CN111424316A - Phosphorus germanium zinc polycrystal pressurizing synthesis device and synthesis method - Google Patents
Phosphorus germanium zinc polycrystal pressurizing synthesis device and synthesis method Download PDFInfo
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- CN111424316A CN111424316A CN202010487797.8A CN202010487797A CN111424316A CN 111424316 A CN111424316 A CN 111424316A CN 202010487797 A CN202010487797 A CN 202010487797A CN 111424316 A CN111424316 A CN 111424316A
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- 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
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
Abstract
The invention relates to a phosphorus germanium zinc polycrystal pressurizing synthesis device and a synthesis method, wherein the device comprises: the ampoule furnace comprises a main furnace body and an ampoule, wherein the main furnace body comprises an inner furnace body, an outer layer heating device, an air pressure control device, a cooling device and a sealing flange; the inner furnace body is divided into nine temperature areas along the axial direction, the cooling device and the outer layer heating device are wrapped around the periphery of the inner furnace body and are arranged at corresponding positions of the temperature areas of the inner furnace body, and the air pressure control devices are arranged at two ends of the inner furnace body; the ampoule comprises a protective container, a synthesis container and a crucible, and is placed in the inner furnace body by taking the limiting spacer as a support; the device is used for synthesizing the phosphorus-germanium-zinc polycrystal, so that the pressure difference between the inside and the outside of the quartz ampoule in the synthesis process is reduced, the explosion danger caused by the out-of-control saturated vapor pressure of phosphorus is eliminated, and the large-batch synthesis can be carried out at a single time; the ampoule protection container can limit the position of the synthesis container, and the limiting spacer can also play a role of a support frame and can be freely adjusted according to different ampoule sizes and temperature zone positions.
Description
Technical Field
The invention relates to preparation of a nonlinear optical material phosphorus germanium zinc crystal, in particular to a phosphorus germanium zinc polycrystal pressurizing synthesis device and a synthesis method.
Background
Chalcopyrite semiconductor materials are recognized to have high far infrared region transmittance and nonlinear optical coefficient in the late 60 s of the 20 th century, and the application of frequency conversion in infrared bands is also regarded by people, so that phosphorus, germanium and zinc are represented by excellent comprehensive properties and are attracted by wide attention, and a plurality of scholars study crystal properties and synthesis processes of the phosphorus, germanium and zinc.
The saturated vapor pressure of phosphorus is exponentially increased along with the temperature rise, the saturated vapor pressure is 4.8atm at 480 ℃, the saturated vapor pressure reaches 7.5atm when the temperature reaches 500 ℃, and the saturated vapor pressure is increased to 11atm at 520 ℃, namely, after the temperature of a reaction system reaches 500 ℃, the small-amplitude temperature rise can bring large vapor pressure change. The phosphorus, germanium and zinc synthesis reaction is an exothermic reaction, and the temperature of a reaction system is difficult to control finely due to the heat release in the reaction process, so that the saturated vapor pressure of phosphorus simple substances is out of control to a certain extent, and the risk is brought to the crystal synthesis. Especially in the large-scale synthesis process of crystals, the problem of saturated vapor pressure not only affects the synthesis speed, but also easily causes explosion.
Disclosure of Invention
The invention provides a device and a method for synthesizing polycrystalline phosphorus germanium zinc by pressurizing aiming at a gas phase transmission synthesis process of polycrystalline phosphorus germanium zinc, aiming at solving the problems of low synthesis rate, easy explosion and the like in the process of synthesizing a large batch of polycrystalline phosphorus germanium zinc.
The technical scheme of the invention is as follows: a phosphorus germanium zinc polycrystal pressure synthesis device is characterized in that: the ampoule furnace comprises a main furnace body and an ampoule, wherein the main furnace body comprises an inner furnace body, an outer layer heating device, an air pressure control device, a cooling device and a sealing flange; the inner furnace body is of a pressure-resistant metal tubular structure and is horizontally placed, the bearable pressure is not lower than 100atm, two sealing flanges are respectively arranged at two ends of the inner furnace body, the two air pressure control devices are respectively an air pressure control device I and an air pressure control device II, one end of the inner furnace body is connected with the air pressure control device I through a flange, and the other end of the inner furnace body is connected with the air pressure device II through a flange; the ampoule is placed in the internal furnace body by taking the limiting spacer as a support;
divide into nine warm areas along the axial in the inside furnace body, arrange from the one end of connecting the air pressure unit, be in proper order: the device comprises a protective temperature zone I, a reaction auxiliary temperature zone I, a reaction main temperature zone, a reaction auxiliary temperature zone II, a transition temperature zone, a synthesis auxiliary temperature zone I, a synthesis main temperature zone, a synthesis auxiliary temperature zone II and a protective temperature zone II, wherein the reaction auxiliary temperature zone I, the reaction main temperature zone and the reaction auxiliary temperature zone II are integrated together to form a reaction temperature zone, and the synthesis auxiliary temperature zone I, the synthesis main temperature zone and the synthesis auxiliary temperature zone II are integrated together to form a synthesis temperature zone;
the outer-layer heating device comprises eight heating devices and a heat preservation device, the eight heating devices and the heat preservation device are respectively wrapped around the periphery of the inner furnace body and are arranged corresponding to nine temperature zones of the inner furnace body, and the heating devices are a protection temperature zone I heating device, a reaction auxiliary temperature zone I heating device, a reaction main temperature zone heating device, a reaction auxiliary temperature zone II heating device, a transition temperature zone heat preservation device, a synthesis auxiliary temperature zone I heating device, a synthesis main temperature zone heating device, a synthesis auxiliary temperature zone II heating device and a protection temperature zone II heating device in sequence;
the cooling device is provided with three sets, namely a protection temperature zone I cooling device, a protection temperature zone II cooling device and a transition temperature zone cooling device, wherein the transition temperature zone cooling device is attached to an internal furnace body and arranged inside the transition temperature zone heat preservation device and is in linkage control with the heating device and the air pressure control device; the cooling device of the protection temperature area I and the cooling device of the protection temperature area II are respectively arranged at the outer sides of the protection temperature area I and the protection temperature area II and are synchronously controlled;
the ampoule comprises a protective container, a synthesis container, a reaction crucible and a synthesis crucible, wherein the reaction crucible and the synthesis crucible are respectively placed at two ends in the synthesis container, and the synthesis container with two crucibles is placed in the protective container; the protective container is a cylinder with two open ends, a plurality of clamping grooves are formed in the lower sides of the two ends of the cylinder, and limiting spacers are respectively inserted into the clamping grooves at the two ends of the protective container according to the size of the synthetic container; the synthesis container is a cylinder with one end open;
the gas pressure control device uses a gas inert to chemical reaction as an additional control gas, preferably high-purity nitrogen; the gas flows into the gas pressure control device from the gas pressure control device, sequentially passes through a protection temperature area, a reaction auxiliary temperature area I, a reaction main temperature area, a reaction auxiliary temperature area II, a transition temperature area, a synthesis auxiliary temperature area I, a synthesis main temperature area and a synthesis auxiliary temperature area II, and flows out of the protection temperature area II to enter the gas pressure control device.
A synthesis method adopting a phosphorus germanium zinc polycrystal pressurizing synthesis device comprises the following steps:
firstly, weighing raw materials and sealing a synthesis container: corroding and cleaning the synthesis container, the reaction crucible and the synthesis crucible (2-32), corroding and cleaning zinc and germanium, sampling and mixing according to the proportion of 1: 1-1.1: 1, then placing the mixture into the synthesis crucible, weighing phosphorus which is 1.1 times of the molar weight of the zinc, placing the phosphorus into the reaction crucible, placing the reaction crucible and the synthesis crucible at two ends of the synthesis container respectively, carrying out vacuum treatment on the open end of the synthesis container, and then welding and sealing;
step two, loading into a furnace body: putting the sealed synthesis container which is welded well into a protective container, selecting a clamping groove with two ends close to the synthesis container to insert a limiting spacer, putting the protective container inserted with the spacer into an inner furnace body of the synthesis furnace by taking the spacer as a support, putting a reaction crucible at a position corresponding to a main reaction temperature area of the inner furnace body, and putting the synthesis crucible at a position corresponding to a main synthesis temperature area of the inner furnace body;
step three, sealing the furnace body and exchanging air: sealing flanges at two ends of the inner furnace body, opening the air pressure control device, introducing chemical reaction inert gas into the inner furnace body, introducing the inert gas into the inner furnace body from the air pressure control device I, introducing the inert gas into the air pressure control device II through each temperature zone in the furnace body, and driving the original air in the furnace while maintaining the standard atmospheric pressure;
step four, reaction of phosphorus and zinc: starting a cooling device, starting a heating device all the time, heating the reaction main temperature zone I, the reaction auxiliary temperature zone I, the reaction main temperature zone heating device, the reaction auxiliary temperature zone II, the transition temperature zone heat preservation device, the synthesis auxiliary temperature zone I, the synthesis main temperature zone heating device, the synthesis auxiliary temperature zone II and the protection temperature zone II through a protection temperature zone I heating device, a reaction auxiliary temperature zone II, a transition temperature zone heat preservation device, a synthesis auxiliary temperature zone I heating device, a synthesis auxiliary temperature zone II heating device and a protection temperature zone II heating device, respectively heating the reaction auxiliary temperature zone I, the reaction main temperature zone and the reaction auxiliary, meanwhile, when the temperature of the reaction auxiliary temperature area I, the reaction main temperature area and the reaction auxiliary temperature area II is raised to 425 ℃, the air pressure in the furnace is started to be increased, meanwhile, the air pressure control device is adjusted according to the temperature of the reaction temperature zone and the reaction progress, and the temperature of the reaction temperature zone is maintained for more than 10 hours in the state of 400 ℃ and 530 ℃; in the process, the phosphorus simple substance in the reaction crucible is sublimated into phosphorus steam which reacts with zinc steam sublimated from the synthesis crucible and zinc melt to generate zinc phosphide and zinc diphosphide, the reaction of phosphorus and zinc is completed after 10h, the generated phosphorus-zinc compound is attached in the reaction container, and only a small amount of excessive phosphorus simple substance remains in the system;
fifthly, synthesizing a phosphorus-zinc compound and germanium: adjusting a cooling device of the transition temperature zone to slow down the cooling speed, increasing the temperatures of the reaction auxiliary temperature zone I, the reaction main temperature zone and the reaction auxiliary temperature zone II, recovering the cooling speed of the transition temperature zone until the temperature of the transition temperature zone is adjusted to be 100-200 ℃ lower than the temperature of the synthesis temperature zone, and slowly increasing the temperatures of the reaction auxiliary temperature zone I, the reaction main temperature zone and the reaction auxiliary temperature zone until the temperature of the transition temperature zone is 10-30 ℃ higher than the temperature of the synthesis temperature zone; meanwhile, adjusting an air pressure control device according to the temperature of a reaction temperature area and the synthesis progress, and maintaining the temperature until the reaction is finished; in the process, along with the rise of the temperature of the reaction temperature zone, the generated phosphorus-zinc compound is vaporized into steam and flows to the synthesis zone to react with germanium in the synthesis crucible to generate molten phosphorus-germanium-zinc, and along with the continuous generation of phosphorus-germanium-zinc, the phosphorus-zinc compound steam continuously flows to the synthesis crucible until the synthesis is finished;
sixthly, cooling: after the reaction is finished, adjusting a cooling device to increase the cooling speed, simultaneously cooling the temperature of the reaction temperature region and the temperature of the synthesis temperature region to 930-;
seventh step, continuously cooling: continuously cooling to room temperature, adjusting the air pressure control device to reduce the internal air pressure to the standard atmospheric pressure, and closing the pressure control device, the heating device and the cooling device;
eighth, taking out the finished product and cleaning the crucible: taking out the ampoule, destroying the synthesis container, taking out the finished product, and cleaning the reaction crucible and the synthesis crucible for the next use.
The invention has the beneficial effects that: according to the invention, a controllable pressurizing device is used for synthesizing the phosphorus-germanium-zinc polycrystal, so that the internal and external pressure difference of the quartz ampoule in the synthesis process is reduced, and the large-batch synthesis can be carried out at one time; the cooling system of the transition temperature zone is in linkage control with the heating device and the air pressure control device, so that the fine control of the reaction temperature can be realized, the temperature gradient is increased in the reaction stage according to the free adjustment of the reaction stage, the temperature gradient is reduced in the synthesis stage, the heat dissipation requirement of the transition temperature zone can be met, the time required by synthesis can be reduced, and meanwhile, the fine control of the reaction temperature enables a large amount of elemental phosphorus to react with zinc to generate a phosphorus-zinc compound before the temperature of the reaction temperature zone is greatly increased, only a small amount of excessive elemental phosphorus exists in the system, so that the explosion danger caused by the out-of-control; the reaction synthesis ampoule protection container can limit the position of the synthesis container, is convenient for adjusting the temperature zone, can play a role of a support frame by limiting the spacer, can be freely customized and reused, and can be freely adjusted according to different ampoule sizes and temperature zone positions.
Drawings
FIG. 1 is a schematic structural view of the present invention;
fig. 2 is a schematic diagram of the ampoule structure of the present invention.
Detailed Description
As shown in figure 1, the pressure synthesis device for the phosphorus-germanium-zinc polycrystal comprises a main body furnace body 1 and an ampoule 2, wherein the main body furnace body 1 comprises an inner furnace body 1-1, an outer layer heating device 1-2, a pressure control device 1-3, a cooling device 1-4 and a sealing flange 1-5; the inner furnace body 1-1 is a pressure-resistant metal tubular structure and is horizontally placed, the bearable pressure is not lower than 100atm, two sealing flanges 1-5 are respectively arranged at two ends of the inner furnace body 1-1, two sets of air pressure control devices 1-3 are respectively an air pressure control device I (1-31) and an air pressure control device II 1-32, one end of the inner furnace body 1-1 is connected with the air pressure control device I (1-31) through the flanges 1-51, and the other end of the inner furnace body is connected with the air pressure device II 1-32 through the flanges 1-52; the ampoule 2 is placed in the inner furnace body 1-1 by taking the limiting spacer 2-11 as a support;
the interior of the inner furnace body 1-1 is divided into nine temperature zones along the axial direction, and the nine temperature zones are arranged from one end connected with the air pressure device (1-31) in sequence: the synthesis device comprises a protection temperature area I1-17, a reaction auxiliary temperature area I1-12, a reaction main temperature area 1-11, a reaction auxiliary temperature area II 1-13, a transition temperature area 1-19, a synthesis auxiliary temperature area I1-15, a synthesis main temperature area 1-14, a synthesis auxiliary temperature area II 1-16, a protection temperature area II 1-18, a reaction auxiliary temperature area I1-12, a reaction main temperature area 1-11 and a reaction auxiliary temperature area II 1-13 which are integrated together to form a reaction temperature area, and a synthesis auxiliary temperature area I1-15, a synthesis main temperature area 1-14 and a synthesis auxiliary temperature area II 1-16 which are integrated together to form a synthesis temperature area;
the outer heating device 1-2 comprises
Eight heating devices and a heat preservation device are respectively wrapped around the periphery of the internal furnace body 1-1 and are arranged corresponding to nine temperature zones of the internal furnace body 1-1, and sequentially comprise a protection temperature zone I heating device 1-27, a reaction auxiliary temperature zone I heating device I1-22, a reaction main temperature zone heating device 1-21, a reaction auxiliary temperature zone II heating device 1-23, a transition temperature zone heat preservation device 1-29, a synthesis auxiliary temperature zone I heating device 1-25, a synthesis main temperature zone heating device 1-24, a synthesis auxiliary temperature zone II heating device 1-26 and a protection temperature zone II heating device 1-28;
the cooling device 1-4 is provided with three sets, namely a protection temperature zone I cooling device 1-47, a protection temperature zone II cooling device 1-48 and a transition temperature zone cooling device 1-49, wherein the transition temperature zone cooling device 1-49 is attached to the inner furnace body 1-1 and arranged inside the transition temperature zone heat preservation device 1-29, and is in linkage control with the heating device 1-2 and the air pressure control device 1-3; the cooling devices 1-47 of the protection temperature zone I and the cooling devices 1-48 of the protection temperature zone II are respectively arranged at the outer sides of the protection temperature zones I1-17 and the protection temperature zones II 1-18 and are synchronously controlled;
as shown in FIG. 2, the ampoule 2 comprises a protective container 2-1, a synthesis container 2-2, a reaction crucible 2-31 and a synthesis crucible 2-32, the reaction crucible 2-31 and the synthesis crucible 2-32 are respectively placed at both ends in the synthesis container 2-2, and the synthesis container 2-2 with two crucibles is placed in the protective container 2-1; the protective container 2-1 is a cylinder with two open ends, a plurality of clamping grooves 2-10 are arranged on the lower sides of the two ends of the cylinder, and limiting spacers 2-11 are respectively inserted into the clamping grooves 2-10 at the two ends of the protective container 2-1 according to the size of the synthetic container 2-2; the synthesis vessel 2-2 is a cylinder with one end open;
as shown in fig. 1, the gas pressure control apparatus 1-3 uses a chemically reactive inert gas as an additional control gas, preferably high-purity nitrogen gas; the gas flows into the gas pressure control device 1-31, sequentially passes through a protective temperature zone I1-17, a reaction auxiliary temperature zone I1-12, a reaction main temperature zone 1-11, a reaction auxiliary temperature zone II 1-13, a transition temperature zone 1-19, a synthesis auxiliary temperature zone I1-15, a synthesis main temperature zone 1-14 and a synthesis auxiliary temperature zone II 1-16, and flows out of the protective temperature zone II 1-18 to enter the gas pressure control device 1-32.
As shown in FIG. 1, the outer layer heating device 1-2 comprises heating resistance wires 1-201, heat insulation materials 1-202 and thermocouples 1-203; the heating resistance wire 1-201 is arranged around the periphery of the whole inner furnace body 1-1; 1-202 heat insulation materials are tightly wrapped on 1-201 heating resistance wires; the heating device 1-2 corresponding to each temperature zone is correspondingly provided with a thermocouple 1-203 at the top end of the inner furnace body 1-1, and the probe extends to the corresponding temperature zone in the inner furnace body 1-1; at least three sets of heating devices control a reaction temperature area, three sets of heating devices control a synthesis temperature area, and two sets of heating devices control a protection temperature area; in order to form better temperature gradient, the heat preservation device 1-29 of the transition temperature zone is completely composed of heat insulation materials 1-202, the shape is concave, the diameters of two ends are consistent with those of the temperature zones at two sides, and the diameter of the central part is 2/3-1/3 of the diameters of the two end parts.
As shown in FIG. 2, the material of the protective container 2-1 of the ampoule 2 is quartz, magnesia or alumina, preferably quartz, the material of the synthesis container 2-2 is preferably quartz, and the material of the reaction crucible 2-31 and the synthesis crucible 2-32 is graphite or boron nitride, preferably boron nitride; the limiting spacers 2-11 are preferably in the shape of a corner rectangle, and are preferably made of quartz.
A synthesis method adopting a phosphorus germanium zinc polycrystal pressurizing synthesis device comprises the following steps:
firstly, weighing raw materials and sealing a synthesis container: corroding and cleaning the synthesis container 2-2, the reaction crucible 2-31 and the synthesis crucible 2-32, according to the metering ratio of phosphorus, germanium and zinc, weighing 65.4g of zinc and 72.6g of germanium after corroding and cleaning the zinc and the germanium, mixing, putting the mixture into the synthesis crucible 2-32, weighing 62.8g of phosphorus into the reaction crucible 2-31, respectively placing the reaction crucible 2-31 and the synthesis crucible 2-32 at two ends of the synthesis container 2-2, and carrying out vacuum treatment on the open end of the synthesis container 2-2 and then welding and sealing;
step two, loading into a furnace body: putting a sealed synthesis container 2-2 which is welded well into a protective container 2-1, selecting a clamping groove 2-10 with two ends close to the synthesis container 2-2 to insert a limiting spacer 2-11, inserting the protective container 2-1 with the spacer 2-11 to make the synthesis container difficult to slide, putting the spacer 2-11 into a furnace body 1-1 in a synthesis furnace by taking the spacer 2-11 as a bracket, putting a reaction crucible 2-31 in a main reaction temperature area 1-11, and putting a synthesis crucible 2-32 in the main synthesis temperature area 1-14;
step three, sealing the furnace body and exchanging air: sealing flanges 1-5 at two ends of an inner furnace body 1-1, starting an air pressure control device 1-3, introducing high-purity nitrogen into the furnace body 1-1, introducing the high-purity nitrogen into the inner furnace body 1-1 from the air pressure control device I1-31, and introducing the high-purity nitrogen into an air pressure control device II 1-32 through each temperature zone in the furnace body, and driving the original air in the furnace while maintaining the standard atmospheric pressure;
step four, reaction of phosphorus and zinc: opening a cooling device 1-47 of a protection temperature zone I, a cooling device 1-48 of a protection temperature zone II and a cooling device 1-49 of a transition temperature zone, opening a heating device 1-2, heating devices 1-27 of the protection temperature zone I, heating devices I1-22 of a reaction auxiliary temperature zone, heating devices 1-21 of a reaction main temperature zone, heating devices 1-23 of a reaction auxiliary temperature zone II, heat preservation devices 1-29 of the transition temperature zone, heating devices 1-25 of the synthesis auxiliary temperature zone I, heating devices 1-24 of the synthesis main temperature zone, heating devices 1-26 of the synthesis auxiliary temperature zone II and heating devices 1-28 of the protection temperature zone II, heating the reaction auxiliary temperature zone I1-12, the reaction main temperature zone 1-11 and the reaction auxiliary temperature zone II 1-13 to 530 ℃, heating devices 1-15 of the synthesis auxiliary temperature zone I, Heating the synthesis main temperature zone 1-14 and the synthesis auxiliary temperature zone II 1-16 to 1060 ℃, and simultaneously starting to increase the pressure in the furnace to 14atm when the temperature of the reaction auxiliary temperature zone I1-12, the reaction main temperature zone 1-11 and the reaction auxiliary temperature zone II 1-13 is increased to 425 ℃, and maintaining for more than 10 hours; in the process, the phosphorus in the reaction crucible 2-31 is sublimated into phosphorus vapor, the phosphorus vapor reacts with zinc vapor sublimated from the synthesis crucible 2-32 and zinc melt to generate zinc diphosphide (Zn 3P 2) and zinc diphosphide (ZnP 2), the reaction of phosphorus and zinc is completed after 10h, the generated phosphorus-zinc compound is attached in the reaction vessel 2-2, and only a small amount of excessive phosphorus is left in the system;
fifthly, synthesizing a phosphorus-zinc compound and germanium: adjusting a cooling device 1-49 of the transition temperature zone 1-19 to slow down the cooling speed, recovering the cooling speed of the transition temperature zone 1-19 when the temperature of the reaction auxiliary temperature zone I1-12, the reaction main temperature zone 1-11 and the reaction auxiliary temperature zone II 1-13 is raised to 950 ℃, continuing to slowly raise the temperature of the reaction auxiliary temperature zone I1-12, the reaction main temperature zone 1-11 and the reaction auxiliary temperature zone II 1-13 to 1070 ℃, and simultaneously adjusting the air pressure in the furnace to 60atm by an air pressure control device until the reaction is finished; in the process, along with the rise of the temperature of the reaction temperature zone, the generated phosphorus-zinc compound is vaporized into steam and flows to the synthesis zone to react with germanium in the synthesis crucibles 2-32 to generate molten phosphorus-germanium-zinc, and along with the continuous generation of phosphorus-germanium-zinc, the phosphorus-zinc compound steam continuously flows to the synthesis crucibles 2-32 until the synthesis is finished;
sixthly, cooling: after the reaction is finished, adjusting a cooling device 1-4 to increase the cooling speed, simultaneously cooling to 930-, forming phosphorus germanium zinc polycrystal by the phosphorus germanium zinc eutectic;
seventh step, continuously cooling: continuously cooling to room temperature, adjusting the air pressure control device 1-3 to reduce the internal air pressure to the standard atmospheric pressure, and closing the pressure control device 1-3, the heating device 1-2 and the cooling device 1-4;
eighth, taking out the finished product and cleaning the crucible: taking out the ampoule 2, destroying the synthesis container 2-1, taking out about 200g of finished product, and cleaning the reaction crucible 2-31 and the synthesis crucible 2-32 for the next use.
The highest temperature of the synthesis process is not higher than 1100 ℃.
Claims (5)
1. A phosphorus germanium zinc polycrystal pressure synthesis device is characterized in that: comprises a main body furnace body (1) and an ampoule (2), wherein the main body furnace
The body (1) comprises an inner furnace body (1-1), an outer layer heating device (1-2), an air pressure control device (1-3), a cooling device (1-4) and a sealing flange (1-5); the internal furnace body (1-1) is of a pressure-resistant metal tubular structure, is horizontally placed and can bear pressure not lower than 100atm, two sealing flanges (1-5) are respectively arranged at two ends of the internal furnace body (1-1), two sets of air pressure control devices (1-3) are respectively an air pressure control device I (1-31) and an air pressure control device II (1-32), one end of the internal furnace body (1-1) is connected with the air pressure control device I (1-31) through the flanges (1-51), and the other end of the internal furnace body is connected with the air pressure device II (1-32) through the flanges (1-52); the ampoule (2) is supported by a limiting spacer (2-11) and placed in the inner furnace body (1-1);
the interior of the inner furnace body (1-1) is divided into nine temperature zones along the axial direction, and the nine temperature zones are arranged from one end connected with the air pressure device (1-31) in sequence: the device comprises a protective temperature area I (1-17), a reaction auxiliary temperature area I (1-12), a reaction main temperature area (1-11), a reaction auxiliary temperature area II (1-13), a transition temperature area (1-19), a synthesis auxiliary temperature area I (1-15), a synthesis main temperature area (1-14), a synthesis auxiliary temperature area II (1-16), a protective temperature area II (1-18), a reaction auxiliary temperature area I (1-12), a reaction main temperature area (1-11) and a reaction auxiliary temperature area II (1-13) which are integrated together to form a reaction temperature area, and a synthesis auxiliary temperature area I (1-15), a synthesis main temperature area (1-14) and a synthesis auxiliary temperature area II (1-16) which are integrated together to form a synthesis temperature area;
the outer-layer heating device (1-2) comprises eight heating devices and a heat preservation device, the eight heating devices and the heat preservation device are respectively wrapped around the periphery of the inner furnace body (1-1) and are arranged corresponding to nine temperature zones of the inner furnace body (1-1), and the eight heating devices are sequentially a protection temperature zone I heating device (1-27), a reaction auxiliary temperature zone I heating device I (1-22), a reaction main temperature zone heating device (1-21), a reaction auxiliary temperature zone II heating device (1-23), a transition temperature zone heat preservation device (1-29), a synthesis auxiliary temperature zone I heating device (1-25), a synthesis main temperature zone heating device (1-24), a synthesis auxiliary temperature zone II heating device (1-26) and a protection temperature zone II heating device (1-28);
the cooling devices (1-4) are three sets, namely a cooling device (1-47) of a protection temperature zone I, a cooling device (1-48) of a protection temperature zone II and a cooling device (1-49) of a transition temperature zone, wherein the cooling device (1-49) of the transition temperature zone is attached to an internal furnace body (1-1) and arranged inside the heat preservation device (1-29) of the transition temperature zone, and is in linkage control with the heating device (1-2) and the air pressure control device (1-3); the cooling devices (1-47) of the protection temperature area I and the cooling devices (1-48) of the protection temperature area II are respectively arranged at the outer sides of the protection temperature areas I (1-17) and the protection temperature areas II (1-18) and are synchronously controlled;
the ampoule (2) comprises a protective container (2-1), a synthesis container (2-2), a reaction crucible (2-31) and a synthesis crucible (2-32), wherein the reaction crucible (2-31) and the synthesis crucible (2-32) are respectively placed at two ends in the synthesis container (2-2), and the synthesis container (2-2) with two crucibles is placed in the protective container (2-1); the protective container (2-1) is a cylinder with two open ends, a plurality of clamping grooves (2-10) are formed in the lower sides of the two ends of the cylinder, and limiting spacers (2-11) are respectively inserted into the clamping grooves (2-10) at the two ends of the protective container (2-1) according to the size of the synthetic container (2-2); the synthesis vessel (2-2) is a cylinder with one open end;
the gas pressure control device (1-3) uses a gas inert to chemical reaction as an additional control gas, preferably high-purity nitrogen; the gas flows into the gas pressure control device (1-31), sequentially passes through a protective temperature area I (1-17), a reaction auxiliary temperature area I (1-12), a reaction main temperature area (1-11), a reaction auxiliary temperature area II (1-13), a transition temperature area (1-19), a synthesis auxiliary temperature area I (1-15), a synthesis main temperature area (1-14) and a synthesis auxiliary temperature area II (1-16), and flows out of the protective temperature area II (1-18) to enter the gas pressure control device (1-32).
2. The apparatus for synthesizing polycrystal of phosphorus, germanium and zinc according to claim 1, wherein: the outer layer heating device (1-2)
Comprises heating resistance wires (1-201), heat insulation materials (1-202) and thermocouples (1-203); the heating resistance wires (1-201) are arranged around the periphery of the whole inner furnace body (1-1); the heat insulation materials (1-202) are tightly wrapped on the heating resistance wires (1-201); the heating device (1-2) corresponding to each temperature zone is correspondingly provided with a thermocouple (1-203) at the top end of the inner furnace body (1-1), and the probe extends to the corresponding temperature zone in the inner furnace body (1-1); at least three sets of heating devices control a reaction temperature area, three sets of heating devices control a synthesis temperature area, and two sets of heating devices control a protection temperature area; the heat preservation device (1-29) of the transition temperature zone is completely composed of heat insulation materials (1-202), the shape is concave, the diameters of two ends of the heat preservation device are consistent with those of the temperature zones on two sides, and the diameter of the central part is 2/3-1/3 of the diameters of the two end parts.
3. The apparatus for synthesizing polycrystal of phosphorus, germanium and zinc according to claim 1, wherein: the protective container of the ampoule (2)
The material of the reactor (2-1) is quartz or magnesia or alumina, preferably quartz, the material of the synthesis container (2-2) is preferably quartz, and the materials of the reaction crucible (2-31) and the synthesis crucible (2-32) are graphite or boron nitride, preferably boron nitride; the limiting spacers (2-11) are preferably in the shape of a corner rectangle, and are preferably made of quartz.
4. The synthesis method adopting the phosphorus germanium zinc polycrystal pressure synthesis device as claimed in claim 1, characterized in that: the method comprises the following steps:
firstly, weighing raw materials and sealing a synthesis container: corroding and cleaning a synthesis container (2-2), a reaction crucible (2-31) and a synthesis crucible (2-32), corroding and cleaning zinc and germanium, sampling and mixing according to a ratio of 1: 1-1.1: 1, then putting the mixture into the synthesis crucible (2-32), weighing phosphorus which is 1.1 times of the molar weight of zinc, putting the phosphorus into the reaction crucible (2-31), respectively placing the reaction crucible (2-31) and the synthesis crucible (2-32) at two ends of the synthesis container (2-2), and carrying out vacuum treatment on the open end of the synthesis container (2-2) and then welding and sealing the open end;
step two, loading into a furnace body: putting a sealed synthesis container (2-2) which is well welded into a protective container (2-1), selecting a clamping groove (2-10) with two ends close to the synthesis container (2-2) to insert a limiting spacer (2-11), putting the protective container (2-1) inserted with the spacer (2-11) into an inner furnace body (1-1) of a synthesis furnace by taking the spacer (2-11) as a support, putting a reaction crucible (2-31) at a position corresponding to a main reaction temperature zone (1-11) of the inner furnace body (1-1), and putting a synthesis crucible (2-32) at a position corresponding to a main synthesis temperature zone (1-14) of the inner furnace body (1-1);
step three, sealing the furnace body and exchanging air: sealing flanges (1-5) at two ends of an internal furnace body (1-1), starting an air pressure control device (1-3), introducing chemical reaction inert gas into the internal furnace body (1-1), introducing the inert gas into the internal furnace body (1-1) from the air pressure control device I (1-31), introducing the inert gas into an air pressure control device II (1-32) through each temperature zone in the furnace body, and keeping the standard atmospheric pressure while driving original air in the furnace;
step four, reaction of phosphorus and zinc: starting a cooling device (1-4), starting the cooling device all the time, starting a heating device (1-2), and respectively heating the reaction auxiliary temperature region I (1-12), the reaction main temperature region (1-11) and the reaction auxiliary temperature region II (1-13) to 400-fold 530 ℃ through a heating device (1-27) of a protection temperature region I, a heating device (1-22) of the reaction auxiliary temperature region, a heating device (1-21) of the reaction main temperature region, a heating device (1-23) of the reaction auxiliary temperature region II, a heat preservation device (1-29) of a transition temperature region, a heating device (1-25) of the synthesis auxiliary temperature region I, a heating device (1-24) of the synthesis main temperature region, a heating device (1-26) of the synthesis auxiliary temperature region II and a heating device (1-28) of the protection temperature region II, The synthesis main temperature zone (1-14) and the synthesis auxiliary temperature zone II (1-16) are heated to 1000-; in the process, the phosphorus simple substance in the reaction crucible (2-31) is sublimated into phosphorus steam which reacts with the zinc steam sublimated from the synthesis crucible (2-32) and the zinc melt to generate zinc phosphide and zinc diphosphide, the reaction of phosphorus and zinc is completed after 10h, the generated phosphorus-zinc compound is attached in the reaction container (2-2), and only a small amount of excessive phosphorus simple substance remains in the system;
fifthly, synthesizing a phosphorus-zinc compound and germanium: adjusting the cooling device (1-49) of the transition temperature zone (1-19) to slow down the cooling speed, increasing the temperatures of the reaction auxiliary temperature zone I (1-12), the reaction main temperature zone (1-11) and the reaction auxiliary temperature zone II (1-13), recovering the cooling speed of the transition temperature zone (1-19) until the temperature of the transition temperature zone (1-19) is adjusted to be lower than the temperature of the synthesis temperature zone by 100 ℃ and 200 ℃, and slowly increasing the temperatures of the reaction auxiliary temperature zone I (1-12), the reaction main temperature zone (1-11) and the reaction auxiliary temperature zone II (1-13) until the temperature of the transition temperature zone (1-19) is higher than the temperature of the synthesis temperature zone (1-14) by 10-30 ℃; meanwhile, the air pressure control device (1-3) is adjusted according to the temperature of the reaction temperature zone and the synthesis progress, and the temperature is maintained until the reaction is finished; in the process, the generated phosphorus-zinc compound is vaporized into steam to flow to the synthesis area along with the rise of the temperature of the reaction temperature area, the steam reacts with germanium in the synthesis crucible (2-32) to generate molten phosphorus-germanium-zinc, and the phosphorus-zinc compound steam continuously flows to the synthesis crucible (2-32) along with the continuous generation of the phosphorus-germanium-zinc until the synthesis is finished;
sixthly, cooling: after the reaction is finished, adjusting a cooling device (1-4) to increase the cooling speed, simultaneously cooling the temperature of the reaction temperature region and the temperature of the synthesis temperature region to 930-960 ℃, and then respectively cooling so that the temperature of the reaction auxiliary temperature region I (1-12), the temperature of the reaction main temperature region (1-11) and the temperature of the reaction auxiliary temperature region II (1-13) are firstly reduced to 290-960 ℃, the temperature of the synthesis auxiliary temperature region I (1-15), the temperature of the synthesis main temperature region (1-14) and the temperature of the synthesis auxiliary temperature region II (1-16) are always higher than that of the reaction auxiliary temperature region I (1-12), the temperature of the reaction main temperature region (1-11) and the temperature of the reaction auxiliary temperature region II (1-13) by more than 50 ℃ and maintained for at least 3 hours, adjusting an air pressure control device (1-3) according to the temperature of the reaction temperature region to ensure that the two temperature, meanwhile, the white phosphorus phase is converted into a relatively stable red phosphorus phase, and a phosphorus-germanium-zinc eutectic is formed;
seventh step, continuously cooling: continuously cooling to room temperature, adjusting the air pressure control device (1-3) to reduce the internal air pressure to the standard atmospheric pressure, and closing the pressure control device (1-3), the heating device (1-2) and the cooling device (1-4);
eighth, taking out the finished product and cleaning the crucible: taking out the ampoule (2), destroying the synthesis container (2-1), taking out the finished product, and cleaning the reaction crucible (2-31) and the synthesis crucible (2-32) for the next use.
5. The use method of the phosphorus germanium zinc polycrystal pressure synthesis device according to claim 4, wherein the method comprises the following steps: the highest temperature of the synthesis process is not higher than 1100 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112851138A (en) * | 2020-12-26 | 2021-05-28 | 云南农业大学 | Smoked carbon device of quartz ampoule wall |
| CN113957523A (en) * | 2021-10-26 | 2022-01-21 | 中国电子科技集团公司第四十六研究所 | Multi-element crystal purification device and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851138A (en) * | 2020-12-26 | 2021-05-28 | 云南农业大学 | Smoked carbon device of quartz ampoule wall |
| CN112851138B (en) * | 2020-12-26 | 2021-07-23 | 云南农业大学 | Smoked carbon device of quartz ampoule wall |
| CN113957523A (en) * | 2021-10-26 | 2022-01-21 | 中国电子科技集团公司第四十六研究所 | Multi-element crystal purification device and method |
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