CN112663135B - Monoclinic phase Ga 2 S 3 Method and apparatus for physical vapor growth of single crystal - Google Patents
Monoclinic phase Ga 2 S 3 Method and apparatus for physical vapor growth of single crystal Download PDFInfo
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- CN112663135B CN112663135B CN202011377984.7A CN202011377984A CN112663135B CN 112663135 B CN112663135 B CN 112663135B CN 202011377984 A CN202011377984 A CN 202011377984A CN 112663135 B CN112663135 B CN 112663135B
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Abstract
The application discloses a monoclinic phase Ga 2 S 3 A physical vapor phase growth method of single crystal and a growth apparatus thereof. Monoclinic phase Ga 2 S 3 A method for physical vapor growth of a single crystal comprising the steps of: will contain Ga 2 S 3 Polycrystalline raw material and monoclinic phase Ga 2 S 3 Heating and keeping the temperature of the vacuum sealed container of the seed crystal in a temperature gradient area; cooling after crystal growth to obtain the monoclinic Ga 2 S 3 A crystal; the Ga 2 S 3 The polycrystalline raw material is positioned in a high temperature area; the monoclinic phase Ga 2 S 3 The seed crystal is located in the low temperature region. The growth method is simple to operate, economical and practical, and can obtain centimeter-level high-quality large-size monoclinic phase Ga meeting practical requirements 2 S 3 And has high transmittance in the ultraviolet-visible near infrared region.
Description
Technical Field
The application relates to a monoclinic Ga 2 S 3 A physical vapor deposition growth method and a growth device of single crystals, belonging to the technical field of single crystal growth.
Background
At present, materials which can be applied in the infrared band are not more, and are mostly ABC 2 Chalcopyrite-structured semiconductor materials, e.g. AgGaS 2 、ZnGeP 2 Etc., but they suffer from some drawbacks, such as a small laser damage threshold; the transmittance of the crystal in the near and middle infrared regions is low (extrinsic defects easily cause light absorption and light scattering); anisotropic thermal expansion is serious, etc., and directly affects practical use. Therefore, the search for novel mid-far infrared nonlinear optical materials with excellent performance has an unprecedented necessity.
Monoclinic phase Ga 2 S 3 The crystal is a middle-far infrared band nonlinear optical crystal with excellent physical and chemical properties, has frequency multiplication response under 2 mu m laser excitation, and has phase matching characteristics, the crystal is not absorbed at 2 mu m, and the laser damage threshold is commercial AgGaS 2 In addition, its birefringence is 30 times that of AgGaS 2 Equivalent. Thus monoclinic phase Ga 2 S 3 The crystal is a potential high-power medium-far infrared nonlinear laser material. However, monoclinic phase Ga is grown 2 S 3 The crystal has the problem of Ga 2 S 3 There are 3 phases (low Wen Lifang, medium Wen Shanxie, high temperature hexagonal) and the phase transition between each phase is overcome by growing high quality monoclinic Ga 2 S 3 The primary problem faced by crystals;
it is well known that chalcogenide crystals cannot be synthesized and grown in an open space due to their strong volatility and susceptibility to oxidation, but rather need to be performed in a closed anhydrous and anaerobic environment. The current melt-process single crystal growth technology is not in the way of single crystal growth of non-uniform melting (or phase change) chalcogenides, and results in certain crystalline materials with excellent performance, but is still in the laboratory research stage, cannot meet the requirement of high technical development, and the industrialization technology level of laboratory achievement to productivity is still behind. Therefore, it is of great importance to explore and develop a method suitable for crystal growth of such compounds.
Disclosure of Invention
In view of the deficiencies of the prior art, the present application aims to provide a monoclinic phase Ga 2 S 3 A method for growing single crystals.
In order to solve the technical problems, the technical scheme of the application is as follows: be applicable to monoclinic phase Ga 2 S 3 The growth method of single crystal adopts vertical physical vapor deposition method, and obtains centimeter grade monoclinic phase Ga meeting practical requirements by regulating and controlling growth temperature 2 S 3 The single crystal has good quality and high transmittance. The growth method of the application is simple in operation, efficient, economical and practical.
According to a first aspect of the present application there is provided a monoclinic phase Ga 2 S 3 A physical vapor phase growth method of single crystals. The growth method is simple to operate, economical and practical, and can obtain centimeter-level high-quality large-size monoclinic phase Ga meeting practical requirements 2 S 3 。
Monoclinic phase Ga 2 S 3 A method for physical vapor growth of a single crystal comprising the steps of:
will contain Ga 2 S 3 Polycrystalline raw material and monoclinic phase Ga 2 S 3 Heating and keeping the temperature of the vacuum sealed container of the seed crystal in a temperature gradient area; cooling after crystal growth to obtain the monoclinic Ga 2 S 3 A crystal;
the temperature gradient zone comprises a high temperature zone and a low temperature zone, and the high temperature zone is positioned at the upper part of the low temperature zone;
the Ga 2 S 3 The polycrystalline raw material is positioned in a high temperature area;
the monoclinic phase Ga 2 S 3 The seed crystal is located in the low temperature region.
Ga 2 S 3 The polycrystalline raw material is decomposed in a high temperature region, and is deposited to monoclinic phase Ga in a low temperature region by physical deposition 2 S 3 And growing on the seed crystal.
Optionally, the preset temperature of the high temperature area is 860-1060 ℃.
Alternatively, the preset temperature of the high temperature zone is independently selected from any value or range of values between any two of 860 ℃, 880 ℃, 900 ℃, 910 ℃, 930 ℃, 950 ℃, 960 ℃, 980 ℃, 1000 ℃, 1010 ℃, 1030 ℃, 1050 ℃, 1060 ℃.
Optionally, the preset temperature of the high temperature region is 910-1010 ℃.
Optionally, the preset temperature of the low temperature region is 820-1020 ℃.
Alternatively, the preset temperature of the low temperature region is independently selected from any value or range of values between any two of 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 910 ℃, 930 ℃, 950 ℃, 960 ℃, 980 ℃, 1000 ℃, 1010 ℃, 1020 ℃.
Optionally, the preset temperature of the low temperature region is 870-970 ℃.
Optionally, the preset temperatures of the high temperature area and the low temperature area are obtained through temperature rise, and the temperature rise rate is 3-10 ℃/min.
Optionally, the temperature gradient is 1-10 ℃/cm;
alternatively, the temperature gradient is 2-5 ℃/cm.
Alternatively, the temperature gradient is independently selected from any value or range of values between any two of 1 ℃/cm, 2 ℃/cm, 3 ℃/cm, 4 ℃/cm, 5 ℃/cm, 6 ℃/cm, 7 ℃/cm, 8 ℃/cm, 9 ℃/cm, 10 ℃/cm.
Specifically, in the actual growth process, according to the condition factors such as the size of the closed container, a high temperature area and a low temperature area are correspondingly arranged, so that the temperature gradient is in a reasonable range.
Optionally, the monoclinic phase Ga 2 S 3 The seed crystal is polished on one side, and the polished surface is a growth surface.
Optionally, the seed crystal is hexahedron with single-sided polishing. The polishing surface was placed on the bottom of the quartz crucible, and the quartz crucible containing the raw material was placed on the upper end of the quartz tube.
Alternatively, the crystal growth time is 150 to 400 hours.
Alternatively, the crystal growth time is 300h.
Optionally, the high temperature region and the low temperature region are cooled to room temperature at a speed of 8-25 ℃/h.
Optionally, the high temperature zone and the low temperature zone are each cooled to room temperature at a rate of 10-25 ℃/h.
Alternatively, the cooling rate is independently selected from any value or range of values between any two of 8 ℃/h, 9 ℃/h, 10 ℃/h, 11 ℃/h, 12 ℃/h, 15 ℃/h, 18 ℃/h, 20 ℃/h, 22 ℃/h, 25 ℃/h.
Specifically, the temperatures of the high temperature region and the low temperature region were raised to 980 ℃ and 880 ℃ at a heating rate of 5 ℃/min, and the temperature was kept constant for 300 hours, and crystal growth was started until crystals of a certain size were obtained, and then cooled to room temperature at a rate of 10 ℃ per hour.
Optionally, the vacuum degree of the vacuum sealed container is less than or equal to 10 -2 Pa。
Optionally, the vacuum closed container is in a water-free and oxygen-free condition.
Optionally, the closed container is a quartz tube.
Optionally, the method comprises the following steps:
1) Monoclinic phase Ga 2 S 3 The seed crystal is arranged at the bottom of the quartz tube; ga is added 2 S 3 The polycrystalline raw material is placed in a small quartz crucible and fixed at the upper end in a quartz tube, and an opening at the bottom of the small quartz crucible is communicated with the bottom of the quartz tube;
2) Vacuum sealing the quartz tube in the step 1);
3) Heating and keeping the temperature of the vacuum-sealed quartz tube in a temperature gradient area; cooling after crystal growth to obtain the monoclinic Ga 2 S 3 And (5) a crystal.
Alternatively, in step 1), the feedstock is 99.99% Ga 2 S 3 Powder, namely placing the raw materials into a mortar for full grinding, then pressing the raw materials into tablets, and placing the pressed raw material blocks into a quartz crucible with holes at the bottom; the grinding time is 10 to 60 minutes, preferably 15 to 30 minutes.
Optionally, in step 2), the vacuum sealing process is to pump air from the quartz tube to make the air pressure in the tube less than or equal to 10 -2 Pa, the sealing is carried out by adopting oxyhydrogen flame.
Optionally, in step 3), the vacuum-sealed quartz tube is placed in a temperature gradient in a growth device with a high temperature area and a low temperature area, heated to a preset temperature, and then is insulated to obtain a stable temperature field.
As a specific embodiment, the method comprises the following steps:
1) By Ga 2 S 3 The method comprises the steps of taking the polycrystalline raw material as a raw material, tabletting to obtain a polycrystalline raw material block, putting the polycrystalline raw material block into a quartz crucible with a hole at the bottom, and sleeving the quartz crucible filled with the raw material into the upper end of a quartz tube with seed crystals at the bottom;
2) The quartz tube filled with seed crystal and raw material is connected into a vacuum line for vacuumizing, and the vacuum degree is superior to 10 -2 Sealing the quartz tube in a melting way under the Pa state;
3) Placing the quartz tube into a high temperature furnace, setting the temperature in a temperature zone, keeping constant for about 300 hours, cooling to room temperature, and obtaining the monoclinic Ga at the bottom of the quartz tube 2 S 3 And (3) single crystals.
Specifically, the step of heating at high temperature in the step 3) specifically includes:
placing the raw material mixture obtained after tabletting in the step 2) in a high-temperature furnace, and then raising the temperature to enable the temperature area in the growth device to reach the preset temperature, keeping the temperature constant, and obtaining a stable temperature field.
Specifically, the cooling step in step 3) specifically includes:
cooling the high temperature region and the low temperature region to obtain the monoclinic phase Ga 2 S 3 Single crystals, the size of which reaches the centimeter level.
As a specific embodiment, the method comprises the following steps:
(1) Preparing seed crystals, mounting the cut and polished seed crystals on the bottom of a quartz tube with the polished surface facing upwards, grinding and tabletting the raw materials, then loading the ground raw materials into a quartz crucible with a hole at the bottom, and placing the quartz crucible at the upper end of the quartz tube;
(2) Vacuum is pumped to the quartz tube, and the vacuum degree is better than 10 -2 Sealing under Pa;
(3) The quartz tube is lowered to a hearth temperature gradient zone, the temperature in the temperature zone is set to be constant, crystal growth is started until crystals with certain size are obtained, and then the temperature is lowered to room temperature, so that the method is simple and convenient to operate and suitable for monoclinic phase Ga 2 S 3 And (3) growing single crystals.
As a preferred embodiment, physical vapor deposition is adopted for growth, and a double-layer heating furnace and a closed quartz tube are used for realizing; then the temperature gradient is kept at 3 ℃/cm for 300 hours; the method specifically comprises the following steps:
(1) Mounting the cut and polished seed crystal at the bottom of a quartz tube, loading the raw materials into a quartz crucible with a hole at the bottom through grinding and tabletting, and placing the quartz crucible at the upper end of the quartz tube;
(2) Vacuum is pumped to the quartz tube, and the vacuum degree is better than 10 -2 Sealing under Pa;
(3) And (3) installing the quartz tube at the tail end of the corundum rod, reducing the temperature to a temperature gradient zone of a hearth, setting the temperature of the temperature zone, starting crystal growth, and cooling to room temperature after crystals with a certain size are obtained.
According to a second aspect of the present application, there is provided a crystal growth apparatus.
A crystal growth apparatus comprising a dual temperature zone heating furnace; a hearth is arranged in the double-temperature-zone heating furnace body; the hearth comprises a high-temperature area positioned at the upper end of the hearth and a low-temperature area positioned at the lower end of the hearth; the upper part of the hearth is provided with a heat-insulating cover, and a corundum rod penetrates through the heat-insulating cover to enter the hearth and is connected with the quartz crucible; the furnace body support is provided with a lifting device.
Specifically, a furnace body bracket is arranged below the furnace body.
Specifically, the hearth is a corundum hearth.
Optionally, the lifting device comprises a linear guide rail, a ball screw and a lifting cross arm;
the lifting cross arm is connected with the corundum rod so as to control the up-and-down motion of the quartz crucible;
the linear guide rail is connected with the lifting cross arm so as to enable the lifting cross arm to reciprocate up and down;
the ball screw is connected with the lifting cross arm, and the lifting cross arm is driven to move up and down by the rotation of the precise ball screw.
Optionally, the crystal growing device further comprises a heating device arranged on the outer peripheral side of the hearth;
the heating device is respectively positioned in a high temperature area and a low temperature area;
optionally, the heating device is a heating wire.
Optionally, the high temperature area and the low temperature area are both provided with temperature control devices;
optionally, the temperature control device is a temperature control thermocouple;
optionally, the temperature control thermocouple is an S-type temperature control thermocouple.
Optionally, the upper, middle and lower ends of the hearth are provided with heat insulation layers for heat preservation.
Optionally, quartz plates are arranged at two ends of the inner side of the upper part of the quartz crucible and used for supporting a small quartz crucible; and the bottom of the small quartz crucible is provided with a hole.
Optionally, two quartz plates are arranged at the upper end inside the quartz tube and used for fixedly placing a small crucible, and the bottom end of the small crucible is provided with a ventilation small hole.
The quartz crucible and the quartz tube are characterized in that: the bottom of the quartz crucible is provided with ventilation small holes, and the upper end of the inside of the quartz tube is provided with two quartz plates for fixing the quartz crucible.
In the present application, unless otherwise specified, the data ranges given are selected from any value in the ranges and include the endpoints of the ranges.
The application has the beneficial effects that:
monoclinic phase Ga provided by the application 2 S 3 Physical vapor phase growth method of single crystal, and vertical vacuum physical vapor deposition method is adopted to prepare monoclinic phase Ga 2 S 3 The monocrystal adopts the polycrystalline raw material of the tabletting to seal the upper end of the quartz tube, the polished seed crystal is placed at the lower end, the quartz tube after being sealed by the stone is placed in a temperature gradient zone, and the high-quality monoclinic phase Ga which can meet the practical requirements is obtained by adjusting parameters such as temperature and the like in the growth process 2 S 3 Single crystal and has high transmittance in ultraviolet, visible and near infrared regions. The single crystal growth method is practical, simple to operate, economical, low in cost and environment-friendly. The crystal growth apparatus provided by the application has simple structure, safety and reliability,
drawings
FIG. 1 is a schematic diagram showing the construction of a crystal growth apparatus using a physical vapor deposition method according to the present application.
FIG. 2 is a cross-sectional view of a quartz crucible of the present application.
In FIG. 1, a ball screw 2, a linear guide rail 3, a furnace body support 4, a corundum furnace chamber 5, a lifting cross arm 6, a corundum rod 7, a heat insulation cover 8, a heat insulation layer 9, a heating furnace body 10, a high-temperature heating wire 11, a thermocouple 12 and a quartz crucible
In FIG. 2, 13, a quartz tube 14, a small quartz crucible 15 with a hole at the bottom, a quartz plate 16 for fixing the quartz crucible, and a seed crystal
FIG. 3 shows monoclinic Ga prepared in example 1 2 S 3 Photographs of the crystals.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
If not specified, the test methods are all conventional methods, and the instrument settings are all recommended by manufacturers.
Unless otherwise indicated, the starting materials and reagents in the examples of the application were purchased commercially, with Ga 2 S 3 Purchased from Kaida semiconductor materials Co., hangzhou with a purity of 99.99%.
The application provides a crystal growth device, which comprises a double-temperature-zone heating furnace body 9, wherein a furnace body support 3 is arranged below the furnace body, a corundum furnace chamber 4 is arranged in the furnace body, and a heat preservation cover 7 is arranged at the upper end of the corundum furnace chamber. The crucible fixing device comprises a corundum rod 6 vertically extending into a corundum hearth, the bottom end of the corundum rod is connected with a quartz crucible 12, the top end of the corundum rod passes through a heat preservation cover at the upper end and then is connected with an outer top lifting cross arm 5, the other end of the lifting cross arm is connected with a vertical ball screw 1 through a ball nut, up-and-down movement adjustment is carried out to realize lifting of the corundum rod, and a linear guide rail 2 is arranged on the lifting cross arm.
In the embodiment of the application, a heating device is arranged on the peripheral side of the corundum hearth, and the heating device comprises a high-temperature heating wire 10; a temperature control device is arranged in the temperature zone, and the temperature control device is a temperature control S-shaped thermocouple 11.
In the embodiment of the application, the corundum hearth and the upper, middle and lower ends are provided with the heat insulation layers 8, so that the constant temperature in the corundum hearth is ensured.
Wherein, as shown in FIG. 2, quartz plates 15 for fixing quartz crucible are arranged on both sides of the inner wall of the upper part of quartz tube 13 to support small quartz crucible 14 with holes at the bottom, ga is contained in small quartz crucible 14 2 S 3 Polycrystalline raw material, and a seed crystal 16 are positioned at the bottom of the quartz tube 13.
Be applicable to monoclinic phase Ga 2 S 3 The single crystal growth method adopts a vertical physical vapor deposition method to grow and is realized by using a double-layer high-temperature furnace, wherein the furnace comprises a corundum hearth, and the upper end of the corundum hearth is provided with a heat preservation cover. The temperature of the high temperature area is 980 ℃, the temperature of the low temperature area is 880 ℃, the temperature gradient is 3 ℃/cm, and the temperature is constantThe fixed time is 300 hours, and the cooling rate is 10 ℃/hour; the method specifically comprises the following steps:
(1) Placing the cut and polished seed crystal at the bottom of a large quartz tube with the polishing surface facing upwards, grinding and tabletting the raw materials, then placing the ground and pressed raw materials into a small quartz crucible with a hole at the bottom, and placing the small quartz crucible at the upper end of the quartz tube;
(2) Vacuum is pumped to the quartz tube, and the vacuum degree is better than 10 -2 Sealing under Pa;
(3) Fixing the fused quartz tube on a corundum rod, then lowering the fused quartz tube into a temperature zone gradient zone in the hearth, setting the temperature of the temperature zone, starting crystal growth, setting the cooling speed and lowering the temperature to the room temperature after crystals with a certain size are obtained.
In the embodiment of the application, the raw material in the step (1) is Ga with the purity not lower than 99.9 percent 2 S 3 And (3) powder.
In the embodiment of the present application, the crystal growth step in the step (3) is specifically:
a) The temperature of the high temperature area is set to 980 ℃, the temperature of the low temperature area is set to 880 ℃, the temperature rising speed is 5 ℃/min, and the temperature gradient is 3 ℃/cm; the temperature field was kept constant for 300 hours.
b) And starting crystal growth until crystals with a certain size are obtained, and cooling to room temperature at a speed of 10 ℃/h.
Example 1
1) Ga with cutting size of 3mm x 1mm 2 S 3 And (3) after single-sided polishing, filling the seed crystal into the bottom of the quartz tube, and enabling the polishing surface to face upwards. Ga with purity of 99.99% is used 2 S 3 The powder is used as raw material, 20g of raw material is placed in a mortar for fully grinding for 30 minutes, then the raw material is pressed into tablets, the pressed raw material blocks are placed in a small quartz crucible with holes at the bottom, and then the small quartz crucible is placed in the upper end of a quartz tube for fixing.
2) Vacuumizing the quartz tube to a vacuum degree of 10 -2 And (5) Pa, and then carrying out melt sealing.
3) And fixing the fused and sealed quartz tube on a corundum rod, and then lowering the fused and sealed quartz tube into a temperature zone gradient zone in a corundum hearth. Wherein the seed crystal is in a low temperature region.
4) Setting the temperature 980 ℃ in a high temperature area, the temperature rising rate is 5 ℃/min, the temperature 880 ℃ in a low temperature area, the temperature rising rate is 5 ℃/min, the temperature gradient is 10 ℃/cm, obtaining a stable temperature field, starting crystal growth, keeping the crystal constant for 300 hours, and setting the cooling rate to 10 ℃/hour and cooling to the room temperature after obtaining crystals with a certain size.
5) After the growth is completed, the method is adopted to finally obtain the centimeter-level large-size monoclinic phase Ga 2 S 3 The single crystal had a crystal size of 25 mm. Times.15 mm. Times.8 mm. Wherein fig. 3 is a photograph thereof, it can be seen that the crystal is smooth and uniform, and has very good quality. The sample is marked as sample # 1.
Measurement of cm-sized monoclinic phase Ga obtained in example 1 2 S 3 Transmittance of the crystal:
1) Monoclinic phase Ga 2 S 3 And (3) crystal cutting and polishing: the monoclinic phase Ga is obtained 2 S 3 The crystals were cut to a size of about 3X 4X 1mm 3 And polishing the two surfaces.
2) Round holes of about 2mm in diameter are punched in a black sheet, and then the polished monoclinic phase Ga is applied 2 S 3 The crystals are stuck to the holes, so that the single crystals block the small holes, then the black plate with the single crystals is used for measuring the transmittance, the transmittance test range is 0.6-5.5 mu m, and the laser just passes through the small holes during measurement. The monoclinic phase Ga in example 1 was measured by this method 2 S 3 The ultraviolet visible near infrared light transmittance of the crystal is 85%.
Example 2
The operation is the same as in example 1, except that: setting the temperature of a high temperature region at 1000 ℃, the temperature rising rate at 5 ℃/min, the temperature of a low temperature region at 920 ℃, the temperature rising rate at 5 ℃/min and the temperature gradient at 8 ℃/cm to obtain a stable temperature field. The resulting sample was designated sample # 2. The dimensions thereof were 15mm×10mm×5mm, and the transmittance of ultraviolet visible near infrared light thereof was 89% as measured by the transmittance method in example 1.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (18)
1. Monoclinic phase Ga 2 S 3 The physical vapor phase growth method of the single crystal is characterized in that the physical vapor phase growth method adopts a vertical physical vapor phase deposition method, and specifically comprises the following steps:
will contain Ga 2 S 3 Polycrystalline raw material and monoclinic phase Ga 2 S 3 Heating and keeping the temperature of the vacuum sealed container of the seed crystal in a temperature gradient area; cooling after crystal growth to obtain the monoclinic Ga 2 S 3 A crystal;
the temperature gradient zone comprises a high temperature zone and a low temperature zone, and the high temperature zone is positioned at the upper part of the low temperature zone;
the Ga 2 S 3 The polycrystalline raw material is positioned in a high temperature area;
the monoclinic phase Ga 2 S 3 The seed crystal is positioned in the low temperature area;
the preset temperature of the high temperature area is 860-1030 ℃;
the preset temperature of the low temperature region is 820-930 ℃;
the temperature gradient is 1-10 ℃/cm.
2. The growth method according to claim 1, wherein the temperature gradient is 2-5 ℃/cm.
3. The growth method according to claim 1, wherein the monoclinic phase Ga 2 S 3 The seed crystal is polished on one side, and the polished surface is a growth surface.
4. The growth method according to claim 1, wherein the crystal growth time is 150 to 400 hours.
5. The growth method according to claim 1, wherein the high temperature region and the low temperature region are cooled to room temperature at a rate of 8-25 ℃/h.
6. The growth method according to claim 1, wherein the high temperature region and the low temperature region are each 10 to 25 o The rate of C/h was reduced to room temperature.
7. The method according to claim 1, wherein the vacuum degree of the vacuum-tight container is 10 or less - 2 Pa。
8. A method of growing according to claim 1, comprising the steps of:
1) Monoclinic phase Ga 2 S 3 The seed crystal is arranged at the bottom of the quartz tube; ga is added 2 S 3 The polycrystalline raw material is placed in a small quartz crucible and fixed at the upper end in a quartz tube, and an opening at the bottom of the small quartz crucible is communicated with the bottom of the quartz tube;
2) Vacuum sealing the quartz tube in the step 1);
3) Heating and keeping the temperature of the vacuum-sealed quartz tube in a temperature gradient area; cooling after crystal growth to obtain the monoclinic Ga 2 S 3 And (5) a crystal.
9. The growing method according to claim 8, wherein in step 3), the vacuum-sealed quartz tube is placed in a temperature gradient in a growing apparatus having a high temperature region and a low temperature region, heated to a predetermined temperature, and then kept warm to obtain a stable temperature field.
10. A crystal growth apparatus comprising monoclinic Ga according to any one of claims 1 to 9 2 S 3 The application of the single crystal physical vapor growth method is characterized in that the crystal growth device comprises a double-temperature-zone heating furnace body; a hearth is arranged in the double-temperature-zone heating furnace body; the hearth comprises a high-temperature area positioned at the upper end of the hearth and a low-temperature area positioned at the lower end of the hearth; the upper part of the hearth is provided with a heat-insulating cover, and a corundum rod penetrates through the heat-insulating cover to enter the hearth and is connected with the quartz crucible; furnace body supportThe frame is provided with a lifting device.
11. The use of claim 10, wherein the lifting device comprises a linear guide, a ball screw, and a lifting cross arm;
the lifting cross arm is connected with the corundum rod so as to control the up-and-down motion of the quartz crucible;
the linear guide rail is connected with the lifting cross arm so as to enable the lifting cross arm to reciprocate up and down;
the ball screw is connected with the lifting cross arm and drives the lifting cross arm to move up and down through rotation of the ball screw.
12. The use according to claim 11, wherein the crystal growing apparatus further comprises a heating apparatus provided on the outer peripheral side of the furnace chamber;
the heating device is respectively positioned in the high temperature area and the low temperature area.
13. The use according to claim 12, wherein the heating means is a heating wire.
14. Use according to claim 10, wherein both the high temperature zone and the low temperature zone are provided with temperature control means.
15. The use according to claim 14, wherein the temperature control device is a temperature control thermocouple.
16. The use of claim 15, wherein the temperature control thermocouple is an S-type temperature control thermocouple.
17. The use according to claim 10, wherein the upper, middle and lower ends of the furnace are provided with heat insulation layers for heat preservation.
18. The use according to claim 10, wherein the quartz crucible upper inner side is provided with quartz plates at both ends for supporting a small quartz crucible; and the bottom of the small quartz crucible is provided with a hole.
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| RU2768954C1 (en) * | 2021-06-09 | 2022-03-25 | Федеральное государственное бюджетное учреждение науки Институт физики твердого тела имени Ю.А. Осипьяна Российской академии наук (ИФТТ РАН) | Method for obtaining gallium sulfide (ii) |
| CN114381800A (en) * | 2022-02-14 | 2022-04-22 | 苏州燎塬半导体有限公司 | Preparation method of single crystal gallium oxide and process equipment for preparing single crystal gallium oxide |
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