CN112410883A - Improved indium phosphide crystal synthesis and growth process and device - Google Patents
Improved indium phosphide crystal synthesis and growth process and device Download PDFInfo
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- CN112410883A CN112410883A CN202011278512.6A CN202011278512A CN112410883A CN 112410883 A CN112410883 A CN 112410883A CN 202011278512 A CN202011278512 A CN 202011278512A CN 112410883 A CN112410883 A CN 112410883A
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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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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/082—Other phosphides of boron, aluminium, gallium or indium
- C01B25/087—Other phosphides of boron, aluminium, gallium or indium of gallium or indium
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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
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Abstract
The invention relates to the technical field of indium phosphide crystal preparation, in particular to a process and a device for synthesizing and growing an indium phosphide crystal. The electromagnetic restraint inductor arranged outside the melt crucible restrains the size and the shape of the transverse cross section of the melt, so that the side surface of the melt is separated from contact with the inner wall of the crucible or partially separated from contact with the inner wall of the crucible. An electromagnetic heating inductor is arranged at the upper part of the crucible to heat the indium phosphide crystal and control the temperature gradient in the crystal. Because an interval is formed between the melt and the wall of the quartz crucible, the contact area between the melt and the crucible is reduced, and the pollution of impurities in the crucible to the indium phosphide crystal is favorably reduced; meanwhile, the contact area of the melt and phosphorus steam is increased, so that phosphorus atoms can be more effectively diffused into the melt, the synthesis and growth speed of the crystal is favorably improved, the transverse section size and shape of the melt and the temperature gradient in the crystal are controlled, and the stability of the crystal growth is favorably improved.
Description
Technical Field
The invention relates to the technical field of indium phosphide crystal preparation, in particular to an improved indium phosphide crystal synthesis and growth process and device.
Background
The indium phosphide crystal synthesis techniques include a solute diffusion synthesis method, a melt solidification synthesis method, and a phosphorus injection synthesis (LEC) method; the LEC method is one of the techniques for growing single crystals.
The solute diffusion synthesis method is a process method for synthesizing indium phosphide at the temperature lower than the melting point of indium phosphide. Schematically referring to fig. 1 and 2, indium metal (not shown in the drawing) and red phosphorus 8 are sealed in a communicated quartz ampoule, namely different areas of a working chamber 1, the indium metal is arranged in a quartz crucible 2, and the red phosphorus 8 is arranged in a phosphorus bubble 3; heating red phosphorus 8 by means of a first heater 4 adjacent to the phosphorus bubble to a determined temperature at which the vapor pressure of the phosphorus vapor in said working chamber 1 is maintained in a determined range below one atmosphere; heating the indium metal to 900-1000 ℃ by a second heater 5 positioned outside the crucible to form an indium metal melt 7, dissolving the phosphorus vapor in the indium metal melt 7 under the environment to form an indium-rich melt 71, keeping the temperature of one end of the indium-rich melt 71 lower than that of the other end, and with the continuous dissolution of the phosphorus vapor, firstly separating out indium phosphide crystals 9 generated by the reaction at the cold end of the indium-rich melt 71, continuously diffusing the phosphorus dissolved in the indium metal melt 7 from the hot end to the cold end and synthesizing the indium phosphide until all the indium metal melt 7 is converted into the indium phosphide crystals 9.
The solute diffusion synthesis method has the advantage of low synthesis temperature, thereby effectively reducing the pollution of silicon element in the quartz crucible 2 to the indium phosphide crystal and obtaining the indium phosphide crystal with higher purity.
The disadvantage of the solute diffusion synthesis method is that 1) the contact area of phosphorus vapor and metallic indium is small; 2) the synthesis temperature is lower. Resulting in a lower indium phosphide synthesis rate.
The melting solidification synthesis method is a process method for synthesizing indium phosphide at the temperature higher than the melting point of indium phosphide. Schematically, referring to fig. 3 and 4, indium metal (not shown in the drawing) and red phosphorus 8 are sealed in different areas of a communicated quartz ampoule (working chamber 1) under vacuum, the indium metal is placed in a quartz crucible 2, and the red phosphorus 8 is placed in a phosphorus bubble 3; red phosphorus 8 is heated to a certain temperature by a first heater 4 adjacent to a phosphorus bubble, so that the vapor pressure of phosphorus vapor in the working chamber 1 is kept higher than the decompression pressure of the indium phosphide melt, the metal indium is heated to be above the melting point of the indium phosphide to form an indium phosphide melt 7, under the environment, the phosphorus vapor is diffused and dissolved in the indium phosphide melt 7 at a higher speed until the phosphorus in the indium phosphide melt 7 is saturated and is completely converted into an indium phosphide melt 72, and the indium phosphide melt 72 is cooled in a gradient manner to obtain an indium phosphide crystal 9.
The melting solidification synthesis method has the advantages that the temperature of the metal indium melt 7 is higher, so the speed of the indium phosphide synthesis reaction is higher than that of the solute diffusion synthesis method; the method has the disadvantages that because the temperatures of the metal indium melt 7 and the indium phosphide melt 72 are high, and the contact area of the working medium melt and the crucible 2 is large, the pollution of impurity silicon introduced from the crucible 2 is heavy, the purity of the indium phosphide crystal 9 is negatively affected, and meanwhile, the contact area of phosphorus steam and the metal indium is small, so that the further improvement of the synthesis speed is limited.
The LEC synthesis method is a synthesis and crystal growth method which comprises injecting gaseous phosphorus into an indium metal melt 7 under the condition of higher than the melting point of indium phosphide, firstly generating an indium phosphide melt 72, and then manufacturing an indium phosphide single crystal by using a CZ method, and is schematically shown in figures 5 and 6.
In a working chamber 1, metal indium and an inert covering agent (such as boron oxide) 12 which is transparent fluid at the synthesis process temperature are put into a quartz crucible 2, red phosphorus 8 is put into a phosphorus bubble 3, the working chamber 1 is vacuumized and injected with inert gas before being heated, the metal indium is heated to be above the melting point of the indium phosphide, the transparent inert fluid covering agent (such as boron oxide) 12 covers an indium phosphide melt 7 in the crucible 2, and the red phosphorus 8 is heated to generate phosphorus vapor, so that the pressure of the phosphorus vapor is higher than that of the inert gas.
During injection synthesis, the phosphorus bubbles 3 move downwards, so that the communicating pipes 11 of the phosphorus bubbles 3 penetrate through the inert fluid covering agent 12 to enter the metal indium melt 7, and the phosphorus steam is blown into the metal indium melt 7 to combine phosphorus and the metal indium melt 7 to generate an indium phosphide melt 72; next, an indium phosphide single-crystal seed crystal 13 is fused with the indium phosphide melt 72 through an inert fluid covering agent 12, and an indium phosphide crystal 9 in a single-crystal state is further pulled.
The LEC synthesis method has the following defects:
1. because the temperature of the metal indium melt 7 and the indium phosphide melt 72 is higher and the contact area with the quartz crucible is larger, the pollution of impurity silicon introduced from the quartz crucible is heavier;
2. in the subsequent crystal pulling process, the cross-sectional area of the liquid level at the top of the indium phosphide melt 72 is larger, so that the distance L from the center of the liquid level to the edge and the temperature difference Delta T are both larger, thereby causing stronger convection action of the melt and being not beneficial to the stability of a crystal growth interface.
3. As the crystal grows, the temperature gradient near the contact surface of the indium phosphide crystal 9 and the indium phosphide melt 72 is uncontrollable, which is not beneficial to the stability of the crystal pulling process and is easy to have the crystal defects.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an improved indium phosphide crystal synthesis and growth process and an improved indium phosphide crystal growth device. The process has the advantages of reducing the pollution of impurity silicon to the indium phosphide crystal, improving the indium phosphide synthesis speed, improving the reaction temperature on the premise of the same tolerable silicon impurity concentration, improving the reaction speed by about 10 percent every time the reaction temperature is improved by 10 ℃, improving the stability of the crystal growth process, reducing the growth defects and improving the quality and the productivity of the indium phosphide crystal, particularly the indium phosphide single crystal.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the first improved technical scheme aims at the LEC synthesis method:
an improved indium phosphide crystal synthesis and growth process comprises the following steps,
step S1, charging:
putting an indium metal working medium and an inert fluid covering agent (such as boron oxide) in a crucible, putting the crucible in a working cavity, vacuumizing and sealing the working cavity for isolation, and filling inert protective gas into the working cavity under 2-4 MPa;
step S2, heating and melt constraining:
heating and melting the metallic indium by an electromagnetic confinement inductor at the periphery of the crucible, keeping the temperature of the metallic indium melt in the crucible and the indium-rich melt and the indium phosphide melt generated by dissolving phosphorus at 1062-1162 ℃ and under the coverage of an inert fluid covering agent, through the interaction of an electromagnetic field generated by an electromagnetic confinement inductor and induced currents generated in the indium metal melt and indium-rich melt and indium phosphide melt generated by dissolving phosphorus, generating electromagnetic pressure pointing to the inside of the melt on the surface of the melt, and enabling the cross section of the melt to be in a size constraint state under the combined action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt, so that the indium metal melt and the indium-rich melt and the indium phosphide melt generated by dissolving phosphorus are separated or partially separated from direct contact with the inner wall of the crucible;
heating red phosphorus by a first heater adjacent to the phosphorus bubble to make the vapor pressure of the phosphorus higher than that of the inert gas in the working chamber;
step S3, synthesizing indium phosphide:
reducing phosphorus bubbles to enable the communicating pipe to be communicated with the inner cavity of the crucible and the inner cavity of the phosphorus bubbles, injecting phosphorus steam into the metal indium melt, and enabling phosphorus and the metal indium melt to react to synthesize an indium phosphide melt until the reaction is finished;
step S4, pulling the crystal:
and (3) utilizing indium phosphide crystal seed crystals to penetrate through an inert fluid covering agent to be welded with the indium phosphide melt, and further utilizing a CZ (Czochralski) method to produce the indium phosphide crystals in a crystalline state.
Furthermore, the top of the indium phosphide melt confined in the crucible is longitudinally convex, and the transverse diameter of the cross section of the upper part of the convex is larger than that of the drawn indium phosphide crystal and smaller than that of the inside of the crucible.
Further, after the indium phosphide crystal grows to a certain length, an electromagnetic heating inductor arranged above the crucible is started, the indium phosphide crystal pulled in the step S4 is heated by the electromagnetic heating inductor, and the longitudinal temperature gradient distribution and the radial temperature gradient distribution in the indium phosphide crystal are controlled.
The apparatus for the first process solution, the improved indium phosphide crystal synthesis and growth process, comprises:
the working cavity is used for maintaining the environment required in the growth process of the indium phosphide crystal;
the crucible is arranged in the working cavity and used for containing working media such as metal indium, indium phosphide and the like and an inert fluid covering agent;
the phosphorus bubble is arranged in the working cavity and used for containing red phosphorus; the inner cavity of the phosphorus bubble is communicated with the crucible cavity through a communicating pipe;
the first heater is positioned near the phosphorus bubble and used for heating red phosphorus and maintaining the phosphorus vapor pressure required by the process;
the electromagnetic constraint inductor is arranged in the working cavity, is positioned at the periphery of the crucible and is used for heating working media in the crucible and constraining the transverse section size and the shape of the metal indium melt or the indium phosphide melt in the crucible so as to ensure that the side surface of the metal indium melt or the indium phosphide melt in the crucible is separated from contact or partially separated from contact with the inner wall of the crucible;
and the electromagnetic heating inductor is arranged in the working cavity, is positioned at the upper part of the crucible and is used for heating the indium phosphide crystal.
A second improved process solution is directed to a solute diffusion synthesis method comprising the steps of:
step A1, charging:
placing metal indium in a crucible, placing red phosphorus in a phosphorus bubble, placing the crucible and the phosphorus bubble in a working cavity, vacuumizing the working cavity, and sealing and isolating the working cavity;
step A2, heating:
heating red phosphorus by a first heater adjacent to a phosphorus bubble to gasify the red phosphorus, and maintaining the phosphorus vapor pressure required for generating indium phosphide by a reaction in a working chamber, wherein the phosphorus vapor pressure is higher than or equal to the dissociation vapor pressure of the indium phosphide at a reaction temperature which is higher than the melting point of metal indium and lower than the melting point of an indium phosphide crystal;
heating and melting the metal indium by an electromagnetic confinement inductor positioned outside the crucible, and keeping the temperature range of the metal indium melt and the indium-rich melt (generated by dissolving phosphorus) at 500-1062 ℃; generating electromagnetic pressure pointing to the inside of the melt on the surface of the melt through the interaction of an electromagnetic field generated by an electromagnetic constraint inductor and induced current generated in the melt, and enabling the cross sections of the indium metal melt and the indium-rich melt to be in a size constraint state under the combined action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt, so that the melt is separated or partially separated from direct contact with the inner wall of the crucible;
step a3, synthesizing indium phosphide:
indium in the metal indium melt and the indium-rich melt is contacted with gaseous phosphorus to react to generate indium phosphide, and indium phosphide crystals are separated out from the indium phosphide at the low-temperature section of the melt until all the metal indium reacts with the gaseous phosphorus to generate the indium phosphide crystals.
The apparatus for the second improved process solution, improved indium phosphide crystal synthesis and growth process, comprises:
the working cavity is used for maintaining the pressure and the atmosphere environment required in the indium phosphide crystal synthesis process;
the crucible is arranged in the working cavity and used for containing working media such as metal indium, indium phosphide and the like;
the inner cavity of the phosphorus bubble is communicated with the crucible cavity through a channel;
the first heater is positioned near the phosphorus bubble and the channel and is used for heating red phosphorus and maintaining the phosphorus vapor pressure required by the working cavity and the channel;
and the electromagnetic constraint inductor is positioned at the periphery of the crucible and used for heating the working medium in the crucible and constraining the transverse section size and the transverse section shape of the indium metal melt and the indium-rich melt in the crucible so as to ensure that the side surface of the melt in the crucible is separated from contact or partially separated from contact with the inner wall of the crucible.
The third improved technical proposal is directed to a melting solidification synthesis method, which comprises the following steps:
step B1, charging:
placing metal indium in a crucible, placing red phosphorus in a phosphorus bubble, placing the crucible and the phosphorus bubble in a working cavity, vacuumizing the working cavity, and sealing and isolating the working cavity;
step B2, heating:
heating red phosphorus by a first heater adjacent to the phosphorus bubble to gasify the red phosphorus, and maintaining the phosphorus vapor pressure required by the growth of indium phosphide crystals in the working cavity, wherein the phosphorus vapor pressure is higher than the dissociation vapor pressure of the indium phosphide crystals at the temperature of 1062 ℃;
melting the metal indium by an electromagnetic confinement inductor positioned at the periphery of the crucible, and keeping the temperature of the metal indium melt or the indium phosphide melt between 1062 ℃ and 1162 ℃; generating electromagnetic pressure pointing to the inside of the melt on the surface of the melt through the interaction of an electromagnetic field generated by an electromagnetic constraint inductor and induced current generated in the melt, and enabling the cross section of the melt to be in a size constraint state under the combined action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt, so that the metal indium melt or the indium phosphide melt is separated or partially separated from direct contact with the inner wall of the crucible;
step B3, synthesizing indium phosphide:
the metal indium melt and gaseous phosphorus are contacted and reacted to generate an indium phosphide melt, and the indium phosphide melt is cooled to generate an indium phosphide crystal.
The apparatus for the third improved process solution, improved indium phosphide crystal synthesis and growth process, comprises:
the working cavity is used for maintaining the pressure and the atmosphere environment required in the indium phosphide crystal synthesis process;
the crucible is arranged in the working cavity and used for containing working media such as metal indium, indium phosphide and the like;
the inner cavity of the phosphorus bubble is communicated with the crucible cavity through a channel;
the first heater is positioned near the phosphorus bubble and the channel and used for heating red phosphorus and maintaining the phosphorus vapor pressure required by the working cavity and the channel;
and the electromagnetic constraint inductor is positioned at the periphery of the crucible and used for heating the working medium in the crucible and constraining the transverse section size and shape of the melt in the crucible so as to ensure that the side surface of the melt in the crucible is separated from contact or partially separated from contact with the inner wall of the crucible.
Compared with the prior art, the invention has the beneficial effects that:
compared with the prior art, the invention restrains the shape of the indium/indium phosphide melt to separate from or partially separate from the quartz crucible by means of the electromagnetic constraint force and the suspension force generated by the electromagnetic constraint inductor, thereby bringing the following advantages:
1. because an interval is formed between the melt and the wall of the quartz crucible, the contact area between the melt and the crucible is reduced, and the pollution of impurity silicon to the indium phosphide crystal is favorably reduced.
2. For the improved solute diffusion synthesis method and the improved melting solidification synthesis method, as the contact area of the melt and phosphorus steam is increased, phosphorus atoms can be more effectively diffused into the melt, which is beneficial to improving the synthesis speed;
3. for the improved solute diffusion synthesis, the reaction temperature can be increased by about 10% for every 10 ℃ increase in reaction temperature, with the same tolerable concentration of silicon impurities.
4. For the improved LEC method, the radial Grashof number can be reduced by melting, and the stability of the crystal growth process is improved.
From the expression of the Grashof number describing the stability of the fluid:
wherein:
GT: grashof number, smaller GTThe stability is higher;
g: acceleration of gravity;
βT: a melt expansion coefficient;
l: characteristic length, where the melt cross-section center to edge distance is considered;
ΔT: temperature differences, here taking into account the temperature difference between the center and the edge of the melt cross section;
v: viscosity coefficient of melt
It can be seen that the Grashof number is strongly and positively correlated with the characteristic length and the temperature difference, because the constrained top of the indium phosphide melt is longitudinally convex, the transverse diameter size of the cross section of the convex upper part can be far smaller than that of the crucible, for the radial component of melt convection, the characteristic size is the melt cross section semi-transverse diameter, the reduction of the characteristic size also reduces the temperature difference delta T between the radial center and the edge of the melt, and therefore the radial Grashof number of the melt is greatly reduced, and the stability of the crystal pulling process is favorably improved.
5. For the LEC method, the invention heats the indium phosphide crystal in an auxiliary way by means of the electromagnetic heating inductor, actively adjusts and controls the temperature gradient in the crystal, is favorable for stabilizing the crystal growth environment, reduces the growth defects and improves the quality and the productivity of the indium phosphide crystal, particularly the indium phosphide single crystal.
Drawings
FIG. 1 is a schematic representation of the melting stage of indium metal by a prior art solute diffusion synthesis process;
FIG. 2 is a schematic representation of the indium phosphide synthesis and crystal growth stages of a prior art solute diffusion synthesis process;
FIG. 3 is a schematic illustration of the melting stage of metallic indium by a prior art melt solidification synthesis process;
FIG. 4 is a schematic representation of the indium phosphide synthesis and crystal growth stages of a prior art melt solidification synthesis process;
FIG. 5 is a schematic representation of the prior art LEC indium phosphide synthesis stage;
FIG. 6 is a schematic representation of the prior art LEC method indium phosphide crystal growth phase;
FIG. 7 is a schematic diagram of an improved indium phosphide crystal synthesis and growth process and apparatus of the present invention, an improved solute diffusion method for melting indium metal;
FIG. 8 is a schematic diagram and schematic diagram of an improved indium phosphide crystal synthesis and growth process and apparatus of the present invention, an improved solute diffusion indium phosphide synthesis and crystal growth stage;
FIG. 9 is a schematic diagram of an improved indium phosphide crystal synthesis and growth process and apparatus of the present invention, an improved melting solidification method for the melting stage of indium metal;
FIG. 10 is a schematic diagram of the improved indium phosphide crystal synthesis and growth process and apparatus of the present invention, an improved melt solidification indium phosphide synthesis and crystal growth phase;
FIG. 11 is a schematic diagram of the improved synthesis and growth process and apparatus of indium phosphide crystal according to the invention, and the improved LEC method indium phosphide synthesis stage.
FIG. 12 is a schematic diagram of the improved synthesis and growth process and apparatus of indium phosphide crystal according to the present invention, and the improved LEC method for indium phosphide crystal growth stage.
In the figure, 1, a working chamber; 2. a crucible; 3. carrying out phosphorus bubble; 4. a first heater; 5. a second heater; 51. an electromagnetic confinement inductor; 52. an electromagnetic heating inductor; 7. a metal indium melt; 71. an indium-rich melt; 72. an indium phosphide melt; 8. red phosphorus; 9. indium phosphide crystals; 11. a communicating pipe; 12. an inert fluid blanketing agent; 13. seed crystal; 14. a balance cavity; 15. a channel.
Detailed Description
The improved indium phosphide crystal synthesis and growth process and device of the invention are further described in detail in the following with reference to the drawings and specific examples.
Example 1
Referring to fig. 7 and 8:
this example is an improved indium phosphide crystal synthesis and growth process for solute diffusion synthesis, comprising the steps of:
step A1, charging:
placing metal indium (not shown in the drawing) in a crucible 2, placing red phosphorus 8 in a phosphorus bubble 3, placing the crucible 2 and the phosphorus bubble 3 in a quartz ampoule (a working chamber 1), vacuumizing the working chamber 1, and sealing and isolating;
step a2, heating and melt constraining:
heating and melting the metal indium by an electromagnetic constraint inductor 51 positioned at the periphery of the crucible 2, on one hand, maintaining the synthesis temperature required by the reaction to generate indium phosphide, and enabling the temperature range of the metal indium melt 7 or the indium-rich melt 71 to be between 700 and 1000 ℃; on the other hand, through the interaction of the electromagnetic field generated by the electromagnetic confinement inductor 51 and the induced current generated in the indium metal melt 7 or the indium-rich melt 71, electromagnetic pressure pointing to the inside of the indium metal melt 7 or the indium-rich melt 71 is generated on the surface of the indium metal melt 7 or the indium-rich melt 71, and the cross section of the indium metal melt 7 or the indium-rich melt 71 is in a size-constrained state and is separated or partially separated from direct contact with the inner wall of the crucible 2 under the combined action of the melt gravity, the electromagnetic pressure and the melt surface tension;
step a3, synthesizing indium phosphide:
the indium metal melt absorbs gaseous phosphorus to generate an indium-rich melt 71, further reacts with the gaseous phosphorus to generate indium phosphide, and the indium phosphide crystals 9 are separated out from the indium phosphide at the low-temperature section of the indium-rich melt 71 until the indium metal melt 7 is completely converted into the indium phosphide crystals 9.
The invention further discloses a device for the indium phosphide crystal synthesis process of embodiment 1, which comprises:
a quartz ampoule (working chamber 1) for maintaining the environment required in the indium phosphide crystal synthesis process;
the crucible 2 is arranged in the working chamber 1 and is used for containing working media such as metal indium, indium phosphide and the like;
the phosphorus bubble 3 is used for containing red phosphorus, and a channel 15 is arranged between the inner cavity of the phosphorus bubble 3 and the cavity of the crucible 2 and communicated with each other;
a first heater 4, which is positioned near the phosphorus bubble 3 and the channel 15 and is used for heating the red phosphorus 8 and maintaining the phosphorus vapor pressure required by the synthesis process;
the electromagnetic restraint inductor 51 is positioned outside the quartz ampoule (working chamber 1) and on the periphery of the crucible 2 and used for heating the working medium of the metal indium and the indium-rich melt, controlling the cooling temperature gradient of the indium phosphide and restraining the section size and the shape of the metal indium melt 7 or the indium-rich melt 71 in the crucible 2 so as to enable the side surface of the metal indium melt in the crucible 2 to be separated from contact with or partially separated from contact with the inner wall of the crucible 2.
Example 2
Referring to fig. 9 and 10, this embodiment is an improved synthesis and growth process of indium phosphide crystal for the melting solidification synthesis method, and includes the following process steps:
step B1, charging:
placing metal indium in a crucible 2, placing red phosphorus 8 in a phosphorus bubble 3, placing the crucible 2 and the phosphorus bubble 3 in a quartz ampoule (a working cavity 1), vacuumizing the working cavity 1, and sealing and isolating;
step B2, heating:
melting the metal indium by an electromagnetic confinement inductor 51 positioned outside the crucible, and keeping the temperature of the metal indium melt 7 between 1062 ℃ and 1162 ℃; through the interaction of an electromagnetic field generated by the electromagnetic confinement inductor 51 and an induced current generated in the indium metal melt 7, electromagnetic pressure pointing to the inside of the melt is generated on the surface of the melt, and the cross section of the indium metal melt 7 is in a size confinement state and is separated or partially separated from direct contact with the inner wall of the crucible 2 under the combined action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt;
the red phosphorus 8 is vaporized by heating it by the first heater 4 adjacent to the phosphorus bubble 3, maintaining a phosphorus vapor pressure in the working chamber 1 that is higher than the dissociation vapor pressure of indium phosphide at a temperature of 1062 ℃. Controlling the heating temperature of the phosphorus bubble 3 according to the corresponding relation of a P-T phase diagram of phosphorus, and simultaneously filling inert gas with corresponding pressure intensity into the space between the balance cavity 14 and the working cavity 1 to balance the pressure in the working cavity 1;
step B3, synthesizing indium phosphide:
the metal indium melt 7 is contacted with gaseous phosphorus to react to generate an indium phosphide melt 72, similarly, the interaction of an electromagnetic field generated by the electromagnetic confinement inductor 51 and an induced current generated in the indium phosphide melt 72 generates electromagnetic pressure pointing to the inside of the melt on the surface of the indium phosphide melt 72, and under the combined action of the melt gravity, the electromagnetic pressure and the melt surface tension, the cross section of the indium phosphide melt 72 is in a size-constrained state and is separated or partially separated from direct contact with the inner wall of the crucible 2. Cooling the indium phosphide melt 72 in a gradient manner to generate an indium phosphide crystal 9;
the invention further discloses a device for the indium phosphide crystal synthesis process of embodiment 2, which comprises:
a quartz ampoule (working chamber 1) for maintaining the environment required in the indium phosphide crystal synthesis process;
the crucible 2 is arranged in the working cavity 1 and is used for containing working media such as metal indium, indium phosphide generated by reaction and the like;
the phosphorus bubble 3 is used for placing red phosphorus, and a channel 15 is arranged between the inner cavity of the phosphorus bubble 3 and the cavity of the crucible 2 and communicated with each other;
a first heater 4, located near the phosphor bubble 3 and the channel 15, for heating the red phosphor 8 to maintain the vapor pressure of the phosphor required for the synthesis process;
the electromagnetic constraint inductor 51 is positioned outside the quartz ampoule (working chamber 1), on the periphery of the crucible 2, and is used for heating the working medium of the metal indium and the indium phosphide, and constraining the sectional sizes and the shapes of the metal indium melt 7 and the indium phosphide melt 72 in the crucible 2, so that the side surfaces of the metal indium melt 7 and the indium phosphide melt 72 in the crucible 2 are separated from contact with the inner wall of the crucible 2 or are partially separated from contact with the inner wall of the crucible 2;
a balance chamber 14 is further provided outside the working chamber 1, and the high pressure inside the working chamber 1 is balanced by charging an inert gas into the balance chamber 14.
Example 3
Referring to fig. 11 and 12, this embodiment is an improved synthesis and growth process of indium phosphide crystal for LEC synthesis, and includes the following steps:
step S1, charging:
coating the indium metal, inert fluid coating agent 12 (B)2O3) Placing the crucible 2 in the crucible 2, placing the crucible 2 in the working cavity 1, placing the red phosphorus 8 in the phosphorus bubble 3, vacuumizing the working cavity 1, filling inert gas with the pressure of 2MPa, and sealing and isolating the working cavity 1;
step S2, heating and melt constraining:
heating the indium metal by an electromagnetic confinement inductor 51 to keep the temperature of the indium metal melt 7 between 1062 ℃ and 1110 ℃ and under the coverage of the inert fluid covering agent 12;
through the interaction of an electromagnetic field generated by the electromagnetic confinement inductor 51 and an induced current generated in the indium metal melt 7, electromagnetic pressure pointing to the inside of the melt is generated on the surface of the indium metal melt 7, and under the resultant force action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt, the cross section of the indium metal melt 7 is in a size confinement state and is separated or partially separated from direct contact with the inner wall of the crucible 2;
heating red phosphorus 8 by a first heater 4 adjacent to a phosphorus bubble 3 to make the vapor pressure of the phosphorus higher than the pressure of inert gas in the working chamber 1;
step S3, synthesizing indium phosphide;
and reducing the phosphorus bubbles 3, enabling the communicating pipe 11 to pass through the inert fluid covering agent 12 to communicate the inner cavity of the crucible 2 with the inner cavity of the phosphorus bubbles 3, injecting phosphorus steam into the indium metal melt 7, and enabling phosphorus and the indium metal melt 7 to react to synthesize an indium phosphide melt 72 until the reaction is finished. Similarly, the interaction between the electromagnetic field generated by the electromagnetic confinement inductor 51 and the induced current generated in the indium phosphide melt 72 generates electromagnetic pressure pointing to the inside of the melt on the surface of the indium phosphide melt 72, so that the cross section of the indium phosphide melt 72 is in a size-confined state and is separated or partially separated from direct contact with the inner wall of the crucible 2 under the combined action of the melt gravity, the electromagnetic pressure and the melt surface tension;
step S4, indium phosphide single crystal growth:
adjusting the electromagnetic confinement inductor 51 to make the top of the confined indium phosphide melt 72 longitudinally in a convex shape, wherein the cross-sectional diameter of the convex upper part is larger than that of the pulled crystal 9 and smaller than that of the crucible;
after the reaction is finished, lowering the indium phosphide single-crystal seed crystal 13, leading the indium phosphide single-crystal seed crystal 13 to pass through the inert fluid covering agent 12 and be welded with the indium phosphide melt 72, and pulling out a single-crystal indium phosphide crystal 9 from the indium phosphide melt 72 by using a Czochralski (CZ) method under the induction of the crystal orientation of the indium phosphide single-crystal seed crystal 13;
step S5, single crystal temperature gradient control
When the indium phosphide crystal grows to a certain length, the high-frequency power supply of the electromagnetic heating inductor 52 is switched on to heat the indium phosphide single-crystal rod so as to control the temperature gradient distribution in the single-crystal rod.
An apparatus for use in the improved indium phosphide crystal synthesis process of example 3, comprising:
the working chamber 1 is used for maintaining the environment required in the indium phosphide crystal synthesis process;
a crucible 2 arranged in the working chamber 1 for placing working substances such as metallic indium, indium phosphide and the like and an inert fluid covering agent 12 (B)2O3)；
The phosphorus bubble 3 is arranged in the working cavity 1 and is used for containing red phosphorus 8;
the communicating pipe 11 is used for realizing communication and non-communication between the phosphorus bubbles 3 and the working medium melt in the crucible 2;
the first heater 4 is arranged outside the phosphorus bubble 3 and used for heating and gasifying red phosphorus 8;
the electromagnetic constraint inductor 51 is positioned at the periphery of the crucible 2 and is used for heating working media such as the metal indium, the indium phosphide and the like, and constraining the sectional size and the shape of the metal indium melt 7 and the indium phosphide melt 72 in the crucible 2 so as to ensure that the side surface of the melt in the crucible 2 is separated from contact or partially separated from contact with the inner wall of the crucible 2; and an electromagnetic heating inductor 52 arranged above the crucible 2 for controlling the temperature gradient distribution in the indium phosphide single crystal.
Claims (8)
1. An improved indium phosphide crystal synthesis and growth process is characterized by comprising the following steps,
step S1, charging:
placing metal indium and an inert fluid covering agent in a crucible, placing red phosphorus in a phosphorus bubble, placing the crucible in a working cavity, vacuumizing and sealing the working cavity for isolation, and filling inert protective gas into the working cavity under 2-4 MPa;
step S2, heating and melt constraining:
heating and melting the metal indium by an electromagnetic confinement inductor positioned on the periphery of a crucible, keeping the temperature of a metal indium melt in the crucible at 1062-1162 ℃ and under the coverage of an inert fluid covering agent, generating electromagnetic pressure pointing to the inside of the melt on the surfaces of the metal indium melt and indium-rich melt and indium phosphide melt generated by dissolving phosphorus through the interaction of an electromagnetic field generated by the electromagnetic confinement inductor and induced current generated in the metal indium melt, and keeping the cross section of the melt in a size-constrained state under the combined action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt so as to separate or partially separate the melt from direct contact with the inner wall of the crucible;
heating red phosphorus by a first heater adjacent to the phosphorus bubble to generate phosphorus vapor, wherein the phosphorus vapor pressure is higher than the pressure of inert gas in the working chamber;
step S3, synthesizing indium phosphide:
communicating the communicating pipe with the inner cavity of the crucible and the inner cavity of the phosphorus bubble, injecting phosphorus steam into the metal indium melt, and reacting phosphorus and the metal indium melt to synthesize an indium phosphide melt until the reaction is finished;
step S4, pulling the crystal:
and (3) utilizing indium phosphide crystal seed crystals to penetrate through the inert fluid covering agent to be welded with the indium phosphide melt, and further pulling out the indium phosphide crystal in a crystalline state.
2. An improved indium phosphide crystal synthesis and growth process as set forth in claim 1 wherein the top of the indium phosphide melt confined in the crucible is longitudinally convex, the cross-sectional dimension of the upper portion of the convex being greater than the cross-sectional dimension of the indium phosphide crystal being drawn and less than the cross-sectional dimension of the interior of the crucible.
3. The improved indium phosphide crystal synthesis and growth process as set forth in claim 1,
and after the indium phosphide crystal grows to a certain length, starting an electromagnetic heating inductor arranged above the crucible, heating the indium phosphide crystal pulled in the step S4 through the electromagnetic heating inductor, and controlling the longitudinal temperature gradient distribution and the radial temperature gradient distribution in the indium phosphide crystal.
4. An apparatus for use in an improved indium phosphide crystal synthesis and growth process as claimed in any one of claims 1 to 3, comprising:
the working cavity is used for maintaining the environment required in the growth process of the indium phosphide crystal;
the crucible is arranged in the working cavity and used for containing metal indium, indium phosphide and an inert fluid covering agent;
the phosphorus bubble is arranged in the working cavity and used for containing red phosphorus;
the inner cavity of the phosphorus bubble is communicated with the crucible cavity through a communicating pipe;
the first heater is positioned near the phosphorus bubble and used for heating red phosphorus and maintaining the phosphorus vapor pressure required by the process;
the electromagnetic constraint inductor is arranged in the working cavity, is positioned at the periphery of the crucible, and is used for heating and melting the working medium in the crucible and constraining the transverse section size and the shape of the working medium melt in the crucible so as to ensure that the side surfaces of the metal indium melt and the indium phosphide melt in the crucible are separated from contact or partially separated from contact with the inner wall of the crucible;
and the electromagnetic heating inductor is arranged in the working cavity, is positioned at the upper part of the crucible and is used for heating the indium phosphide crystal.
5. An improved indium phosphide crystal synthesis process is characterized by comprising the following steps:
step A1, charging:
placing metal indium in a crucible, placing red phosphorus in a phosphorus bubble, placing the crucible and the phosphorus bubble in a working cavity, vacuumizing the working cavity, and sealing and isolating the working cavity;
step a2, heating and melt constraining:
heating red phosphorus by a first heater adjacent to a phosphorus bubble to gasify the red phosphorus, and maintaining the phosphorus vapor pressure required for generating indium phosphide by a reaction in a working chamber, wherein the phosphorus vapor pressure is higher than or equal to the dissociation vapor pressure of the indium phosphide at a reaction temperature which is higher than the melting point of metal indium and lower than the melting point of an indium phosphide crystal;
heating and melting the metal indium through an electromagnetic confinement inductor positioned at the periphery of the crucible, and keeping the temperature range of the metal indium melt or the indium-rich melt formed by phosphorus vapor diffusion at 500-1062 ℃; through the interaction of an electromagnetic field generated by an electromagnetic constraint inductor and induced current generated in the indium metal melt or the indium-rich melt, electromagnetic pressure pointing to the inside of the melt is generated on the surface of the melt, and under the combined action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt, the cross section of the indium metal melt or the indium-rich melt is in a size constraint state, so that the indium metal melt or the indium-rich melt is separated or partially separated from direct contact with the inner wall of the crucible;
step a3, synthesizing indium phosphide:
the metal indium melt reacts with gaseous phosphorus to generate indium phosphide, and indium phosphide crystals are separated out from the indium phosphide at the low-temperature section of the melt until all the metal indium melt reacts with the gaseous phosphorus to generate the indium phosphide crystals.
6. An improved indium phosphide crystal synthesis process is characterized by comprising the following steps:
step B1, charging:
placing metal indium in a crucible, placing red phosphorus in a phosphorus bubble, placing the crucible and the phosphorus bubble in a working cavity, vacuumizing the working cavity, and sealing and isolating the working cavity;
step B2, heating and melt constraining:
heating red phosphorus by a first heater adjacent to the phosphorus bubble to gasify the red phosphorus, and maintaining the phosphorus vapor pressure required by the growth of indium phosphide crystals in the working cavity, wherein the phosphorus vapor pressure is higher than the dissociation vapor pressure of the indium phosphide crystals at the temperature of 1062 ℃;
melting the metal indium through an electromagnetic confinement inductor positioned at the periphery of the crucible, and keeping the temperature of the metal indium melt between 1062 ℃ and 1162 ℃; generating electromagnetic pressure pointing to the inside of the melt on the surface of the metal indium melt through the interaction of an electromagnetic field generated by an electromagnetic constraint inductor and induced current generated in the metal indium melt, and enabling the cross section of the metal indium melt, the indium-rich melt or the indium phosphide melt to be in a size constraint state under the combined action of the gravity of the melt, the electromagnetic pressure and the surface tension of the melt, and separating or partially separating from direct contact with the inner wall of the crucible;
step B3, synthesizing indium phosphide:
the metal indium melt and gaseous phosphorus are contacted and reacted to generate an indium phosphide melt, and the indium phosphide melt is cooled to generate an indium phosphide crystal.
7. An apparatus for the improved indium phosphide crystal synthesis process as set forth in any one of claims 5 to 6, characterized by comprising:
the working cavity is used for maintaining the pressure and the atmosphere environment required in the indium phosphide crystal synthesis process;
the crucible is arranged in the working cavity and used for containing working media such as metal indium, indium phosphide and the like;
the inner cavity of the phosphorus bubble is communicated with the crucible cavity through a channel;
the first heater is positioned near the phosphorus bubble and the channel and is used for heating red phosphorus and maintaining the required phosphorus vapor pressure of the working cavity;
and the electromagnetic constraint inductor is positioned at the periphery of the crucible and used for heating the working medium in the crucible and constraining the transverse section size and the transverse section shape of the indium metal melt, the indium-rich melt and the indium phosphide melt in the crucible so as to ensure that the side surfaces of the indium metal melt, the indium-rich melt and the indium phosphide melt in the crucible are separated from contact or partially separated from contact with the inner wall of the crucible.
8. The improved indium phosphide crystal synthesis and growth process apparatus as set forth in claim 7, further comprising a balance chamber located outside the working chamber for balancing the pressure in the working chamber, and an inert gas is filled during operation.
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