CN117265655A - Method and device for synthesizing gallium selenide in large scale - Google Patents
Method and device for synthesizing gallium selenide in large scale Download PDFInfo
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- CN117265655A CN117265655A CN202311250264.8A CN202311250264A CN117265655A CN 117265655 A CN117265655 A CN 117265655A CN 202311250264 A CN202311250264 A CN 202311250264A CN 117265655 A CN117265655 A CN 117265655A
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- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 59
- 229910052711 selenium Inorganic materials 0.000 claims description 46
- 239000011669 selenium Substances 0.000 claims description 46
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 42
- 239000010453 quartz Substances 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 29
- 229910052733 gallium Inorganic materials 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 5
- 238000009489 vacuum treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 7
- 238000003466 welding Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000013094 purity test Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
- C30B28/06—Production of homogeneous polycrystalline material with defined structure from liquids by normal freezing or freezing under temperature gradient
-
- 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
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
Abstract
The invention discloses a method and a device for synthesizing gallium selenide in a large scale, and belongs to the technical field of material synthesis. According to the method, through the arrangement of the specific device structure and the specific processing technology, the VGF method can be used for mass production of gallium selenide polycrystal, and the production process is high in production efficiency and good in safety.
Description
Technical Field
The invention relates to the technical field of material synthesis, in particular to a method and a device for synthesizing gallium selenide polycrystal in large scale.
Background
Gallium selenide (GaSe) is a high-performance infrared optical material, and is generally classified into gallium selenide single crystal and gallium selenide polycrystal, wherein the method for synthesizing gallium selenide polycrystal is generally a single Wen Oufa and double temperature zone method, and single Wen Oufa means that only one constant temperature processing area is arranged in the synthesis process, and the method is simpler to operate, but because selenium has higher vapor pressure at high temperature, the selenium can reach 14atm at 960 ℃, and therefore, the situation of cracking of a furnace tube in the synthesis process is very easy to occur. In contrast, the dual-temperature region rule is that a high-temperature region and a low-temperature region are arranged in a quartz furnace tube, a selenium raw material is placed in the low-temperature region, and selenium steam is transferred to contact gallium for reaction to generate gallium selenide through gas phase transmission, however, the efficiency of producing gallium selenide polycrystal is very low, and meanwhile, the temperature of the whole furnace tube gradually rises along with accumulation and heat conduction of selenium steam, and the pressure in the furnace tube still continuously increases. At present, some researchers try to combine two methods, for example, a single Wen Oushui open hearth furnace is adopted in the prior art, the furnace temperature is set to be the melting point of gallium selenide, one end of a double-temperature-zone synthetic quartz tube, where gallium is placed, is inserted into a furnace body of the single-temperature-zone furnace, one end of the double-temperature-zone synthetic quartz tube, where selenium is placed, is exposed out of the furnace body, and the quartz tube is gradually pushed into the single-temperature-zone synthetic furnace under the condition that the volatilization rate and the condensation rate of the selenium are consistent.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide a method and a device for synthesizing gallium selenide in a large scale, and through the arrangement of a specific structure and a specific processing technology, gallium selenide polycrystal can be produced in a large scale by adopting a VGF method, and the production process has high production efficiency and good safety.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the device for synthesizing the gallium selenide polycrystal in batches comprises a first closed cavity and a second closed cavity from bottom to top along the vertical direction, wherein a first crucible is arranged in the first cavity, a second crucible is arranged in the second cavity, a quartz plug for isolating the two cavities is arranged between the first cavity and the second cavity, and a guide pipe for communicating the two cavities is arranged on the quartz plug.
Preferably, the chamber walls of the first chamber and the second chamber are quartz.
Preferably, the guide pipes are quartz pipes in the vertical direction, and the number of the guide pipes is more than or equal to 2.
Another object of the present invention is to provide a method for synthesizing gallium selenide polycrystalline in large quantities, comprising the steps of:
(1) Placing elemental selenium in a first crucible of the device, and placing elemental gallium in a second crucible;
(2) Placing the device on a heating furnace for preheating, vacuumizing and sealing treatment;
(3) Heating a first chamber of the device to 250-400 ℃ at a heating rate of 10-20 ℃/min, simultaneously heating a second chamber of the device to 950-1005 ℃ at a heating rate of 4-6 ℃/min, and then preserving heat for 1.5-2.5 h;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced at a temperature difference of 5-10 ℃/cm, and then the temperature is increased at a rate of 0.5-2 ℃/min until the upper part of the first chamber reaches 650-750 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 8-12 ℃ higher than the second chamber and is kept for 2-5 hours;
(6) Cooling to 700-800 ℃ in a gradient way until the temperature of the second chamber of the device is reduced, and cooling to obtain the gallium selenide polycrystal.
In the prior art, the VGF method is mostly used for preparing gallium selenide single crystals, namely, gallium selenide polycrystal is put into a quartz tube to serve as a raw material, a vertical heating program is adopted to produce single crystal products at a seed crystal, the VGF method is not used for producing gallium selenide polycrystal, the single-temperature-zone method is mainly implemented by a vertical device in the production process of gallium selenide polycrystal, the double-temperature-zone method is high in danger, and is theoretically suitable for VGF furnace tubes, but in the vertically placed furnace tubes, the efficiency of selenium vapor conduction and gallium simple substance contact reaction to produce gallium selenide is lower, and meanwhile, the situation of rapid local aggregation of pressure and heat is easier to occur. In the technical scheme of the invention, the inventor develops a novel gallium selenide polycrystal production device which is similar to a common quartz tube device, but two chambers for placing selenium simple substances and gallium simple substances are isolated by a quartz plug, and meanwhile, a plurality of communicated guide tubes are arranged; on the other hand, when the device is used for heating, selenium and gallium simple substances are heated to different temperatures at specific different heating rates in advance to form temperature intervals, then the vertical temperature gradient setting is carried out on the chamber where the selenium is located, the temperature is increased to the boiling point of the selenium so that the selenium steam is fully converted, and finally the temperature of the chamber where the gallium is located is matched. Under the program setting, the evaporation and transfer rates of selenium and the synthesis rate of gallium selenide polycrystal are effectively controlled, so that the raw material is converted into gallium selenide polycrystal products with high efficiency and high conversion speed, and the production of mass products can be realized.
Through the verification of the inventor, if the conventional VGF quartz tube is adopted for heating synthesis or the heating program which is not limited by the invention is adopted for synthesis, the gallium selenide polycrystalline product cannot be efficiently synthesized, and even the risks of tube cracking and tube explosion can occur.
Preferably, in the step (1), the molar ratio of elemental selenium to elemental gallium is (1.002-1.005): 1.
more preferably, the elemental selenium is selenium particles, and the average particle size is 2-4 mm.
Preferably, in the step (2), the temperature of the preheating treatment is 200 to 350 ℃.
Preferably, in the step (2), the degree of vacuum in the apparatus after the vacuuming treatment is 0.8 to 1.2X10 -4 Pa。
Preferably, in the step (2), the sealing treatment is performed by using a hydrogen and oxygen seal.
Preferably, in the step (6), the specific way of gradient cooling is as follows: the gradient temperature is set by the temperature difference of 1-10K/cm from bottom to top, and then the temperature of the device is reduced at the speed of 0.1-2 ℃/min.
The device is cooled in a gradient cooling mode, so that raw materials in the device can react completely, and meanwhile, overlarge pressure change amplitude of the device caused by too fast local cooling can be avoided, and the service life of the device is prolonged.
The invention has the beneficial effects that the invention provides the method and the device for synthesizing the gallium selenide in large quantities, the gallium selenide polycrystal can be produced in large quantities by adopting the VGF method through the arrangement of the specific structure and the specific processing technology, and the production process has high production efficiency and good safety.
Drawings
FIG. 1 is a schematic diagram of a device for synthesizing gallium selenide polycrystal in large quantities.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
Example 1
According to one embodiment of the method and the device for synthesizing the gallium selenide in large quantities, as shown in fig. 1, the device comprises a quartz material pipe from bottom to top in a vertical direction, wherein the quartz material pipe comprises a first closed cavity and a second closed cavity, and the upper part of the second cavity is closed by a quartz pipe cap; the first PBN crucible is arranged in the first chamber, the second PBN crucible is arranged in the second chamber, a quartz middle ring plug isolating the two chambers is arranged between the first chamber and the second chamber, and a quartz air duct communicated with the two chambers is arranged on the quartz middle ring plug.
The method for synthesizing gallium selenide polycrystal in large batch comprises the following steps:
(1) Selenium simple substance particles with the average diameter of 3mm are placed in a first PBN crucible of the device, and gallium simple substance strips are placed in a second PBN crucible; the molar ratio of the selenium simple substance to the gallium simple substance is 1.003:1 (total 5 kg); the simple selenium is selenium particles, and the average particle size is 3mm;
(2) Heating the device to 300 deg.C in a heating furnace, preheating, and vacuumizing to 1×10 -4 After Pa, welding the tube by using hydrogen and oxygen so that the tube cap and the quartz middle ring plug are completely connected with the quartz tube;
(3) Heating a first chamber of the device to 300 ℃ at a heating rate set to 15 ℃/min, simultaneously heating a second chamber of the device to 1000 ℃ at a heating rate set to 5 ℃/min, and then preserving heat for 2 hours;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced by a temperature difference of 8 ℃/cm, a temperature gradient is formed, and then the temperature is increased at a rate of 1 ℃/min until the upper part of the first chamber reaches 680 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 10 ℃ higher than the second chamber and is kept warm for 3 hours;
(6) Cooling the mixture to the temperature of 750 ℃ in a gradient way to obtain gallium selenide polycrystal;
the specific mode of gradient cooling is as follows: the apparatus was set to a gradient temperature at a temperature difference of 5K/cm from bottom to top, and then cooled at a rate of 1℃per minute.
Example 2
In one embodiment of the method and apparatus for synthesizing gallium selenide in large quantities of the present invention, the apparatus is the same as in embodiment 1.
The method for synthesizing gallium selenide polycrystal in large batch comprises the following steps:
(1) Selenium simple substance particles with the average diameter of 3mm are placed in a first PBN crucible of the device, and gallium simple substance strips are placed in a second PBN crucible; the molar ratio of the selenium simple substance to the gallium simple substance is 1.003:1 (total 5 kg); the simple selenium is selenium particles, and the average particle size is 3mm;
(2) Heating the device to 200deg.C in a heating furnace, preheating, and vacuumizing to vacuum degree of 1×10 -4 After Pa, welding the tube by using hydrogen and oxygen so that the tube cap and the quartz middle ring plug are completely connected with the quartz tube;
(3) Heating a first chamber of the device to 250 ℃ at a heating rate of 10 ℃/min, simultaneously heating a second chamber of the device to 1000 ℃ at a heating rate of 5 ℃/min, and then preserving heat for 2 hours;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced by a temperature difference of 8 ℃/cm, a temperature gradient is formed, and then the temperature is increased at a rate of 0.5 ℃/min until the upper part of the first chamber reaches 670 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 10 ℃ higher than the second chamber and is kept warm for 3 hours;
(6) Cooling the mixture to the temperature of 750 ℃ in a gradient way to obtain gallium selenide polycrystal;
the specific mode of gradient cooling is as follows: the apparatus was set to a gradient temperature at a temperature difference of 5K/cm from bottom to top, and then cooled at a rate of 1℃per minute.
Example 3
In one embodiment of the method and apparatus for synthesizing gallium selenide in large quantities of the present invention, the apparatus is the same as in embodiment 1.
The method for synthesizing gallium selenide polycrystal in large batch comprises the following steps:
(1) Selenium simple substance particles with the average diameter of 3mm are placed in a first PBN crucible of the device, and gallium simple substance strips are placed in a second PBN crucible; the molar ratio of the selenium simple substance to the gallium simple substance is 1.003:1 (total 5 kg); the simple selenium is selenium particles, and the average particle size is 3mm;
(2) Heating the device to 400 deg.C in a heating furnace, preheating, and vacuumizing to 1×10 -4 After Pa, welding the tube by using hydrogen and oxygen so that the tube cap and the quartz middle ring plug are completely connected with the quartz tube;
(3) Heating a first chamber of the device to 400 ℃ at a set heating rate of 5 ℃/min, simultaneously heating a second chamber of the device to 950 ℃ at a set heating rate of 5 ℃/min, and then preserving heat for 2 hours;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced by a temperature difference of 8 ℃/cm, a temperature gradient is formed, and then the temperature is increased at a rate of 2 ℃/min until the upper part of the first chamber reaches 700 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 10 ℃ higher than the second chamber and is kept warm for 3 hours;
(6) Cooling the mixture to the temperature of 750 ℃ in a gradient way to obtain gallium selenide polycrystal;
the specific mode of gradient cooling is as follows: the apparatus was set to a gradient temperature at a temperature difference of 5K/cm from bottom to top, and then cooled at a rate of 1℃per minute.
Comparative example 1
The method and the device for synthesizing gallium selenide in large quantities are different from the embodiment 1 only in that the device is a quartz material pipe and comprises a first closed cavity and a second closed cavity from bottom to top along the vertical direction, wherein the upper part of the second cavity is closed by a quartz pipe cap; the first cavity is internally provided with a first PBN crucible, the second cavity is internally provided with a second PBN crucible, and the first cavity and the second cavity are directly communicated.
Comparative example 2
The method and apparatus for synthesizing gallium selenide in large quantities differ from example 1 only in that the method for synthesizing gallium selenide polycrystal in large quantities comprises the following steps:
(1) Selenium simple substance particles with the average diameter of 3mm are placed in a first PBN crucible of the device, and gallium simple substance strips are placed in a second PBN crucible; the molar ratio of the selenium simple substance to the gallium simple substance is 1.003:1 (total 5 kg); the simple selenium is selenium particles, and the average particle size is 3mm;
(2) Heating the device to 300 deg.C in a heating furnace, preheating, and vacuumizing to 1×10 -4 After Pa, welding the tube by using hydrogen and oxygen so that the tube cap and the quartz middle ring plug are completely connected with the quartz tube;
(3) Heating a first chamber of the device to 300 ℃ at a heating rate set to 15 ℃/min, simultaneously heating a second chamber of the device to 1000 ℃ at a heating rate set to 5 ℃/min, and then preserving heat for 2 hours;
(4) Maintaining the second chamber of the device at a constant temperature, and heating the first chamber at a rate of 1 ℃/min until the upper part of the first chamber reaches 680 ℃ under the condition that no temperature gradient is set;
(5) After the temperature is stable, the first chamber of the device is heated to 10 ℃ higher than the second chamber and is kept warm for 3 hours;
(6) Cooling the mixture to the temperature of 750 ℃ in a gradient way to obtain gallium selenide polycrystal;
the specific mode of gradient cooling is as follows: the apparatus was set to a gradient temperature at a temperature difference of 5K/cm from bottom to top, and then cooled at a rate of 1℃per minute.
Comparative example 3
The method and apparatus for synthesizing gallium selenide in large quantities differ from example 1 only in that the method for synthesizing gallium selenide polycrystal in large quantities comprises the following steps:
(1) Selenium simple substance particles with the average diameter of 3mm are placed in a first PBN crucible of the device, and gallium simple substance strips are placed in a second PBN crucible; the molar ratio of the selenium simple substance to the gallium simple substance is 1.003:1 (total 5 kg); the simple selenium is selenium particles, and the average particle size is 3mm;
(2) Heating the device to 300 deg.C in a heating furnace, preheating, and vacuumizing to 1×10 -4 After Pa, welding the tube by using hydrogen and oxygen so that the tube cap and the quartz middle ring plug are completely connected with the quartz tube;
(3) Heating a first chamber of the device to 300 ℃ at a set heating rate of 15 ℃/min, simultaneously heating a second chamber of the device to 1000 ℃ at a set heating rate of 15 ℃/min, and then preserving heat for 2 hours;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced by a temperature difference of 8 ℃/cm, a temperature gradient is formed, and then the temperature is increased at a rate of 1 ℃/min until the upper part of the first chamber reaches 680 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 10 ℃ higher than the second chamber and is kept warm for 3 hours;
(6) Cooling the mixture to the temperature of 750 ℃ in a gradient way to obtain gallium selenide polycrystal;
the specific mode of gradient cooling is as follows: the apparatus was set to a gradient temperature at a temperature difference of 5K/cm from bottom to top, and then cooled at a rate of 1℃per minute.
Comparative example 4
The method and apparatus for synthesizing gallium selenide in large quantities differ from example 1 only in that the method for synthesizing gallium selenide polycrystal in large quantities comprises the following steps:
(1) Selenium simple substance particles with the average diameter of 3mm are placed in a first PBN crucible of the device, and gallium simple substance strips are placed in a second PBN crucible; the molar ratio of the selenium simple substance to the gallium simple substance is 1.003:1 (total 5 kg); the simple selenium is selenium particles, and the average particle size is 3mm;
(2) Heating the device to 300 deg.C in a heating furnace, preheating, and vacuumizing to 1×10 -4 After Pa, welding the tube by using hydrogen and oxygen so that the tube cap and the quartz middle ring plug are completely connected with the quartz tube;
(3) Heating a first chamber of the device to 300 ℃ at a heating rate set to 15 ℃/min, simultaneously heating a second chamber of the device to 1000 ℃ at a heating rate set to 5 ℃/min, and then preserving heat for 2 hours;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced by a temperature difference of 15 ℃/cm, a temperature gradient is formed, and then the temperature is increased at a rate of 1 ℃/min until the upper part of the first chamber reaches 680 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 10 ℃ higher than the second chamber and is kept warm for 3 hours;
(6) Cooling the mixture to the temperature of 750 ℃ in a gradient way to obtain gallium selenide polycrystal;
the specific mode of gradient cooling is as follows: the apparatus was set to a gradient temperature at a temperature difference of 5K/cm from bottom to top, and then cooled at a rate of 1℃per minute.
Comparative example 5
The method and apparatus for synthesizing gallium selenide in large quantities differ from example 1 only in that the method for synthesizing gallium selenide polycrystal in large quantities comprises the following steps:
(1) Selenium simple substance particles with the average diameter of 3mm are placed in a first PBN crucible of the device, and gallium simple substance strips are placed in a second PBN crucible; the molar ratio of the selenium simple substance to the gallium simple substance is 1.003:1 (total 5 kg); the simple selenium is selenium particles, and the average particle size is 3mm;
(2) Heating the device to 300 deg.C in a heating furnace, preheating, and vacuumizing to 1×10 -4 After Pa, welding the tube by using hydrogen and oxygen so that the tube cap and the quartz middle ring plug are completely connected with the quartz tube;
(3) Heating a first chamber of the device to 300 ℃ at a heating rate set to 15 ℃/min, simultaneously heating a second chamber of the device to 1000 ℃ at a heating rate set to 5 ℃/min, and then preserving heat for 2 hours;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced by a temperature difference of 8 ℃/cm, a temperature gradient is formed, and then the temperature is increased at a rate of 5 ℃/min until the upper part of the first chamber reaches 680 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 10 ℃ higher than the second chamber and is kept warm for 3 hours;
(6) Cooling the mixture to the temperature of 750 ℃ in a gradient way to obtain gallium selenide polycrystal;
the specific mode of gradient cooling is as follows: the apparatus was set to a gradient temperature at a temperature difference of 5K/cm from bottom to top, and then cooled at a rate of 1℃per minute.
Effect example 1
To explore the preference of the method and the device of the invention, the gallium selenide polycrystal prepared in each example and comparative example is subjected to purity test and yield statistics, wherein the purity test method is a GDMS method, and the calculation formula of the yield statistics is as follows: yield (%) = weight remaining after treatment of polycrystalline rod/total weight of material x 100% (gallium-rich, or other defects may cut off the resulting polycrystalline rod). If the problem occurs in the production process of the device, the device is also recorded, the pressure monitoring is arranged in the device, and if the dangerous conditions such as the pressure is too high, namely, a frying furnace and the like occur, the operation is directly stopped, and the yield is not counted any more.
The test results are shown in Table 1.
TABLE 1
| Product(s) | Purity (impurity element content) | Yield rate | Product case |
| Example 1 | <10ppm | 99％ | |
| Example 2 | <10ppm | 98％ | |
| Example 3 | <10ppm | 96％ | |
| Comparative example 1 | <10ppm | 0 | Risk of frying |
| Comparative example 2 | <10ppm | 80％ | The product is rich in gallium |
| Comparative example 3 | <10ppm | 85％ | The product is rich in gallium |
| Comparative example 4 | <10ppm | 83％ | The product is rich in gallium |
| Comparative example 5 | <10ppm | 96％ |
As can be seen from Table 1, the method for synthesizing gallium selenide polycrystal in large quantities can synthesize products with the yield of more than 96% in a single batch under the condition that the raw material amount is up to 5kg, and the impurity element content of the products is less than 10ppm. In contrast, if the conventional furnace tube of comparative example 1 is used for vertical heating to prepare gallium selenide polycrystalline products, the risk of a frying furnace is extremely easily generated due to the characteristic of selenium vapor, and products cannot be synthesized in large quantities, but even if the specific processing apparatus of the present invention is used, if gradient temperature control programming is not performed or the program is improperly set, as shown in comparative example 2 and comparative examples 3 to 4, gallium enrichment phenomenon may occur in the products, and the yield becomes low. In comparative example 5, however, the gradient heating rate in step (4) was too fast, and the productivity was reduced by 3% compared with the case of example 1, which means that the parameters in each temperature-controlled heating procedure should be studied to ensure good uniformity and high productivity of the product.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The device for synthesizing the gallium selenide polycrystal in large quantities is characterized by comprising a first closed cavity and a second closed cavity from bottom to top in the vertical direction, wherein a first crucible is arranged in the first cavity, a second crucible is arranged in the second cavity, a quartz plug isolating the two cavities is arranged between the first cavity and the second cavity, and a guide pipe communicated with the two cavities is arranged on the quartz plug.
2. The apparatus for mass synthesis of gallium selenide polycrystalline according to claim 1, wherein the walls of the first chamber and the second chamber are quartz.
3. The device for synthesizing gallium selenide polycrystal in large batch is characterized in that the guide pipes are quartz pipes along the vertical direction, and the number of the guide pipes is more than or equal to 2.
4. The method for synthesizing the gallium selenide polycrystal in large batch is characterized by comprising the following steps:
(1) Placing elemental selenium in a first crucible of the apparatus of any one of claims 1-3, and elemental gallium in a second crucible;
(2) Placing the device on a heating furnace for preheating, vacuumizing and sealing treatment;
(3) Heating a first chamber of the device to 250-400 ℃ at a heating rate of 10-20 ℃/min, simultaneously heating a second chamber of the device to 950-1005 ℃ at a heating rate of 4-6 ℃/min, and then preserving heat for 1.5-2.5 h;
(4) The second chamber of the device keeps constant temperature, vertical gradient temperature is set for the first chamber, the temperature from top to bottom is reduced at a temperature difference of 5-10 ℃/cm, and then the temperature is increased at a rate of 0.5-2 ℃/min until the upper part of the first chamber reaches 650-750 ℃;
(5) After the temperature is stable, the first chamber of the device is heated to 8-12 ℃ higher than the second chamber and is kept for 2-5 hours;
(6) Cooling to 700-800 ℃ in a gradient way until the temperature of the second chamber of the device is reduced, and cooling to obtain the gallium selenide polycrystal.
5. The method for mass synthesis of gallium selenide polycrystalline according to claim 4, wherein in the step (1), the molar ratio of elemental selenium to elemental gallium is (1.002 to 1.005): 1, a step of; the simple selenium is selenium particles, and the average particle size is 2-4 mm.
6. The method for mass synthesis of gallium selenide polycrystalline according to claim 4, wherein the temperature of the preheating treatment in the step (2) is 200 to 350 ℃.
7. The method for mass synthesis of gallium selenide polycrystalline according to claim 4, wherein in the step (2), the degree of vacuum in the apparatus after the vacuum treatment is 0.8 to 1.2x10 -4 Pa。
8. The method for mass synthesis of gallium selenide polycrystalline according to claim 4, wherein the sealing treatment is performed by hydrogen and oxygen sealing in step (2).
9. The method for synthesizing gallium selenide polycrystal in large quantities according to claim 4, wherein in the step (6), the specific way of gradient cooling is as follows: the gradient temperature is set by the temperature difference of 1-10K/cm from bottom to top, and then the temperature of the device is reduced at the speed of 0.1-2 ℃/min.
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