CN111041550B - Gas phase doping crystal growth method based on VGF method - Google Patents

Gas phase doping crystal growth method based on VGF method Download PDF

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CN111041550B
CN111041550B CN201911405446.1A CN201911405446A CN111041550B CN 111041550 B CN111041550 B CN 111041550B CN 201911405446 A CN201911405446 A CN 201911405446A CN 111041550 B CN111041550 B CN 111041550B
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quartz tube
pressure
quartz
mpa
temperature
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CN111041550A (en
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赵有文
段满龙
刘鹏
卢伟
杨俊�
刘京明
谢辉
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Zhuhai Dingtai Xinyuan Crystal Co ltd
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Zhuhai Dingtai Xinyuan Crystal Co ltd
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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
    • 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
    • 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
    • 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

Abstract

The invention discloses a gas phase doping crystal growth method based on a VFG method; relates to the technical field of crystal preparation. The method comprises the following steps: s1, putting polycrystal for crystal growth, seed crystal and red phosphorus into a crucible; s2, placing the crucible in a quartz tube; the method is characterized in that step S2 is followed by step S3, covering a quartz seal cap connected with a dopant on the quartz tube, and enabling the dopant to be located in the quartz tube, wherein the dopant is not in contact with polycrystal, seed crystal and red phosphorus; and then sealing the quartz sealing cap with the quartz tube. Through the improvement of quartz sealing cap and temperature rising process for VGF crystal growth, the dopant is separated from other raw materials for crystal growth, and the dopant Fe element enters the melt through gas phase diffusion, so that the uniform doping concentration is realized, and the resistivity uniformity and the crystallization rate of the crystal are improved; meanwhile, the doping amount of the dopant Fe can be reduced, and the cost is saved.

Description

Gas phase doping crystal growth method based on VGF method
Technical Field
The invention relates to the technical field of crystal preparation, in particular to a gas phase doping crystal growth method based on a VGF method.
Background
The compound semiconductor InP material has high electron mobility and large forbidden band width, and can be widely applied to long-wave optical fiber communication technology, microwave and millimeter wave devices, space anti-radiation solar cells and the like as a new electronic functional material. With the increasing maturity of InP-based microelectronic fabrication technology, the semi-insulating SI-InP is more important for high frequency devices and optoelectronic integrated circuits, so that the quality of InP-based semiconductor substrate materials with excellent properties is critical to the quality of devices.
Currently, high-quality indium phosphide (InP) single crystals with low defect density are mainly prepared by a vertical gradient freezing method (VGF). In order to improve the quality of the InP single crystal and reduce the dislocation density, the dislocation density can be effectively reduced by doping impurities (namely dopants) in the growing process of the InP single crystal (such as Sn, S, Zn, Fe, Ga, Sb and the like), and the crystal quality of the InP single crystal is improved.
When Fe (iron) doping is used to prepare a semi-insulating InP single crystal material, where Fe functions as a deep acceptor in the InP crystal and compensates for shallow donors, it is necessary to achieve a high concentration of Fe initially doped when preparing a semi-insulating InP single crystal; in the prior art, the dopant iron is mixed with other materials and placed in a crucible for crystal growth, so that the concentration of the iron can be ensured by doping with higher iron content.
In addition, in the prior art, a doping agent Fe is directly mixed with an indium phosphide polycrystal material and heated simultaneously, and the doping agent Fe and the indium phosphide polycrystal material are mixed in a molten state; in the temperature rise stage of crystal growth, the temperature rise rate is too fast, and the mixing of Fe element and indium phosphide polycrystal in a molten state can cause the uneven distribution of Fe in the indium phosphide melt, thereby destroying the uniformity and the integrity of the crystal.
Furthermore, the crystal growth process is generally divided into a temperature-raising stage (raising the temperature to the melting point of the indium phosphide polycrystal), a constant-temperature stage (the indium phosphide polycrystal is gradually converted into a melt, and simultaneously Fe is diffused into the indium phosphide melt) and a temperature-lowering stage (crystallization stage); in the prior art, the temperature rise rate in the temperature rise stage is higher, so that more iron is precipitated, and Fe in the semi-insulating InP substrate is diffused to an epitaxial layer in the epitaxial growth process, so that the performance of a device manufactured by InP single crystal is reduced.
Disclosure of Invention
The invention provides a VGF method-based gas phase doping crystal growth method, which separates a dopant from other raw materials for crystal growth, enables the dopant to be doped into a crystal in a gas phase manner, and can ensure the uniform doping of the dopant, thereby improving the resistivity uniformity and the crystallization rate of the crystal; the invention is realized by the following technical scheme:
a crystal growth method based on gas phase doping of a VGF method comprises the following steps:
s1, putting polycrystal for crystal growth, seed crystal and red phosphorus into a crucible;
s2, placing the crucible in a quartz tube;
characterized in that, step S2 is followed by the step of,
s3, capping the quartz tube with the dopant connected thereon, so that the dopant is positioned in the quartz tube and the dopant is not in contact with the polycrystal, the seed crystal and the red phosphorus; and then sealing the quartz sealing cap with the quartz tube.
Specifically, the polycrystal is an indium phosphide polycrystal.
Specifically, the dopant is elemental iron; the simple substance iron exists in the form of iron wires, a quartz ring is arranged at the top end of the inner side of the quartz sealing cap, and the simple substance iron is hung on the quartz ring;
or the doping agent is elementary iron; the simple substance iron exists in the form of an iron sheet or an iron block, a quartz hook is arranged at the top end of the inner side of the quartz sealing cap, and the simple substance iron is hung on the quartz hook.
Specifically, the purity of the red phosphorus is 6N; the purity of the iron wire is 6N.
Further, the step S3 of sealing the quartz sealing cap and the quartz tube specifically includes covering the quartz sealing cap on the quartz tube, first evacuating the quartz tube with a vacuum degree of 10-4Pa～10-3Pa; then, an oxyhydrogen flame is used for sintering and sealing between the quartz sealing cap and the quartz tube.
Further, step S3 is followed by the step of,
s4, putting the quartz tube into a growth furnace;
and S5, controlling the temperature and the pressure of the quartz tube in the growth furnace to grow the crystal.
As a specific technical solution, the controlling of the temperature and the pressure of the quartz tube in the growth furnace in step S5 sequentially includes a temperature rising stage, a constant temperature stage and a temperature lowering stage, wherein the temperature rising stage includes:
step one, heating to 350-450 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 750-850 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 2.0-2.8 Mpa;
thirdly, heating to 1000-1150 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 2.3-3.0 Mpa;
the pressure in the quartz tube gradually increases in each stage of the temperature rising stage.
Preferably, the temperature, duration and quartz tube pressure of each of the temperature raising stages are specifically:
step one, heating to 400 ℃, and keeping for 1h, wherein the pressure in the quartz tube is increased to 0 Mpa;
step two, heating to 800 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 2.4 Mpa;
and step three, heating to 1100 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 2.7 Mpa.
As another specific technical solution, the controlling of the temperature and the pressure of the quartz tube in the growth furnace in step S5 includes a temperature raising stage, a constant temperature stage, and a temperature lowering stage in this order, and the temperature raising stage includes:
step one, heating to 150-250 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 380-450 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 0-0.1 Mpa;
thirdly, heating to 450-550 ℃, keeping the temperature for 0.5-1.5 h, and increasing the pressure in the quartz tube to 1.0-2.0 Mpa;
fourthly, heating to 550-650 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 2.0-2.8 Mpa;
fifthly, heating to 750-850 ℃, keeping for 1.5-2.5 h, and increasing the pressure in the quartz tube to 2.3-3.2 Mpa;
sixthly, heating to 1000-1150 ℃, lasting for 2.5-3.5 h, and increasing the pressure in the quartz tube to 2.4-3.5 Mpa;
the pressure in the quartz tube gradually increases in each stage of the temperature rise stage.
Preferably, the temperature, duration and quartz tube pressure of each of the temperature raising stages are specifically:
step one, heating to 200 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 433 ℃, and keeping for 1h, wherein the pressure in the quartz tube is increased to 0.05 Mpa;
step three, heating to 500 ℃, lasting for 1 hour, and increasing the pressure in the quartz tube to 1.5 Mpa;
step four, heating to 600 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 2.4 Mpa;
fifthly, heating to 800 ℃, lasting for 2 hours, and increasing the pressure in the quartz tube to 2.6 Mpa;
and sixthly, heating to 1100 ℃, lasting for 3 hours, and increasing the pressure in the quartz tube to 2.9 MPa.
The beneficial technical effects produced by the invention are as follows:
through the improvement of quartz sealing cap and temperature rising process for VGF crystal growth, the dopant is separated from other raw materials for crystal growth, and the dopant Fe element enters the melt through gas phase diffusion, so that the uniform doping concentration is realized, and the resistivity uniformity and the crystallization rate of the crystal are improved; meanwhile, the doping amount of the dopant Fe can be reduced, and the cost is saved.
Drawings
FIG. 1 is a schematic structural diagram of a quartz sealing cap provided by an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a crystal growing apparatus according to an embodiment of the present invention;
FIG. 3 is one of the temperature and pressure curves in the quartz tube during the ramp-up phase provided by the embodiment of the present invention;
FIG. 4 is a second graph of the temperature and pressure in the quartz tube during the temperature raising stage according to the embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
In combination with, 1, 2, this example provides a crystal growth apparatus and a crystal growth method for growing an indium phosphide single crystal by vapor phase doping of iron element based on VGF method.
Referring to fig. 2, the crystal growth apparatus comprises a growth furnace 10, a graphite crucible holder 20, a boron nitride crucible 40, a quartz tube 50 and a quartz sealing cap 60; a plurality of heating devices 30 are sequentially arranged in the growth furnace 10 from bottom to top; each heating device is connected with the control system through a galvanic couple 80; the graphite susceptor 20 is located within the growth furnace 10. Wherein the bottom of the boron nitride crucible 40 has a seed plug that carries a seed crystal.
During crystal growth, various raw materials are placed in the boron nitride crucible 40, the boron nitride crucible 40 is placed in the quartz tube 50, and the quartz sealing cap 60 covers the opening above the quartz tube 50 to realize sealing of the quartz tube 50; a sealed quartz tube is placed in a graphite crucible holder 20 in the growth furnace 10; each heating device 20 is disposed around a quartz tube 50 placed in the growth furnace 10 to provide a desired temperature for crystal growth.
The crystal growth method of the embodiment comprises the following steps:
step 1: preparing and treating raw materials;
the raw materials comprise indium phosphide polycrystal 93, seed crystal 94, dopant Fe, red phosphorus and liquid sealing agent 92; in this embodiment, boron oxide is used as the liquid sealing agent 92. The dopant Fe exists in the form of simple substance, in this embodiment, high-purity iron wire 91 is used, wherein the purity of iron wire 91 is 6N; the purity of red phosphorus was 6N.
In other embodiments, the dopant Fe may be present in other forms such as iron flakes or iron blocks.
The method comprises the step of cleaning the indium phosphide polycrystal 93 and the high-purity iron wire 91.
The cleaning method of the indium phosphide polycrystal 93 was as follows: according to the weight of the indium phosphide polycrystal 93, preparing an etching solution containing ammonia water, hydrogen peroxide and deionized water according to a certain proportion, placing the indium phosphide polycrystal 93 in the etching solution for surface etching and cleaning, and washing the surface for multiple times by using the deionized water to remove oxides and residual impurities on the surface of the indium phosphide polycrystal 93. Then, the cleaned indium phosphide polycrystal 93 was placed in a fume hood and dried for use.
The seed crystal 94 is cleaned as follows: soaking and corroding the substrate by aqua regia for 10 seconds, quickly washing the substrate by deionized water for multiple times to remove oxides and residual impurities on the surface, and then drying the substrate in a fume hood for later use.
Step 2: selecting a proper boron nitride crucible 40, a proper quartz tube 50 and a proper quartz sealing cap 60, and cleaning and drying the crucible for later use;
the specific method comprises the steps of scrubbing the quartz tube 50, the boron nitride crucible 40 and the quartz sealing cap 60 by using a cleaning agent, soaking the quartz tube in aqua regia for two hours, washing the quartz tube with deionized water for multiple times to remove surface stains, and then drying the quartz tube in a fume hood for later use.
And step 3: vacuum annealing the quartz tube 50, the quartz sealing cap 60 and the boron nitride crucible 40;
and 4, step 4: the required raw materials are loaded into the boron nitride crucible 40, wherein the seed crystal 94 is first placed, the seed crystal 94 is placed at the plug of the seed crystal in the boron nitride crucible 40, and then the indium phosphide polycrystal 93, red phosphorus and boron oxide liquid sealant are placed.
Referring to fig. 1, in the present embodiment, the quartz sealing cap has an isolation structure for keeping the iron wire 91 from contacting other materials and for positioning the iron wire 91 inside the quartz tube; specifically, with reference to fig. 2, the isolation structure is a quartz ring 61 disposed inside the quartz sealing cap, and the iron wire 91 is hung on the quartz ring 61, so that the iron wire 91 is located above and isolated from other raw materials; when the dopant Fe exists in the form of an iron sheet or an iron block, the isolation structure is a quartz hook arranged in the quartz sealing cap, and the iron sheet or the iron block is hung on the quartz hook, so that the iron sheet or the iron block is positioned above other raw materials.
Placing the boron nitride crucible 30 in the quartz tube 50, then covering the quartz sealing cap 60, vacuumizing the quartz tube 50, covering the quartz sealing cap 60 when the vacuum degree reaches the design requirement, sintering and sealing by oxyhydrogen flame to seal the quartz tube 50, wherein the vacuum degree of the quartz tube 50 is 10-4Pa～10-3Pa。
And 5: placing the graphite crucible holder 20 with the quartz tube 50 in the growth furnace 10, and performing crystal growth by controlling the temperature of each heating device; at high temperature, part of iron wires 91 and part of red phosphorus are subjected to chemical reaction to generate FeP2 Indium phosphide polycrystal 93 in P atmosphere and FeP2The growth is carried out in the co-existing atmosphere, and the whole process of the crystal growth generally needs 160-240 h.
Putting the sealed quartz tube into a growth furnace 10, and controlling the temperature in the growth furnace 10 through an automatic control system; specifically, the method comprises the following three stages:
a temperature rise stage, in which the temperature is raised to above the melting point of indium phosphide, generally 1000 to 1150 ℃, and in this embodiment, the temperature is raised to 1100 ℃;
maintaining constant temperature to dissolve indium phosphide polycrystal into melt, gasifying red phosphorus, reacting Fe with phosphorus vapor in quartz tube to grow FeP2Fe atoms enter the melt through gas phase diffusion to realize effective and uniform doping of Fe; generally, the constant temperature needs 100-120 hours;
and in the cooling stage, gradually cooling to room temperature, and finishing crystal growth in the process, wherein the duration of the growth in the stage is generally 140-150 hours, and finally the high-quality SI-InP can be obtained.
In one embodiment, the temperature of the quartz tube and the pressure in the quartz tube in the growth furnace 10 are controlled simultaneously during the temperature-raising phase, which is generally divided into three phases:
step one, heating to 350-450 ℃, preferably 400 ℃, lasting for 0.5-1.5 h, preferably 1h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 750-850 ℃, preferably 800 ℃, lasting for 0.5-1.5 h, preferably 1h, and increasing the pressure in the quartz tube to 2.0-2.8 Mpa, preferably 2.4 Mpa;
and step three, raising the temperature to 1000-1150 ℃, preferably 1100 ℃, for 0.5-1.5 h, preferably 1h, and raising the pressure in the quartz tube to 2.3-3.0 MPa, preferably 2.7 MPa.
Wherein, the pressure in the quartz tube is gradually increased in each stage of the temperature rise stage; that is, the pressure in stage three is greater than that in stage two, and the pressure in stage two is greater than that in stage one.
In connection with table one, the temperature and pressure relationship in the quartz tube is given in a preferred embodiment of the ramp-up phase, which takes about 3 hours.
Phases Temperature of Pressure of
Stage one Room temperature- -400 ℃ for 1h 0Mpa
Stage two 400C℃----800℃ 1h 2.4Mpa
Stage three 800C℃---1100℃ 1h 2.7Mpa
Watch 1
In the preferred embodiment, referring to fig. 3, the temperature-pressure curve in the quartz tube shows that, due to the faster heating rate, the iron element and the phosphorus vapor cannot be sufficiently combined, so that more iron element can be separated out for the sufficient amount of Fe element diffused into the melt; meanwhile, the Fe element is not uniformly distributed in the melt in the constant temperature stage, so that the crystallization quality is influenced.
Therefore, there is a modification that, in another embodiment, the temperature raising process is generally divided into the following stages:
step one, heating to 150-250 ℃, preferably 200 ℃, lasting for 0.5-1.5 h, preferably 1h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 380-450 ℃, preferably 433 ℃, for 0.5-1.5 h, preferably 1h, and raising the pressure in the quartz tube to 0-0.1 Mpa, preferably 0.05 Mpa;
step three, heating to 450-550 ℃, preferably 500 ℃, lasting for 0.5-1.5 h, preferably 1h, and increasing the pressure in the quartz tube to 1.0-2.0MPa, preferably 1.5 MPa;
step four, heating to 550-650 ℃, preferably 600 ℃, lasting for 0.5-1.5 h, preferably 1h, and increasing the pressure in the quartz tube to 2.0-2.8 Mpa, preferably 2.4 Mpa;
fifthly, heating to 750-850 ℃, preferably 800 ℃, lasting for 1.5-2.5 hours, preferably 2 hours, and increasing the pressure in the quartz tube to 2.3-3.2 MPa, preferably 2.6 MPa;
and sixthly, raising the temperature to 1000-1150 ℃, preferably 1100 ℃, for 2.5-3.5 hours, preferably 3 hours, and raising the pressure in the quartz tube to 2.4-3.5 MPa, preferably 2.9 MPa.
Wherein, the pressure in the quartz tube is gradually increased between each stage of the temperature rising stage.
The corresponding relation between the temperature and the pressure in the quartz tube in one application example of the improved scheme is shown in the table II:
phases Temperature of Pressure of
Stage one Room temperature- -200 ℃ for 1h 0Mpa
Stage two 200℃----433℃ 1h 0.05Mpa
Stage three 433℃----500℃ 1h 1.5Mpa
Stage four 500℃----600℃ 1h 2.4Mpa
Stage five 600℃----800℃ 2h 2.6Mpa
Stage six 800℃----1100℃ 3h 2.9Mpa
Watch two
In the preferable technical scheme, the temperature rise stage needs about 9 hours, the temperature control points (200 ℃, 433 ℃, 500 ℃, 600 ℃ and 800 ℃) are added, although the time is prolonged, the temperature of the quartz tube can be slowly raised, the pressure in the quartz tube is controlled in the temperature rise process, and the temperature and the pressure of the quartz tube can form a unique temperature and pressure curve (refer to fig. 4), so that the elemental iron element and the elemental red phosphorus can be fully combined in the temperature rise process, and then the elemental iron element and the elemental red phosphorus are diffused into the indium phosphide melt in a gas phase transmission mode in the constant temperature stage, and the purpose of preparing the low-doped high-quality semi-insulating indium phosphide crystal is achieved.
In the technical scheme, the pressure in the quartz tube is jointly completed through a temperature and pressure balance system, and the temperature is controlled through a heating device in the growth furnace; in the temperature rising stage, the temperature is controlled to rise slowly, the relationship between the temperature and the pressure at a certain temperature point is controlled, and the effect of gas phase diffusion influenced by the too fast reaction of Fe and P in each stage of the temperature rising stage is prevented.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (8)

1. A crystal growth method based on gas phase doping of a VFG method comprises the following steps:
s1, putting polycrystal for crystal growth, seed crystal and red phosphorus into a crucible;
s2, placing the crucible in a quartz tube;
characterized in that, step S2 is followed by the step of,
s3, capping the quartz tube with the dopant connected thereon, so that the dopant is positioned in the quartz tube and the dopant is not in contact with the polycrystal, the seed crystal and the red phosphorus; then sealing the quartz sealing cap with the quartz tube;
the top end of the inner side of the quartz sealing cap is provided with a quartz ring, and the dopant is hung on the quartz ring; or a quartz hook is arranged at the top end of the inner side of the quartz sealing cap, and the dopant is hung on the quartz hook;
the polycrystal is an indium phosphide polycrystal; the dopant is elemental iron.
2. The crystal growth method according to claim 1, wherein the purity of the red phosphorus is 6N; the purity of the elementary substance iron is 6N.
3. The crystal growth method according to claim 1 or 2, wherein the step S3 of sealing the quartz sealing cap and the quartz tube specifically comprises covering the quartz sealing cap on the quartz tube, and first evacuating the quartz tube to a vacuum degree of 10 "4 Pa to 10" 3 Pa; then, an oxyhydrogen flame is used for sintering and sealing between the quartz sealing cap and the quartz tube.
4. The crystal growth method of claim 3, further comprising, after step S3,
s4, placing the quartz tube into a growth furnace;
and S5, controlling the temperature and the pressure of the quartz tube in the growth furnace to grow the crystal.
5. The crystal growth method of claim 4, wherein the step S5 comprises a temperature-raising stage, a constant-temperature stage and a temperature-lowering stage in sequence for controlling the temperature and the pressure of the quartz tube in the growth furnace, wherein the temperature-raising stage comprises:
step one, heating to 350-450 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 750-850 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 2.0-2.8 Mpa;
thirdly, heating to 1000-1150 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 2.3-3.0 Mpa;
the pressure in the quartz tube gradually increases in each stage of the temperature rising stage.
6. The crystal growth method of claim 5, wherein the temperature, duration and quartz tube pressure of each of the temperature-raising stages are specified as:
step one, heating to 400 ℃, and keeping for 1h, wherein the pressure in the quartz tube is increased to 0 Mpa;
step two, heating to 800 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 2.4 Mpa;
and step three, heating to 1100 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 2.7 Mpa.
7. The crystal growth method according to claim 4,
the temperature and pressure control of the quartz tube in the growth furnace in the step S5 sequentially comprises a temperature rise stage, a constant temperature stage and a temperature reduction stage, wherein the temperature rise stage comprises:
step one, heating to 150-250 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 380-450 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 0-0.1 Mpa;
thirdly, heating to 450-550 ℃, and keeping the temperature for 0.5-1.5 h, wherein the pressure in the quartz tube is increased to 1.0-2.0 Mpa;
fourthly, heating to 550-650 ℃, lasting for 0.5-1.5 h, and increasing the pressure in the quartz tube to 2.0-2.8 Mpa;
fifthly, heating to 750-850 ℃, keeping for 1.5-2.5 h, and increasing the pressure in the quartz tube to 2.3-3.2 Mpa;
sixthly, heating to 1000-1150 ℃, lasting for 2.5-3.5 h, and increasing the pressure in the quartz tube to 2.4-3.5 Mpa;
the pressure in the quartz tube gradually increases in each stage of the temperature rise stage.
8. The crystal growth method of claim 7, wherein the temperature, duration and quartz tube pressure of each of the ramp-up stages are specified as:
step one, heating to 200 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 0 Mpa;
step two, heating to 433 ℃, and keeping for 1h, wherein the pressure in the quartz tube is increased to 0.05 Mpa;
step three, heating to 500 ℃, lasting for 1 hour, and increasing the pressure in the quartz tube to 1.5 Mpa;
step four, heating to 600 ℃, lasting for 1h, and increasing the pressure in the quartz tube to 2.4 Mpa;
fifthly, heating to 800 ℃, lasting for 2 hours, and increasing the pressure in the quartz tube to 2.6 Mpa;
and sixthly, heating to 1100 ℃, lasting for 3 hours, and increasing the pressure in the quartz tube to 2.9 MPa.
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