CN113735071B - Preparation method and device of high-purity gallium telluride - Google Patents
Preparation method and device of high-purity gallium telluride Download PDFInfo
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- CN113735071B CN113735071B CN202110948849.1A CN202110948849A CN113735071B CN 113735071 B CN113735071 B CN 113735071B CN 202110948849 A CN202110948849 A CN 202110948849A CN 113735071 B CN113735071 B CN 113735071B
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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Abstract
The invention belongs to the field of semiconductor material preparation, and discloses a preparation method and a device of high-purity gallium telluride, wherein the preparation method comprises the following steps: s1, mixing tellurium and gallium and filling the mixture into a crucible boat; s2, placing the crucible boat in the step S1 in a quartz tube, and keeping the nitrogen/hydrogen atmosphere in the quartz tube; s3, controlling a heater to integrally heat the quartz tube so as to react the tellurium and the gallium; s4, controlling a heater, sequentially dividing the quartz tube into a plurality of small sections from one end of the quartz tube to the other end of the quartz tube, and controlling the heater to sequentially cool the quartz tube to the temperature of the middle section; s5, controlling the heater to integrally cool the quartz tube to room temperature, and taking out the crucible boat in the quartz tube to obtain the high-purity gallium telluride. The preparation method of the high-purity gallium telluride is simple in process and high in efficiency, the prepared gallium telluride is good in performance, high in purity, free of defects such as air bubbles and inclusions, high in repetition rate and qualified in yield of 80-90%.
Description
Technical Field
The invention belongs to the field of semiconductor material preparation, and particularly relates to a preparation method and a device of high-purity gallium telluride.
Background
Gallium telluride is an important doping material, is widely applied to growth of antimonide single crystals, and can greatly improve the electrical property of the antimonide single crystals and reduce dislocation. The use of high purity gallium telluride as the dopant facilitates the production of good performing antimonide single crystals.
At present, the preparation method of gallium telluride mainly uses a traditional VB method, the cost of equipment and time required by preparation is relatively high, the production efficiency is low, impurities are not easy to discharge by the VB method, the purity of the product is low, and the product performance is reduced.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for preparing high-purity gallium telluride, which has the advantages of simple process, high efficiency, good performance of the prepared gallium telluride, high purity, and no defects such as bubbles and inclusions.
The invention also aims to provide a preparation device of high-purity gallium telluride.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of high-purity gallium telluride comprises the following steps:
s1, mixing tellurium and gallium according to a specified molar ratio, wherein tellurium is excessive relative to gallium, and filling the mixed material into a crucible boat.
S2, placing the crucible boat in the quartz tube in the step S1, placing the quartz tube in a heater, exhausting air in the quartz tube, continuously introducing nitrogen and hydrogen serving as protective gases, and keeping the nitrogen/hydrogen atmosphere in the quartz tube.
And S3, controlling the heater to enable the whole quartz tube to be heated to 850 to 1000 ℃ at a first heating rate, and keeping the temperature for a period of time to enable tellurium and gallium to react.
S4, controlling a heater, sequentially dividing the quartz tube into a plurality of small sections from one end of the quartz tube to the other end, controlling the heater, and sequentially cooling to the target temperature of 550-620 ℃ at a first cooling rate, wherein the method specifically comprises the following steps: the temperature of the former section is kept after reaching the target temperature, and the temperature of the latter section is kept until reaching the target temperature of the last section; in the solidification process, impurities with the segregation coefficient smaller than 1 are concentrated in the backward solidification part, and impurities with the segregation coefficient larger than 1 are concentrated in the early solidification part. The middle section is high-purity material with low impurity.
And S5, controlling the heater to enable the whole quartz tube to be cooled to the room temperature at a second cooling rate. Stopping introducing nitrogen and hydrogen, stopping heating, taking out the crucible boat in the quartz tube, and removing the parts with high impurities at the head and the tail, wherein the middle section is the required high-purity gallium telluride.
Further, in step S1, the tellurium is 7N tellurium, and the gallium is 7N gallium.
Further, in step S1, the molar ratio of tellurium to gallium is 1.002 to 1.005:1.
further, in step S2, the air in the quartz tube is exhausted by introducing nitrogen gas into the quartz tube.
Further, in the step S2, the introduced gas is 5N high-purity gas. The gas keeps flowing in the quartz tube, the two ends of the quartz tube are connected and sealed by adopting metal flanges, the tail end of the quartz tube is provided with a solid particle filtering device, and the gas finally enters the tail gas absorption tank and is discharged.
Further, in the steps S3, S4 and S5, the mixed gas of hydrogen and nitrogen with the hydrogen concentration of 20 to 30% is kept as the protective gas, so that the oxygen content in the quartz tube can be greatly reduced, the material oxidation is avoided, and the purity of the product is further improved.
Further, in the step S3, the first heating rate is 200 to 500 ℃/h.
Furthermore, the temperature of the melt is kept for 1 to 2h after the temperature is raised to 750 to 820 ℃, so that the temperature of the melt is uniform, and the melt is fully melted and mixed.
Further, in the step S4, the first cooling rate is 30 to 50 ℃/h.
Further, in step S4, the temperature is decreased to the target temperature of 600 ℃ at a first temperature decrease rate.
In the invention, the temperature is reduced at the cooling rate of 30-50 ℃/h in sequence, and impurities are effectively removed by the temperature gradient and the cooling rate, so that the gallium telluride with higher purity is obtained.
And further, in the step S4, after the last section reaches the target temperature, keeping the temperature, and controlling the heater to keep the temperature for 1 to 2h.
Further, in the step S5, the second cooling rate is 60 to 80 ℃/h. During step S5, too fast a temperature decrease may cause thermal stress concentration, resulting in cracking of the quartz boat and the gallium telluride. Too slow will affect production efficiency, and the cooling rate is moderate, meeting the production requirements of quality and efficiency.
In the invention, after the step S4 is finished, the temperature is kept for 1 to 2h, the temperature in the crystal is balanced, and then the crystal enters a cooling stage, wherein the cooling rate is 60 to 80 ℃/h, and the cooling rate can reduce the pressure stress between the crystal and the quartz boat caused by different thermal expansion coefficients, so that the crystal is prevented from cracking and the quartz boat is prevented from being broken.
The invention also discloses a preparation device of the high-purity gallium telluride, which comprises a quartz tube, a crucible boat arranged in the quartz tube and a heater arranged around the tube wall of the quartz tube.
Furthermore, the heater includes a plurality of independently controlled heat-generating bodies, every the heat-generating body is established in proper order according to certain interval outside the quartz capsule pipe wall.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the high-purity gallium telluride is simple in process and high in efficiency, the prepared gallium telluride is good in performance, high in purity, free of defects such as air bubbles and inclusions, high in repetition rate and qualified in yield of 80-90%.
(2) The preparation method of high-purity gallium telluride has the advantages of short production flow, large treatment capacity, realization of industrialization, popularization of the method and remarkable economic benefit.
(3) The preparation method of the high-purity gallium telluride adopts a production mode of flowing protective gas flow in the resynthesis reaction process, and the designed device has simple structure requirement and lower cost.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for producing high-purity gallium telluride in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
As shown in fig. 1, the embodiment discloses a high-purity gallium telluride preparing apparatus, which includes a quartz tube 110, a quartz boat 120 disposed in the quartz tube 110, and a set of heaters 130 disposed around the tube wall of the quartz tube 110, wherein the heaters 130 include 9 independently controlled heating elements 131, and the 9 heating elements are sequentially sleeved outside the tube wall of the whole quartz tube at intervals of 20 mm.
Example 2
This example discloses a method for preparing high-purity gallium telluride, using the apparatus as described in example 1, comprising the following steps:
s1, selecting 7N high-purity tellurium and 7N high-purity gallium with the total weight of 3kg, wherein the molar ratio is 1.003:1 weighing the materials, putting the materials into a quartz boat, and uniformly mixing the materials to form a uniformly mixed material;
s2, placing the quartz boat in the middle section of the quartz tube in the step S1, placing the quartz tube in a heater, introducing 5N nitrogen into the quartz tube to replace air in the quartz tube, keeping for 20min, and introducing 5N hydrogen into the quartz tube to control the hydrogen concentration to be 20%;
s3, controlling a heater, heating all the heating elements to 1000 ℃ at a speed of 250 ℃/h, keeping the temperature for 1h, and heating and melting the high-purity raw materials to obtain a gallium telluride melt;
s4, controlling a heater to sequentially cool the heating body to 600 ℃ from beginning to end at a cooling rate of 40 ℃/h, namely: keeping the temperature of the former heating element after reaching the target temperature of 600 ℃, and cooling the latter heating element until the last heating element is cooled, and when the temperature of the last heating element reaches 600 ℃, completing the whole solidification process, and keeping the temperature of 600 ℃ for 1.5 hours;
s5, controlling the heater to enable all the heating bodies to start to cool to room temperature at the same cooling rate of 80 ℃/h, stopping ventilation and heating, and taking out the quartz boat and the gallium telluride in the quartz boat after all mixed gas is removed. The obtained gallium telluride is analyzed after head and tail removal, and the product purity is 6N and has no defects such as air holes, cracks and the like.
Comparative example 1
This comparative example is substantially the same as example 2 except for the points S4 and S5.
In the comparative example, S4/S5 is combined into one step, which specifically comprises: controlling the heater to enable all the heating bodies to start to cool to room temperature at the same cooling rate of 80 ℃/h, stopping ventilation and heating, and taking out the quartz boat and gallium telluride in the quartz boat after all mixed gas is removed. When the quartz boat is discharged, the quartz boat is broken, and the obtained gallium telluride has obvious cracks and fine cracks. After the head and the tail are removed, the product has more impurities and the purity is 5N.
Example 3
As shown in fig. 1, the present embodiment discloses a preparation apparatus of high purity gallium telluride, the apparatus includes a quartz tube 110, a quartz boat 120 disposed in the quartz tube 110, and a set of heaters 130 disposed around the tube wall of the quartz tube 110, the heaters 130 include 7 independently controlled heating elements 131, and the 7 heating elements are sequentially sleeved outside the tube wall of the whole quartz tube at an interval of 20 mm.
Example 4
This example discloses a method for preparing high-purity gallium telluride using the apparatus as described in example 3, comprising the steps of:
s1, selecting 7N high-purity tellurium and 7N high-purity gallium with the total weight of 5kg, wherein the molar ratio is 1.003:1 weighing the materials, putting the materials into a quartz boat, and uniformly mixing the materials to form a uniformly mixed material;
s2, placing the quartz boat in the middle section of the quartz tube in the step S1, placing the quartz tube in a heater, introducing nitrogen into the quartz tube to replace air in the quartz tube, keeping for 30min, and then introducing hydrogen into the quartz tube, wherein the concentration of the hydrogen is controlled to be 30%;
s3, controlling a heater, heating all the heating elements to 1000 ℃ at a speed of 350 ℃/h, keeping the temperature for 1.5h, and heating and melting the high-purity raw materials to obtain a gallium telluride melt;
s4, controlling a heater to sequentially cool the heating body to 600 ℃ from beginning to end at a cooling rate of 30 ℃/h, namely: keeping the temperature of the former heating element after reaching the target temperature of 600 ℃, and cooling the latter heating element until the last heating element is cooled, and when the temperature of the last heating element reaches 600 ℃, completing the whole solidification process, and keeping the temperature of 600 ℃ for 1h;
s5, controlling the heater to enable all the heating bodies to start to cool to room temperature at the same cooling rate of 60 ℃/h, stopping ventilation and heating, and taking out the quartz boat and the gallium telluride in the quartz boat after all mixed gas is removed. The obtained gallium telluride has the purity of 6N and has no defects of air holes, cracks and the like through analysis after head and tail removal.
Comparative example 2
This comparative example is substantially the same as example 4 except for the points S4 and S5.
In the comparative example, S4/S5 is combined into one step, and specifically comprises the following steps: controlling the heater to enable all the heating bodies to start to cool to room temperature at the same cooling rate of 60 ℃/h, stopping ventilation and heating, and taking out the quartz boat and gallium telluride in the quartz boat after all mixed gas is removed. The obtained gallium telluride has obvious cracking and fine cracks. After the head and the tail are removed, the product has more impurities and the purity of 5N.
Comparative example 3
This comparative example is substantially the same as example 4 except for the difference in S2.
The method comprises the following specific steps: and (2) placing the quartz boat in the middle section of the quartz tube in the step (S1), placing the quartz tube in a heater, introducing 5N nitrogen into the quartz tube to replace air in the quartz tube, keeping for 20min, and introducing 5N hydrogen into the quartz tube, wherein the concentration of the hydrogen is controlled to be 10%.
The purity of the product of the gallium telluride finally obtained by the comparative example is 5.5N after head and tail removal, wherein the content of As and Pb elements is higher, and the product has no defects such As air holes, cracks and the like.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A preparation method of high-purity gallium telluride is characterized by comprising the following steps:
s1, mixing tellurium and gallium according to a specified molar ratio, wherein the tellurium is excessive relative to the gallium, and filling the mixed material into a crucible boat;
s2, placing the crucible boat in the quartz tube in the step S1, placing the quartz tube in a heater, exhausting air in the quartz tube, and keeping the atmosphere of nitrogen and hydrogen in the quartz tube;
s3, controlling a heater to enable the whole quartz tube to be heated to 850 to 1000 ℃ at a first heating rate, and keeping the temperature for a period of time to enable tellurium and gallium to react;
s4, controlling a heater, sequentially dividing the quartz tube into a plurality of small sections from one end of the quartz tube to the other end of the quartz tube, controlling the heater, and sequentially cooling each section of the quartz tube to the target temperature of 550-620 ℃ at a first cooling rate, wherein the specific steps are as follows: the temperature of the first section is kept constant after reaching the target temperature, the temperature of the second section is kept constant until reaching the target temperature, and the temperature of the last section is kept constant for 1 to 2h after the temperature of the first section is kept constant;
s5, controlling the heater to enable the whole quartz tube to be cooled to the room temperature at a second cooling rate, stopping introducing nitrogen and hydrogen, stopping heating, and taking out the crucible boat in the quartz tube to obtain high-purity gallium telluride;
wherein in the step S1, the tellurium is 7N tellurium, and the gallium is 7N gallium; the specified molar ratio of tellurium to gallium is 1.002 to 1.005:1; in the step S3, the first heating rate is 200 to 500 ℃/h; in the step S4, the first cooling rate is 30 to 50 ℃/h; in the step S5, the second cooling rate is 60-80 ℃/h.
2. The method for preparing high-purity gallium telluride according to claim 1, wherein in step S2, a mixed gas of hydrogen and nitrogen with a hydrogen concentration of 20 to 30% is kept as a shielding gas.
3. The method of producing high purity gallium telluride as defined in claim 1 wherein the production apparatus for high purity gallium telluride is a quartz tube, a crucible boat placed in the quartz tube, and a heater provided around the wall of the quartz tube.
4. The method of claim 3, wherein the heater comprises a plurality of independently controlled heating elements, each heating element being sequentially disposed around the wall of the quartz tube at a distance.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120090656A1 (en) * | 2010-10-19 | 2012-04-19 | California Institute Of Technology | Self-tuning of carrier concentration for high thermoelectric performance |
| CN106953231A (en) * | 2017-05-02 | 2017-07-14 | 中山大学 | The method that one kind realizes telluride gallium (GaTe) two-dimensional material exciton Laser emission |
| CN111019631A (en) * | 2018-10-09 | 2020-04-17 | Tcl集团股份有限公司 | Preparation method of core-shell structure nanocrystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120090656A1 (en) * | 2010-10-19 | 2012-04-19 | California Institute Of Technology | Self-tuning of carrier concentration for high thermoelectric performance |
| CN106953231A (en) * | 2017-05-02 | 2017-07-14 | 中山大学 | The method that one kind realizes telluride gallium (GaTe) two-dimensional material exciton Laser emission |
| CN111019631A (en) * | 2018-10-09 | 2020-04-17 | Tcl集团股份有限公司 | Preparation method of core-shell structure nanocrystal |
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