterized in that the limiting device of the bottom of the injection system (10) and the top of the isolation cover (1-1) are mutually matched is that the top of the isolation cover (1-1) is provided with a groove (14-2), and the bottom of the injection tank (10-1) is provided with a lug (14-1) at a corresponding position.
5. A method for preparing indium phosphide crystal by vertical temperature gradient solidification, which is based on the device for preparing indium phosphide crystal by vertical temperature gradient solidification as claimed in any one of claims 1 to 4, and is characterized in that the method comprises the following steps:
step 1, placing a seed crystal (19) into a seed crystal groove (1-2) of a crucible (1), and placing metal indium (16) and boron oxide (5) into the crucible (1); placing red phosphorus (9) in an injection tank (10-1) and assembling the device;
step 2, charging 4.0-8.0MPa pressure protection into the furnace body;
step 3, heating the crucible (1) to 500-600 ℃ by a multi-section heater (3) to melt boron oxide (5) and metal indium (16); the driving device (17) drives the detachable moving rod (15), the injection system (10) is placed on the isolation cover (1-1), and the limiting device is fitted; the disengageable travel bar (15) disengages the injection system (10);
step 4, starting the centrifugal motor (7) to drive the supporting rod (6) and the crucible (1) to rotate, wherein the rotation speed of the centrifugal motor (7) is 500-5000 r/min;
step 5, heating the crucible (1) to be 30-200 ℃ above the melting point of indium phosphide by using a multi-section heater (3);
starting the auxiliary heating system (8) to ensure that the temperature of the injection tank (10-1) reaches 600-900 ℃, sublimating red phosphorus (9) in the injection tank (10-1), and allowing gas discharged from the injection pipe (10-3) to enter the metal melt (4) for centrifugal injection synthesis;
step 6, adjusting the power of each sectional heater of the multi-sectional heater (3) after the synthesis is finished, so that the temperature of a thermocouple E (18-5), a thermocouple A (18-1) and a thermocouple D (18-4) is 500-800 ℃, the synthesized indium phosphide is solidified into a cylindrical solid, and the boron oxide (5) is in a liquid state;
gradually reducing the rotating speed of the centrifugal motor (7) until the rotating speed is stopped, and enabling all the boron oxide (5) to flow to the bottom of the crucible (1);
step 7, inserting a thermocouple B (18-2) and a thermocouple C (18-3), adjusting the power of each segmented heater of the multi-segment heater (3), enabling the thermocouple E (18-5) to be 20-50 ℃ lower than the melting point of indium phosphide, enabling the thermocouple A (18-1) and the thermocouple D (18-4) to be 50-200 ℃ higher than the melting point of indium phosphide, enabling the cylindrical solid indium phosphide to be melted again and to flow to the bottom of the crucible (1), and lifting the injection system (10);
the temperature gradient of 5-50 cm/DEG C is established by the indium phosphide melt in the crucible (1), and the temperature close to the direction of the seed crystal (19) is the low-temperature direction;
and 8, adjusting the power of each sectional heater of the multi-section heater (3) to realize the growth of the indium phosphide single crystal, cooling the system to room temperature after the growth is finished, and taking out the single crystal.
6. The method of claim 5, wherein:
step 6, adjusting the power of each segmented heater of the multi-segment heater (3) after the synthesis is finished, wherein a thermocouple E (18-5) is higher than the melting point of indium phosphide by 20-50 ℃, and a thermocouple A (18-1) and a thermocouple D (18-4) are higher than the melting point of indium phosphide by 50-200 ℃; gradually reducing the rotating speed of the centrifugal motor (7) until the rotating speed is stopped, and slowly flowing the boron oxide (5) and the melt to the bottom of the crucible (1); after the centrifugal motor (7) stops, the injection system (10) is lifted;
and 7, inserting a thermocouple B (18-2) and a thermocouple C (18-3), adjusting the power of each segmented heater of the multi-segment heater (3), establishing a temperature gradient of 5-50 cm/DEG C for the indium phosphide melt in the crucible (1), and setting the temperature in the direction close to the seed crystal (19) as a low-temperature direction.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210829230.3A CN115198370B (en) | 2022-07-15 | 2022-07-15 | Device and method for preparing indium phosphide crystal through vertical temperature gradient solidification |
| PCT/CN2022/138863 WO2024011843A1 (en) | 2022-07-15 | 2022-12-14 | Device and method for preparing indium phosphide crystal by means of vertical temperature gradient freezing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210829230.3A CN115198370B (en) | 2022-07-15 | 2022-07-15 | Device and method for preparing indium phosphide crystal through vertical temperature gradient solidification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115198370A CN115198370A (en) | 2022-10-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4267154A (en) * | 1978-09-29 | 1981-05-12 | Georg Mueller | Apparatus for manufacturing high quality crystals |
| US5650008A (en) * | 1995-12-01 | 1997-07-22 | Advanced Materials Processing, Llc | Method for preparing homogeneous bridgman-type single crystals |
| CN112410883A (en) * | 2020-11-16 | 2021-02-26 | 宇泽半导体(云南)有限公司 | Improved indium phosphide crystal synthesis and growth process and device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4267154A (en) * | 1978-09-29 | 1981-05-12 | Georg Mueller | Apparatus for manufacturing high quality crystals |
| US5650008A (en) * | 1995-12-01 | 1997-07-22 | Advanced Materials Processing, Llc | Method for preparing homogeneous bridgman-type single crystals |
| CN112410883A (en) * | 2020-11-16 | 2021-02-26 | 宇泽半导体(云南)有限公司 | Improved indium phosphide crystal synthesis and growth process and device |
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