CN211620660U - Quartz sealing cap for crystal growth based on VGF method and crystal growth device - Google Patents
Quartz sealing cap for crystal growth based on VGF method and crystal growth device Download PDFInfo
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- CN211620660U CN211620660U CN201922459336.5U CN201922459336U CN211620660U CN 211620660 U CN211620660 U CN 211620660U CN 201922459336 U CN201922459336 U CN 201922459336U CN 211620660 U CN211620660 U CN 211620660U
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Abstract
The utility model discloses a quartz sealing cap for crystal growth based on a VGF method and a crystal growth device; the quartz sealing cap is matched with the quartz tube for use so as to realize the sealing of the quartz tube, a crucible for crystal growth is sealed in the quartz tube, raw materials for crystal growth are contained in the crucible, and a free space is arranged between the raw materials and the quartz sealing cap; the quartz tube has an opening; the quartz sealing cap comprises a cover body covering the opening of the quartz tube; the quartz sealing cap is characterized by comprising a temperature control part, wherein the temperature control part protrudes upwards from the cover body, and the temperature control part is provided with an inner cavity leading to the quartz tube. By improving the matching of the quartz sealing cap, the crystal growth device and the heating process for VGF crystal growth, the vapor pressure of the free space can be easily controlled; the vapor pressure of the free space is always in a stable state, so that the uniformly doped single crystal is obtained.
Description
Technical Field
The utility model relates to a crystal preparation technical field especially relates to a based on VGF method crystal growth is with quartzy sealing cap and crystal growth device.
Background
Indium phosphide (InP) is one of important iii-v group compound semiconductor materials, has the advantages of direct transition band structure, high electron mobility, high operating temperature and the like, is an important optoelectronic and microelectronic base material, and is widely used for manufacturing lasers and detectors for optical fiber communication, integrated circuits for network communication, high-frequency microwave and millimeter wave devices and the like.
Currently, high-quality indium phosphide (InP) single crystals with low defect density are mainly prepared by a vertical gradient freezing method (VGF). The dislocation density can be effectively reduced by doping impurities (such as Sn, S, Zn, Fe, Ga, Sb and the like) in the growth process of the InP single crystal, and the crystal quality of the InP single crystal is improved. Among them, the dopant of the commonly used N-type InP single crystal is S atom, and indium sulfide (In) is mostly doped at present2S3) Preparing a polycrystal; but the dopant indium sulfide (In)2S3) the composition of the polycrystal is influenced by its own synthesis process to have various crystal forms, for example, a polycrystalline material obtained according to the difference of bonding sites of S has alpha-In2S3and β -In2S3structure of, which β -In2S3The structure has two sub-structures respectively marked as T-In2S3And C-In2S3. Indium sulfide polycrystal with various crystal structures is used as a dopant in the growth process of an indium phosphide single-crystal material, and phosphorus capable of influencing growthThe doping uniformity of the indium phosphide single-crystal material even reduces the crystallization rate of the indium phosphide single-crystal material.
Generally, various raw materials (including red phosphorus) prepared from indium phosphide are placed in a crucible, the crucible is placed in a quartz tube, a quartz sealing cap is covered on the crucible, then the quartz tube is vacuumized and sintered and sealed by oxyhydrogen flame, and then the quartz tube is placed in a heating furnace to be heated so as to realize crystal growth; the heating furnace is provided with a plurality of temperature zones for controlling the temperature of crystal growth, and the general temperature control comprises three stages: a temperature rising stage, a constant temperature stage and a crystallization stage; in the constant temperature stage, the doping agent indium sulfide polycrystal and the indium phosphide polycrystal are mixed in a molten state, and because the indium sulfide polycrystal has various crystal forms and the impurity segregation effect exists in the crystal growth process, the amount of the effective doping agent in the melt is uneven and unstable, so that the sulfur doping uniformity of the sulfur-doped indium phosphide single crystal is poor.
SUMMERY OF THE UTILITY MODEL
The first purpose of the utility model is to provide a quartz sealing cap for crystal growth based on VGF method, which can control the vapor pressure in the free space of the raw material and the quartz sealing cap in the crystallization stage, so as to uniformly dope the dopant in the raw material for crystal growth; the utility model discloses a first purpose is realized through following technical scheme:
a quartz sealing cap for crystal growth based on a VGF method is used in cooperation with a quartz tube to realize the sealing of the quartz tube, a crucible for crystal growth is sealed in the quartz tube, a raw material for crystal growth is contained in the crucible, and a free space is arranged between the raw material and the quartz sealing cap; the quartz tube has an opening; the quartz sealing cap comprises a cover body covering the opening of the quartz tube; the quartz sealing cap is characterized by comprising a temperature control part, wherein the temperature control part protrudes upwards from the cover body, and the temperature control part is provided with an inner cavity leading to the quartz tube.
Specifically, the temperature control part is in an elongated shape perpendicular to the cover body; the inner cavity is elongated.
The second purpose of the utility model is to provide a crystal growing device based on VGF method; the utility model discloses a second purpose is realized through following technical scheme:
a crystal growth device comprises a heating furnace, a quartz tube, a quartz sealing cap and a crucible; the raw materials for crystal growth are placed in the crucible, the crucible is placed in the quartz tube, the quartz sealing cap is matched with the quartz tube for use so as to realize the sealing of the quartz tube, the quartz tube is placed in the heating furnace, the heating furnace is provided with at least one heating device for controlling the temperature of the quartz tube, and the heating devices are sequentially arranged from top to bottom; the quartz sealing cap is characterized in that the quartz sealing cap is the quartz sealing cap used in the technical scheme of the first purpose; the heating furnace also comprises at least one heating device for controlling the temperature of the temperature control part of the quartz sealing cap.
The utility model discloses produced profitable technological effect is:
by improving the quartz sealing cap, the heating furnace and the heating process for VGF crystal growth, the vapor pressure of the free space in the quartz tube can be easily controlled; in the crystallization stage, the vapor pressure of the free space is always in a stable state, so that the dopant is uniformly diffused into the melt, and then the VGF-InP single crystal uniformly doped with sulfur is obtained; meanwhile, the doping amount of the dopant can be reduced, and the cost is saved.
Drawings
FIG. 1 is a schematic diagram of a prior art crystal growing apparatus;
FIG. 2 is a schematic structural diagram of a crystal growing apparatus according to an embodiment of the present invention;
fig. 3 is a graph of temperature control curve of the quartz tube at the temperature control stage according to the embodiment of the present invention;
fig. 4 is a temperature control curve diagram of the temperature control portion of the quartz sealing cap at the temperature control 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.
Combine the graphs 1-4 to growcarrier concentration of 4 × 1018cm-3The technical scheme of the utility model is explained by taking the N-type indium phosphide single crystal ingot as an example:
as shown in fig. 1, the prior art apparatus for crystal growth based on the VGF method comprises a boron nitride crucible 30 for containing various raw materials 60 and a carrier for crystal growth, a quartz tube 20, a quartz cap 10, and a heating furnace (not shown), wherein a plurality of heating devices 40 are arranged in the heating furnace in sequence from bottom to top; the boron nitride crucible 30 is positioned in the quartz tube 20, and the quartz sealing cap 10 covers the opening above the quartz tube 20 to realize the sealing of the quartz tube 20; each heating device 40 is disposed around the quartz tube 20 to provide the desired temperature for crystal growth. Each heating device of the crystal growth device shown in fig. 1 controls the heating furnace to form four temperature zones, which are sequentially from bottom to top: a first temperature zone, a second temperature zone, a third temperature zone and a fourth temperature zone; the crystal growth is realized by controlling the temperature of each temperature zone.
When used to grow an N-type indium phosphide single crystal, the raw material 60 includes an indium phosphide polycrystal, an indium phosphide seed crystal, a dopant, and red phosphorus having a purity of 6N grade; the dopant is selected according to the doping requirement of the indium phosphide single crystal, and in the embodiment, a sulfur simple substance with the purity of 6N grade is adopted.
The process of crystal growth comprises a temperature control process, and the general temperature control process comprises a temperature rise stage, a constant temperature stage and a crystallization stage; in the prior art, a dopant and an indium phosphide polycrystal are mixed in a molten state at a constant temperature stage, and the dopant is completely mixed in the indium phosphide polycrystal, but the doping in the molten state causes the phenomenon of uneven doping of the dopant, so that the amount of sulfur diffused into the melt is uneven and unstable, and the uniformity of sulfur doping of the sulfur-doped indium phosphide single crystal is poor.
The utility model discloses an in the mode doping with dopant gasification advances indium phosphide polycrystal material, generally, after quartz capsule 20 accomplishes sealedly, raw and other materials 60 and quartz sealing cap 10 leave certain free space 50 within a definite time, melt the in-process that forms the fuse-element at the indium phosphide polycrystal, let the temperature in the quartz capsule 20 reach above the melting point of indium phosphide polycrystal, above the gasification temperature of dopant through the control to the temperature, the dopant of gasification rises to in the free space 50, lets the dopant diffuse gradually and advances the fuse-element. However, during the crystallization phase, as the sulfur gradually diffuses into the melt, the sulfur content decreases, which results in a pressure drop in the free space 50, which ultimately results in non-uniform doping of the melt with the resulting crystalline sulfur.
In view of the above problem, referring to fig. 2, the present invention provides a crystal growth apparatus based on VGF method, the quartz sealing cap 10 of the present invention is a temperature control part 11 extending upward and communicating with the free space, so as to facilitate the control of the temperature and pressure of the free space 50; the temperature control part 11 in the embodiment is a slender part arranged in the middle part of the quartz sealing cap 10; the elongated temperature control portion 11 has an inner cavity, which is also elongated and communicates with the free space 50.
Correspondingly, at least one heating device 20 arranged around the temperature control part 11 is additionally arranged above the fourth temperature zone in the heating furnace, and a fifth temperature zone and a sixth temperature zone are additionally arranged so as to control the temperature of the temperature control part 11 and finally achieve the purpose of achieving the pressure stabilization of the free space 50 through the temperature control; the heating devices 20 (including the heating devices for heating the quartz tube 20 and the temperature control part 11) of the heating furnace are arranged in sequence from top to bottom, and six temperature zones are formed; it should be appreciated that in other embodiments, the temperature zone is set according to the actual application requirements. .
The temperature control of the quartz tube 20 and the temperature control unit 11 in the heating furnace includes four stages:
a temperature raising stage, in which the temperature of the quartz tube 20 and the temperature of the temperature control part 11 are gradually raised to above the melting point of the indium phosphide polycrystal, the temperature is raised to 1070 ℃ to 1300 ℃, in this embodiment, the temperature is set at 1200 ℃, the temperature is far greater than the gasification temperature of sulfur and phosphorus, the indium phosphide polycrystal is gradually melted to form a melt at this stage, and sulfur and red phosphorus are gasified into steam; in the stage, the general temperature rise rate is 1-3 ℃/min, and the duration is 6-20 h;
a constant temperature stage, wherein after the temperature rise is finished, the temperature is kept constant for 30 hours so that the indium phosphide polycrystal is fully melted; while sulfur gradually diffuses into the melt;
in the crystallization stage, the temperature of the quartz tube 20 is controlled to be gradually reduced until crystallization is completed; simultaneously, the temperature control part 11 of the quartz sealing cap 10 is heated for the second time, so that the pressure of the free space 50 is kept stable, and the pressure of the free space 50 is not lower than the dissociation pressure of the melt;
in this stage, the temperature of the quartz tube 20 is gradually lowered to a temperature lower than the melting point of the melt, so that the melt is crystallized.
In the stage, the temperature of the temperature control part 11 of the quartz sealing cap 10 is secondarily raised to be not lower than 1500 ℃, and the temperature raising rate is 0.1-0.5 ℃/min; the temperature is raised to 1500 ℃ by adopting 0.3 ℃.
In the temperature reduction stage, the temperature control part 11 of the quartz tube 20 and the quartz sealing cap 10 is controlled to be reduced to room temperature; wherein the cooling rate of the quartz tube 20 is controlled to be 0.1-1 ℃/min, preferably 0.4 ℃/min; the cooling rate of the quartz sealing cap 10 is controlled to be 0.1-1 ℃/min, preferably 0.75 ℃/min.
The utility model also provides a crystal growth method, including following process flow:
s1, preparing and processing raw materials;
the raw materials comprise indium phosphide polycrystal, indium phosphide seed crystal, dopant (sulfur simple substance with the purity of 6N grade in the embodiment) and red phosphorus with the purity of 6N grade; the mass of the red phosphorus is calculated according to the decompression of indium phosphide at the melting point temperature, and the mass of the elemental sulfur is determined according to the carrier concentration and the growth temperature of the crystal to be grown, which is not described herein.
Preparing an etching solution containing ammonia water, hydrogen peroxide and deionized water according to a certain proportion according to the weight of the indium phosphide polycrystal, placing the indium phosphide polycrystal 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. And then, drying the cleaned indium phosphide polycrystal in a fume hood for later use.
Soaking and corroding indium phosphide seed crystals for 10 seconds by aqua regia, quickly washing the seed crystals for multiple times by deionized water to remove oxides and residual impurities on the surfaces, and then placing the seed crystals in a fume hood for drying for later use.
S2: the quartz tube 20, the quartz sealing cap 10 and the boron nitride crucible 30 are cleaned in the following way:
after the quartz tube 20, the boron nitride crucible 30 and the quartz sealing cap 10 are soaked in aqua regia for two hours, the quartz tube, the boron nitride crucible and the quartz sealing cap are washed with deionized water for many times to remove surface contamination, and then the quartz tube, the boron nitride crucible and the quartz sealing cap are placed in a fume hood to be dried for standby.
S3: carrying out vacuum annealing on the quartz tube 20, the quartz sealing cap 10 and the boron nitride crucible 30;
s4: the required raw material 60 is filled into the boron nitride crucible 30, the boron nitride crucible 30 is placed in the quartz tube 20, then the quartz sealing cap 10 is covered, the quartz tube 20 is vacuumized, and when the vacuum degree reaches the design requirement, the tube sealing treatment is carried out on the quartz tube 20; the vacuum degree inside the quartz tube 20 in this embodiment is less than 10-3Pa, then sintering the quartz sealing cap 10 by oxyhydrogen flame for sealing; the position of the seal is as indicated by reference numeral 12 in fig. 3;
s5: and a temperature control stage, namely, putting the closed quartz tube 20 into a crystal growth furnace, and controlling the temperature of each temperature zone to control the temperature rise temperature gradient, the constant temperature process and the temperature reduction rate of the quartz tube 20 and the temperature control part 11 so as to complete crystal growth in the boron nitride crucible 30. As shown in fig. 2, the temperature of the temperature control part 11 is controlled mainly by controlling the temperatures of the fifth temperature zone and the sixth temperature zone at this stage; the temperature of the quartz tube 20 is controlled by controlling the temperatures of the first to fourth temperature zones.
Referring to fig. 3 and 4, in the present invention, the temperature control of step S5 mainly includes the following stages:
a temperature raising stage, in which the temperature of the quartz tube 20 and the temperature of the temperature control part 11 are gradually raised to above the melting point of the indium phosphide polycrystal, the temperature is raised to 1070 ℃ to 1300 ℃, in this embodiment, the temperature is set at 1200 ℃, the temperature is far greater than the gasification temperature of sulfur and phosphorus, the indium phosphide polycrystal is gradually melted to form a melt at this stage, and sulfur and red phosphorus are gasified into steam; in the stage, the general temperature rise rate is 1-3 ℃/min, and the duration is 6-20 h;
a constant temperature stage, wherein after the temperature rise is finished, the temperature is kept constant for 30 hours so that the indium phosphide polycrystal is fully melted; while sulfur gradually diffuses into the melt; the phosphorus vapor provides a certain vapor pressure for crystal growth.
In the crystallization stage, the temperature of the quartz tube 20 is controlled to be gradually reduced until crystallization is completed; simultaneously, the temperature control part 11 of the quartz sealing cap 10 is heated for the second time, so that the pressure of the free space 50 is kept stable, and the pressure of the free space 50 is not lower than the dissociation pressure of the melt; in this stage, the temperature of the quartz tube 20 is gradually lowered to a temperature lower than the melting point of the melt, so that the melt is crystallized.
In the stage, the temperature of the temperature control part 11 of the quartz sealing cap 10 is secondarily raised to be not lower than 1500 ℃, and the temperature raising rate is 0.1-0.5 ℃/min; the temperature is raised to 1500 ℃ by adopting 0.3 ℃.
In the temperature reduction stage, the temperature control part 11 of the quartz tube 20 and the quartz sealing cap 10 is controlled to be reduced to room temperature; wherein the cooling rate of the quartz tube 20 is controlled to be 0.1-1 ℃/min, preferably 0.4 ℃/min; the cooling rate of the quartz sealing cap 10 is controlled to be 0.1-1 ℃/min, preferably 0.75 ℃/min.
During the crystallization stage, the content of sulfur is reduced along with the gradual diffusion of sulfur into the melt, so that the pressure in the free space 50 is reduced, and the temperature control part 11 is heated for the second time in the crystallization stage so as to increase the pressure of steam in the free space 50, so that the pressure in the free space 50 is kept balanced during the doping process of the sulfur diffused into the melt, so that the sulfur is uniformly diffused into the melt, and the InP single crystal with uniformly doped sulfur is obtained; meanwhile, the doping amount of the dopant can be reduced, and the cost is saved.
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, improvement and the like without creativity within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (3)
1. A quartz sealing cap for crystal growth based on a VGF method is used in cooperation with a quartz tube to realize the sealing of the quartz tube, a crucible for crystal growth is sealed in the quartz tube, a raw material for crystal growth is contained in the crucible, and a free space is arranged between the raw material and the quartz sealing cap; the quartz tube has an opening; the quartz sealing cap comprises a cover body covering the opening of the quartz tube; the quartz sealing cap is characterized by comprising a temperature control part, wherein the temperature control part protrudes out of the cover body upwards, and the temperature control part is provided with an inner cavity leading to the free space.
2. The quartz cap of claim 1, wherein the temperature control portion is elongated perpendicular to the cover; the inner cavity is elongated.
3. A crystal growth device based on a VGF method comprises a heating furnace, a quartz tube, a quartz sealing cap and a crucible; the raw materials for crystal growth are placed in the crucible, the crucible is placed in the quartz tube, the quartz sealing cap is matched with the quartz tube for use so as to realize the sealing of the quartz tube, the quartz tube is placed in the heating furnace, the heating furnace is provided with at least one heating device for controlling the temperature of the quartz tube, and the heating devices are sequentially arranged from top to bottom; the quartz sealing cap is characterized in that the quartz sealing cap is the quartz sealing cap of claim 1 or 2; the heating furnace also comprises at least one heating device for controlling the temperature of the temperature control part of the quartz sealing cap.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201922459336.5U CN211620660U (en) | 2019-12-31 | 2019-12-31 | Quartz sealing cap for crystal growth based on VGF method and crystal growth device |
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| CN201922459336.5U CN211620660U (en) | 2019-12-31 | 2019-12-31 | Quartz sealing cap for crystal growth based on VGF method and crystal growth device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110952133A (en) * | 2019-12-31 | 2020-04-03 | 珠海鼎泰芯源晶体有限公司 | Quartz sealing cap for crystal growth based on VGF method, crystal growth device and crystal growth process |
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2019
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110952133A (en) * | 2019-12-31 | 2020-04-03 | 珠海鼎泰芯源晶体有限公司 | Quartz sealing cap for crystal growth based on VGF method, crystal growth device and crystal growth process |
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