CN112281214A - Method and device for growing rare earth sesquioxide crystal based on double-crucible method - Google Patents

Method and device for growing rare earth sesquioxide crystal based on double-crucible method Download PDF

Info

Publication number
CN112281214A
CN112281214A CN202011179598.7A CN202011179598A CN112281214A CN 112281214 A CN112281214 A CN 112281214A CN 202011179598 A CN202011179598 A CN 202011179598A CN 112281214 A CN112281214 A CN 112281214A
Authority
CN
China
Prior art keywords
crucible
rhenium
crystal
tungsten
growth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011179598.7A
Other languages
Chinese (zh)
Inventor
尹延如
王贵吉
陶绪堂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN202011179598.7A priority Critical patent/CN112281214A/en
Publication of CN112281214A publication Critical patent/CN112281214A/en
Pending legal-status Critical Current

Links

Images

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
    • 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
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/002—Crucibles or containers for supporting the melt
    • 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the melt
    • C30B15/12—Double crucible methods

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention relates to a method and a device for growing rare earth sesquioxide crystals based on a double-crucible method, wherein the growing method comprises the following steps: providing a rhenium crucible for containing raw materials; a tungsten crucible is sleeved outside the rhenium crucible and is used as a main heating body to form a double crucible together with the rhenium crucible; and (3) using the double crucible as a growth device, and performing crystal growth by adopting a melt method to obtain the rare earth sesquioxide crystal. The growth device comprises a growth furnace body, wherein the growth furnace body is provided with a furnace chamber, a rhenium crucible is arranged in the furnace chamber, and a tungsten crucible is sleeved outside the rhenium crucible. The invention replaces the rhenium crucible with the double crucibles, which can not only prevent the reaction of the raw materials and the tungsten crucible, but also reduce the loss of the rhenium crucible, more importantly, can reduce the wall thickness of the rhenium crucible, greatly reduce the production cost, and simultaneously grow the large-size and high-quality (Ln)xRe1‑x)2O3And (4) crystals.

Description

Method and device for growing rare earth sesquioxide crystal based on double-crucible method
Technical Field
The invention relates to a crystal growth method of rare earth sesquioxide, in particular to a preparation method of a low-cost large-size rare earth sesquioxide crystal material.
Background
Rare earth sesquioxide crystal Re2O3(Re＝Y、Sc、Lu and Gd) has the characteristics of low phonon energy, high thermal conductivity, high damage threshold, high quantum efficiency and the like, is an oxide crystal material with excellent comprehensive performance, and is applied to high-concentration rare earth ions Ln3+(Ln) is formed when doping (Yb, Ce, Tb, Nd, Dy, Ho, Er, Tm, Pr)xRe1-x)2O3The crystal still keeps high thermal conductivity, and has great application prospect in the fields of high-power laser, microchip laser, high-energy ray detection and the like.
(LnxRe1-x)2O3Crystal (x is more than or equal to 0)<0.5) extremely high melting point (both more than 2400 ℃), and obtaining high-quality, large-size single crystals is extremely difficult. When the crystal grows by a melt method (such as a pulling method, a die-guiding method, a heat exchange method and a temperature gradient method), rhenium (3180 ℃) with high melting point can be used as a crucible material. The rhenium crucible does not react with the melt at high temperature, and relatively stable physical and chemical properties are maintained. Patent document CN105671629A mentions that it is possible to grow such crystals using a tungsten crucible, but the solution using a tungsten crucible is not feasible because before the raw material is melted, even under a weakly reducing atmosphere, metallic tungsten reacts violently with the raw material, causing the crucible to be melted through, as shown in fig. 1. Further, in patent documents CN108893776A and CN209194101U, the crucible is a tungsten crucible, a rhenium crucible, a molybdenum crucible or a graphite crucible, and a graphite hard felt insulating layer is used. However, when there is a graphite device in the furnace, such as a graphite felt, a graphite barrel, and a graphite crucible, as a heat insulating material or a heating body, during the crystal growth process, the carbon atmosphere causes graphite to enter the raw material, causing serious pollution, causing the raw material to be black, and cannot be eliminated by the post air annealing process, as shown in fig. 2. More importantly, the rhenium crucible is very easy to carbonize in the graphite atmosphere at high temperature, and the rhenium metal is seriously embrittled and reacts with raw materials, so that the crucible cannot be normally used. Therefore, the above prior art schemes for growing rare earth sesquioxide crystals are not effective.
At present, when the crystal is grown by a melt method (such as a pulling method, a die-guiding method, a heat exchange method and a temperature gradient method), the rhenium metal crucible can be only used reluctantly under the protection of a stronger reducing atmosphere. But because the melting point of rhenium is more than 3400 ℃, the rhenium crucible can not be processed and formed by adopting the traditional casting method, but adopts a powder metallurgy mode; however, the yield of powder metallurgy is low, the processing period is long, the processing difficulty is high, and the price is high. Moreover, when the rhenium crucible is used as a main heating body in induction heating, the crucible wall needs larger thickness (generally more than 5mm) to provide the extremely high temperature required by the growth of the ultrahigh melting point sesquioxide single crystal, thereby greatly increasing the growth cost of the crystal. In addition, when the sesquioxide crystal with large size grows, the local part of the crucible is very easy to overheat, as shown in figure 3, and the crucible is melted through and scrapped.
Therefore, it is urgent to develop a method and apparatus for growing a rare earth sesquioxide crystal that reduces the cost of crucible use. The invention is therefore proposed.
Disclosure of Invention
The invention provides a method and a device for growing rare earth sesquioxide crystals based on a double-crucible method, aiming at the problems that when the rare earth sesquioxide crystals are prepared by the existing melt method, such as a pulling method, a mold guiding method, a heat exchange method, a temperature gradient method and the like, a rhenium crucible is large in loss, high in cost, harsh in use conditions and the like.
The invention adopts a double-crucible crystal growth method, and the tungsten crucible is used as a main heating body to provide a proper temperature field environment for the growth of the sesquioxide crystal; the rhenium crucible was placed in place in the tungsten crucible, primarily as a container for the melt of the sesquioxide. The method can separate the raw material from the tungsten crucible and prevent the raw material and the tungsten crucible from generating violent chemical reaction; the possibility of local overheating of the rhenium crucible can be reduced, and the loss of the crucible is reduced; more importantly, the thickness of the rhenium crucible used as a raw material container is reduced, the production cost is greatly reduced, and the method is suitable for industrial popularization.
The technical scheme of the invention is as follows:
a method for growing rare earth sesquioxide crystals based on a double-crucible method comprises the following steps:
providing a rhenium crucible for containing raw materials;
a tungsten crucible is sleeved outside the rhenium crucible and is used as a main heating body to form a double crucible together with the rhenium crucible;
and (3) using the double crucible as a growth device, and performing crystal growth by adopting a melt method to obtain the rare earth sesquioxide crystal.
According to the invention, the rhenium crucible and the tungsten crucible are preferably separated by a rhenium support in the double crucible.
According to the invention, it is preferred that the upper edge of the tungsten crucible in the double crucible is higher than the upper edge of the rhenium crucible. Namely: the height of the tungsten crucible is greater than the sum of the heights of the rhenium crucible and the rhenium bracket;
preferably, the wall thickness of the rhenium crucible is smaller than that of the tungsten crucible;
preferably, the rhenium crucible and the tungsten crucible are both cylindrical, and the diameter difference between the rhenium crucible and the tungsten crucible is more than 10 mm.
According to the invention, preferably, the rare earth sesquioxide crystal is (Ln)xRe1-x)2O3Crystal, x is not less than 0<0.5; re ═ Y, Sc, Lu or Gd, Ln ═ Yb, Ce, Tb, Nd, Dy, Ho, Er, Tm or Pr;
preferably, the raw material is Re2O3And Ln2O3And (3) powder.
According to the present invention, preferably, the melt method is a czochralski method, a die-guiding method, a heat exchange method or a temperature gradient method.
According to the invention, the heating mode in the crystal growth process of the melt method is preferably heating by a medium-frequency induction power supply.
According to the invention, preferably, protective gas is adopted for protection during the crystal growth process by a melt method; more preferably, the protective gas is a flowable single or mixed reducing gas; preferably, the reducing gas is H2+Ar。
According to the present invention, preferably, the melt-process crystal growth process comprises: melting, adding seed crystals, reducing diameter, shouldering, growing in an equal diameter manner, and cooling and removing after the growth is finished to obtain rare earth sesquioxide crystals;
preferably, when the crystal is grown by a heat exchange method or a temperature gradient method, the seeding step is omitted.
According to the invention, preferably, in the crystal growth process by the melt method, the raw materials are put into a double crucible to be heated and melted, the double crucible is overheated by 10-30 ℃, the melt state is stabilized by constant temperature, and then the melt is cooled to the temperature of seed crystal;
preferably, Re is used2O3Taking the crystal as a seed crystal, descending the seed crystal to the surface of the melt and reducing the diameter of the seed crystal, shouldering when the diameter of the seed crystal is reduced to 2-3mm, and then starting isodiametric growth; when the Czochralski method is adopted for growth, the pulling speed is 0.5-5 mm.h-1。
The crystal growth method related in the invention comprises a melt method such as a pulling method, a die guiding method, a heat exchange method, a temperature gradient method and the like, wherein the heating mode of the crystal growth method is heating by adopting a medium-frequency induction power supply; a preferred embodiment, comprising the steps of:
weighing and pressing: according to Re2O3And Ln2O3Respectively weighing Re according to the stoichiometric ratio2O3And Ln2O3Mixing the powder and pressing into blocks;
charging: placing a tungsten crucible in a heat-insulating material, placing a rhenium support in the tungsten crucible, and then placing the rhenium crucible in the center of the tungsten crucible and on the rhenium support; after seed crystals are installed, sealing a hearth, vacuumizing, and introducing protective gas, wherein the protective gas is a single or mixed reducing gas with fluidity;
melting: heating to raise the temperature to completely melt the raw materials to form a melt, overheating for 10-30 ℃, keeping the temperature to stabilize the state of the melt, and then cooling to a seeding temperature;
growth: growing crystal by Czochralski method, mold-guiding method, heat exchange method or temperature gradient method, and using Re2O3Taking the crystal as seed crystal, lowering the seed crystal to the surface of the melt and reducing the diameter, shouldering when the diameter of the seed crystal is reduced to 2-3mm, then starting isodiametric growth, and pulling at a speed of 0.5-5 mm.h-1(ii) a When a heat exchange method and a temperature gradient method are adopted, the next step is omitted;
cooling: and (4) separating the crystal from the melt after the growth is finished, and cooling to room temperature to obtain the rare earth sesquioxide crystal.
According to the invention, the device for growing the rare earth sesquioxide crystal comprises a growing furnace body, wherein the growing furnace body is provided with a furnace chamber, a rhenium crucible is arranged in the furnace chamber, and a tungsten crucible is sleeved outside the rhenium crucible.
According to the invention, preferably, the bottom of the rhenium crucible is provided with a rhenium bracket;
preferably, the bottom of the tungsten crucible is provided with a tungsten bracket.
According to the present invention, it is preferable that the tungsten crucible has a cylindrical structure or a cylindrical structure without a bottom surface. When the tungsten crucible is of a cylindrical structure, the rhenium support supports the rhenium crucible and is jointly arranged on the bottom surface of the cylinder, and the rhenium support separates the rhenium crucible from the tungsten crucible. When the tungsten crucible is a cylinder structure without a bottom surface, the rhenium support supports the rhenium crucible and is jointly arranged on the upper part of the insulating brick.
According to the invention, the upper edge of the tungsten crucible is preferably higher than the upper edge of the rhenium crucible. Namely: the height of the tungsten crucible is greater than the sum of the heights of the rhenium crucible and the rhenium bracket;
preferably, the wall thickness of the rhenium crucible is smaller than that of the tungsten crucible;
preferably, the difference between the diameters of the rhenium crucible and the tungsten crucible is larger than 10 mm.
According to the invention, preferably, the rhenium crucible top is provided with a rhenium crucible cover.
According to the invention, preferably, a rhenium mould is arranged in the rhenium crucible and is vertical to the bottom surface of the rhenium crucible. The device arranged in this way is suitable for growing crystals by the guided mode method.
According to the invention, preferably, the bottom of the rhenium crucible is provided with a heat exchanger. The device arranged in this way is suitable for growing crystals by a heat exchange method.
According to the invention, preferably, the periphery, the upper surface and the bottom surface of the growth furnace body are provided with heat preservation layers; preferably, the heat-insulating layer is a zirconia heat-insulating brick or a zirconia fiber cotton;
preferably, quartz tubes are arranged on the outer side of the heat preservation layer on the periphery of the growth furnace body, and induction heating coils are arranged on the periphery of the quartz tubes. The tungsten crucible is separated from the heat-insulating layer by a tungsten bracket.
The invention has the following beneficial effects:
the tungsten crucible is used as a main heating body, the rhenium crucible is used as a raw material container, and the tungsten crucible and the rhenium crucible jointly form a double-crucible system. The double-crucible replaceable melt method in the invention, such as a pulling method, a mold guiding method, a heat exchange method and a temperature gradient method, can prevent the reaction of the raw material and the tungsten crucible, greatly reduce the possibility of local overheating of the rhenium crucible, reduce the loss of the rhenium crucible, and more importantly, can reduce the wall thickness of the rhenium crucible, and the cost of the tungsten crucible is lower, thereby greatly reducing the production cost of the crystal, and simultaneously growing the large-size and high-quality (Ln) crystalxRe1-x)2O3And (4) crystals.
Drawings
FIG. 1 is a photograph showing the crucible being melted through during the growth of rare earth sesquioxide crystals using a tungsten crucible in the prior art.
Fig. 2 is a photograph showing that in the process of growing rare earth sesquioxide crystals by using a device with graphite in a hearth in the prior art, graphite enters raw materials due to a carbon atmosphere, and the raw materials are black.
FIG. 3 is a photograph showing that during the growth of a large-sized sesquioxide crystal according to the prior art, the crucible is locally overheated, which causes the crucible to be seriously volatilized and scrapped.
FIG. 4 is a schematic view of a double crucible apparatus using a tungsten crucible in example 1 of the present invention.
FIG. 5 is a schematic view of a double crucible apparatus using a tungsten bucket in example 2 of the present invention.
FIG. 6 is a schematic view of a double crucible apparatus using a heat exchange method in example 3 of the present invention.
Wherein: 1. an induction heating coil; 2. a quartz tube; 3. a heat-insulating layer; 4. a tungsten crucible; 5. a rhenium crucible; 6. seed crystal; 7. a rhenium mold; 8. melting the materials; 9. a tungsten stent; 10. a rhenium stent; 11. a rhenium crucible cover; 12. a heat exchanger.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1:
as shown in fig. 4, the device for growing rare earth sesquioxide crystals comprises a growth furnace body, wherein the growth furnace body is provided with a furnace chamber, a rhenium crucible 5 is arranged in the furnace chamber, and a tungsten crucible 4 is sleeved outside the rhenium crucible 5.
The periphery, the upper surface and the bottom surface of the growth furnace body are provided with heat preservation layers 3, and the heat preservation layers 3 are zirconia heat preservation bricks;
the growth furnace is characterized in that quartz tubes 2 are arranged on the outer sides of the heat preservation layers on the periphery of the growth furnace body, and induction heating coils 1 are arranged on the periphery of the quartz tubes 2.
The bottom of the rhenium crucible 5 is provided with a rhenium bracket 10, and the bottom of the tungsten crucible 4 is provided with a tungsten bracket 9. The rhenium holder 10 separates the rhenium crucible 5 from the tungsten crucible 4. The method can prevent the reaction of the raw materials and the tungsten crucible, greatly reduce the possibility of local overheating of the rhenium crucible, reduce the loss of the rhenium crucible, and more importantly, can reduce the wall thickness of the rhenium crucible, and the tungsten crucible has lower cost, thereby greatly reducing the production cost of crystals.
The rhenium crucible cover 11 is arranged at the top of the rhenium crucible 5, and the rhenium mold 7 is vertically arranged in the rhenium crucible 5 and on the bottom surface of the rhenium crucible 5.
The upper edge of the tungsten crucible 4 is higher than the upper edge of the rhenium crucible 5. Namely: the height of the tungsten crucible is larger than the height of the rhenium crucible and the rhenium bracket, the wall thickness of the rhenium crucible 5 is smaller than that of the tungsten crucible 4, and the diameter difference between the rhenium crucible 5 and the tungsten crucible 4 is 12 mm.
Example 2:
as shown in fig. 5, an apparatus for growing a rare earth sesquioxide crystal has the same structure as that of example 1, except that:
the tungsten crucible 4 is a cylinder structure without a bottom surface, and the rhenium support 10 supports the rhenium crucible 5 and is jointly arranged on the upper part of the zirconia insulating brick 3.
Example 3:
as shown in fig. 6, the device for growing rare earth sesquioxide crystals comprises a growth furnace body, wherein the growth furnace body is provided with a furnace chamber, a rhenium crucible 5 is arranged in the furnace chamber, and a tungsten crucible 4 is sleeved outside the rhenium crucible 5. The bottom of the rhenium crucible 5 is provided with a rhenium bracket 10, and the bottom of the tungsten crucible 4 is provided with a tungsten bracket 9. The rhenium holder 10 separates the rhenium crucible 5 from the tungsten crucible 4.
The periphery, the upper surface and the bottom surface of the growth furnace body are provided with heat preservation layers 3, and the heat preservation layers 3 are made of zirconia heat preservation cotton;
the growth furnace is characterized in that quartz tubes 2 are arranged on the outer sides of the heat preservation layers on the periphery of the growth furnace body, and induction heating coils 1 are arranged on the periphery of the quartz tubes 2.
The rhenium crucible cover 11 is arranged at the top of the rhenium crucible 5, and the heat exchanger 12 is arranged at the bottom of the rhenium crucible 5.
The tungsten crucible 4 is a cylinder structure without a bottom surface, and the rhenium support 10 supports the rhenium crucible 5 and is jointly arranged on the upper part of the zirconia insulating brick 3.
The upper edge of the tungsten crucible 4 is higher than the upper edge of the rhenium crucible 5. Namely: the height of the tungsten crucible is larger than the height of the rhenium crucible and the rhenium bracket, the wall thickness of the rhenium crucible 5 is smaller than that of the tungsten crucible 4, and the diameter difference between the rhenium crucible 5 and the tungsten crucible 4 is 15 mm.
Example 4: growing (Er) by double crucible guided mode method0.01Lu0.99)2O3Crystal
According to Lu2O3And Er2O3The raw material powders are weighed respectively according to the stoichiometric ratio, and are pressed into blocks after being uniformly mixed, and the rhenium crucibles 5 (the inner diameter is 70mm, and the wall thickness is 5mm) of the rhenium molds 7 are filled. As shown in FIG. 4, a zirconia insulating brick 3, a tungsten holder 9, a tungsten crucible 4 (inner diameter 100mm, wall thickness 10mm), a rhenium holder 10, and a rhenium crucible 5 were installed. Mounting Lu2O3After seed crystal, the growth furnace chamber is sealed, and after vacuum pumping, 1% H is introduced2+ Ar as protective gas. Heating to raise the temperature to melt all the raw materials into a melt, overheating the melt by 10 ℃, keeping the temperature constant to stabilize the state of the melt, then cooling to a seeding temperature, lowering the seed crystal 6 to the surface of a rhenium mould 7 and reducing the diameter, shouldering when the diameter of the seed crystal 6 is reduced to 2-3mm, and then starting isodiametric growth, wherein the pulling speed is 0.5 mm.h-1. And (4) separating the crystal from the melt 8 after the growth is finished, and cooling the crystal to room temperature.
Example 5: growth of (Dy) by double crucible guided mode method0.02Lu0.98)2O3Crystal
According to Lu2O3And Dy2O3The raw material powders are weighed respectively according to the stoichiometric ratio, and are pressed into blocks after being uniformly mixed, and the rhenium crucibles 5 (the inner diameter is 60mm, and the wall thickness is 2mm) of the rhenium molds 7 are filled. The zirconia insulating brick 3, the tungsten bracket 9, the tungsten barrel 4 (inner diameter 100mm, wall thickness 10mm), the rhenium bracket 10 and the rhenium crucible 5 are installed as shown in FIG. 5. Mounting Lu2O3After seed crystal 6, the furnace chamber of the sealed growth furnace is vacuumized and then 2 percent H is introduced2+ Ar as protective gas. Heating to raise the temperature to melt all the raw materials into a melt, overheating the melt by 10 ℃, keeping the temperature constant to stabilize the state of the melt, then cooling to a seeding temperature, lowering the seed crystal 6 to the surface of a rhenium mould 7 and reducing the diameter, shouldering when the diameter of the seed crystal 6 is reduced to 2-3mm, and then starting isodiametric growth, wherein the pulling speed is 0.5 mm.h-1. And (4) separating the crystal from the melt 8 after the growth is finished, and cooling the crystal to room temperature.
Example 6: adopting a double-crucible pulling method to grow (Nd)0.05Sc0.95)2O3Crystal
According to Sc2O3And Nd2O3The raw material powders are respectively weighed according to the stoichiometric ratio, evenly mixed and pressed into blocks, and the rhenium crucibles 6 (the inner diameter is 50mm, and the wall thickness is 1mm) are filled. As shown in FIG. 4, a zirconia insulating brick 3, a tungsten holder 9, a tungsten crucible 4 (inner diameter 70mm, wall thickness 12mm), a rhenium holder 10, and a rhenium crucible 5 were installed. Mounting Sc2O3After seed crystal 6, the furnace chamber of the sealed growth furnace is vacuumized and then 5 percent H is introduced2+ Ar as protective gas. Heating to raise temperature to melt the material completely to form melt, overheating to 20 deg.C, maintaining the temperature to stabilize the melt state, cooling to seeding temperature, lowering seed crystal 6 to the melt surface and reducing diameter, shouldering when the seed crystal diameter is reduced to 2-3mm, and then starting isodiametric growth at a pulling speed of 1 mm.h-1. And (4) separating the crystal from the melt 8 after the growth is finished, and cooling the crystal to room temperature.
Example 7: adopting a double crucible pulling method to grow (Yb)0.07Sc0.93)2O3Crystal
According to Sc2O3And Yb2O3The raw material powders are respectively weighed according to the stoichiometric ratio, evenly mixed and pressed into blocks, and the rhenium crucibles 5 (the inner diameter is 40mm, and the wall thickness is 0.5mm) are filled. The zirconia insulating brick 3, the tungsten bracket 9, the tungsten barrel 4 (inner diameter 70mm, wall thickness 10mm), the rhenium bracket 9 and the rhenium crucible 5 are installed as shown in FIG. 5. Mounting Sc2O3After seed crystal 6, the furnace chamber of the sealed growth furnace is vacuumized and then 7 percent H is introduced2+ Ar as protective gas. Heating to raise the temperature to melt all the raw materials into a melt, overheating to 20 ℃, keeping the temperature constant to stabilize the state of the melt, then cooling to a seeding temperature, lowering the seed crystal 6 to the surface of a rhenium mould 7 and reducing the diameter, shouldering when the diameter of the seed crystal 6 is reduced to 2-3mm, and then starting isodiametric growth, wherein the pulling speed is 1.5 mm.h-1. And (4) separating the crystal from the melt 8 after the growth is finished, and cooling the crystal to room temperature.
Example 8: growth by double crucible heat exchange method (Ce)0.1Y0.9)2O3Crystal
According to Y2O3And Ce2O3Respectively weighing raw material powder according to the stoichiometric ratio, uniformly mixing and briquetting. Mounting Y in seed crystal area at bottom of rhenium crucible 52O3Seed 6, and then rhenium crucible 5 (inner diameter 80mm, wall thickness 2mm) was filled with the block. The zirconia insulating brick 3, the tungsten bracket 9, the tungsten barrel 4 (inner diameter 114mm, wall thickness 12mm), the rhenium bracket 10 and the rhenium crucible 5 are installed as shown in FIG. 6. After the chamber of the sealed growth furnace is vacuumized, 10 percent of H is introduced2+ Ar as protective gas. Heating to completely melt the raw materials, carrying out constant-temperature heat treatment for 17h, and controlling the seed crystal 6 not to be melted by controlling the power and the speed of introducing inert gas. Slowly cooling at the speed of 0.5-1.0 ℃/h to crystallize the melt 8 in the rhenium crucible 5 from bottom to top. After the crystal growth is finished, the temperature is reduced to a certain temperature at 1.5-2.2 ℃/h, the annealing process is finished, and the temperature is reduced to the room temperature according to the cooling speed of 10-25 ℃/h.
Example 6: growth (Tb) by double crucible heat exchange method0.15Y0.85)2O3Crystal
According to Y2O3And Tb2O3Respectively weighing raw material powder at stoichiometric ratio, and mixingAnd (6) pressing the mixture into blocks after the mixture is evenly mixed. Mounting Y in seed crystal area at bottom of rhenium crucible 52O3The seed crystal was then filled with a block of rhenium crucible 5 (inner diameter 90mm, wall thickness 3 mm). The zirconia insulating surface 3, the tungsten holder 9, the tungsten barrel 4 (inner diameter 126mm, wall thickness 12mm), the rhenium holder 10, and the rhenium crucible 5 were installed as shown in FIG. 6. After the closed growth furnace chamber is vacuumized, 15 percent of H is introduced2+ Ar as protective gas. Heating until the raw materials are completely melted, carrying out constant-temperature heat treatment for 17h, and controlling the seed crystal not to be melted by controlling the power and the speed of introducing inert gas. Slowly cooling at the speed of 0.5-1.0 ℃/h to crystallize the melt 8 in the rhenium crucible 5 from bottom to top. After the crystal growth is finished, the temperature is reduced to a certain temperature at 1.5-2.2 ℃/h, the annealing process is finished, and the temperature is reduced to the room temperature according to the cooling speed of 10-25 ℃/h.
Example 7: growing by double crucible temperature gradient method (Ho)0.2Gd0.8)2O3Crystal
According to Gd2O3And Ho2O3Respectively weighing raw material powder according to the stoichiometric ratio, uniformly mixing and briquetting. Gd is arranged in a seed crystal area at the bottom of the rhenium crucible 52O3The seed crystal was then filled with a block of rhenium crucible 5 (inner diameter 100mm, wall thickness 3 mm). According to the figure 4, the zirconia insulating brick 3, the tungsten bracket 9, the tungsten crucible 4 (the inner diameter is 126mm, the wall thickness is 15mm), the rhenium bracket 10 and the rhenium crucible 5 are arranged, and the proper temperature field structure and the favorable temperature gradient are constructed by adjusting the thickness of the insulating brick, so that the seed crystal is controlled not to be melted. After the growth furnace chamber of the closed furnace is vacuumized, 20 percent of H is introduced2+ Ar as protective gas. Heating until the raw materials are completely melted, carrying out constant-temperature heat treatment for 17h, and slowly cooling at the speed of 0.5-1.0 ℃/h to crystallize the melt 8 in the rhenium crucible 5 from bottom to top. After the crystal growth is finished, the temperature is reduced to a certain temperature at 1.5-2.2 ℃/h, the annealing process is finished, and the temperature is reduced to the room temperature according to the cooling speed of 10-25 ℃/h.
Example 8: growing by double-crucible temperature gradient method (Pr)0.25Gd0.75)2O3Crystal
According to Gd2O3And Pr2O3Respectively weighing raw material powder according to the stoichiometric ratio, uniformly mixing and briquetting. Gd is arranged in a seed crystal area at the bottom of the rhenium crucible 52O3Seed 6, and then rhenium crucible 5 (inner diameter 100mm, wall thickness 3mm) was filled with the block. According to the figure 5, the zirconia insulating brick 3, the tungsten bracket 9, the tungsten barrel 4 (the inner diameter is 126mm, the wall thickness is 15mm), the rhenium bracket 10 and the rhenium crucible 5 are arranged, and the proper temperature field structure and the favorable temperature gradient are constructed by adjusting the thickness of the insulating brick, so that the seed crystal is controlled not to be melted. After the growth furnace chamber of the closed furnace is vacuumized, 25 percent of H is introduced2+ Ar as protective gas. Heating until the raw materials are completely melted, carrying out constant-temperature heat treatment for 17h, and slowly cooling at the speed of 0.5-1.0 ℃/h to crystallize the melt in the rhenium crucible 5 from bottom to top. After the crystal growth is finished, the temperature is reduced to a certain temperature at 1.5-2.2 ℃/h, the annealing process is finished, and the temperature is reduced to the room temperature according to the cooling speed of 10-25 ℃/h.
Example 9: growing (Er) by double crucible guided mode method0.01(Lu1/2Y1/2)0.99)2O3Crystal
According to Lu2O3、Er2O3And Y2O3The raw material powders are weighed respectively according to the stoichiometric ratio, and are pressed into blocks after being uniformly mixed, and the rhenium crucibles 5 (the inner diameter is 70mm, and the wall thickness is 5mm) of the rhenium molds 7 are filled. The zirconia thermal insulation cotton 3, the tungsten support 9, the tungsten crucible 4 (inner diameter 100mm, wall thickness 10mm), the rhenium support 10 and the rhenium crucible 5 were installed as shown in FIG. 4. Mounting Lu2O3After seed crystal, the furnace chamber of the sealed growth furnace is vacuumized and then 1 percent of H is introduced2+ Ar as protective gas. Heating to melt the raw materials to form a melt, overheating to 10 ℃, keeping the temperature constant to stabilize the state of the melt, then cooling to a seeding temperature, lowering the seed crystal to the surface of a die and reducing the diameter, shouldering when the diameter of the seed crystal is reduced to 2-3mm, and then starting isodiametric growth, wherein the pulling speed is 0.5 mm.h-1. And (4) separating the crystal from the melt after the growth is finished, and cooling the crystal to room temperature.
Example 10: growing (Er) by double crucible heat exchange method0.02(Lu1/2Sc1/2)0.98)2O3Crystal
According to Lu2O3、Er2O3And Sc2O3Respectively weighing raw material powder according to the stoichiometric ratio, uniformly mixing and briquetting. In a rhenium crucible5 bottom seed crystal region mounting Lu2O3The seed crystal was then filled with a block of rhenium crucible 5 (inner diameter 90mm, wall thickness 3 mm). The zirconia insulating brick 3, the tungsten bracket 9, the tungsten barrel 4 (inner diameter 126mm, wall thickness 12mm), the rhenium bracket 10 and the rhenium crucible 5 are installed as shown in FIG. 6. After the closed growth furnace chamber is vacuumized, 15 percent of H is introduced2+ Ar as protective gas. Heating until the raw materials are completely melted, carrying out constant-temperature heat treatment for 17h, and controlling the seed crystal not to be melted by controlling the power and the speed of introducing inert gas. Slowly cooling at the speed of 0.5-1.0 ℃/h to crystallize the melt in the rhenium crucible 5 from bottom to top. After the crystal growth is finished, the temperature is reduced to a certain temperature at 1.5-2.2 ℃/h, the annealing process is finished, and the temperature is reduced to the room temperature according to the cooling speed of 10-25 ℃/h.
Comparative example 1: growing (Er) by double crucible guided mode method0.01Lu0.99)2O3Crystal
As described in example 4, except that:
according to Lu2O3And Er2O3The raw material powders are respectively weighed according to the stoichiometric ratio, the raw material powders are evenly mixed and then pressed into blocks, the tungsten crucible 4 with the tungsten mould 7 is filled, the rhenium crucible 5 is replaced by the tungsten crucible, and the rhenium bracket is replaced by the tungsten bracket according to the graph shown in figure 4. Respectively installing a zirconium oxide heat-insulating material, a tungsten bracket, a tungsten crucible, a tungsten bracket and a tungsten crucible. Namely: the double crucible system adopted in this comparative example was a tungsten crucible, and a rhenium crucible was not used. Because the metal tungsten reacts violently with the raw materials, the tungsten crucible is melted through, and the crystal cannot grow.
Comparative example 2: growing (Er) by double crucible guided mode method0.01Lu0.99)2O3Crystal
As described in example 4, except that:
the graphite insulation material, the graphite crucible, the rhenium bracket and the rhenium crucible are installed as shown in FIG. 4. When a graphite device is arranged in a hearth, such as a graphite felt, a graphite barrel and a graphite crucible, and is used as a heat insulation material or a heating body, in the crystal growth process, graphite enters into a raw material due to a carbon atmosphere, so that serious pollution is caused, the raw material is black, and the black graphite cannot be eliminated through a later-stage air annealing process. More importantly, at high temperature, the rhenium crucible is very easy to carbonize in the graphite atmosphere, and the rhenium metal is seriously embrittled and reacts with raw materials, so that the crucible cannot be normally used and the crystal growth fails.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.

Claims (10)

1. A method for growing rare earth sesquioxide crystals based on a double-crucible method comprises the following steps:
providing a rhenium crucible for containing raw materials;
a tungsten crucible is sleeved outside the rhenium crucible and is used as a main heating body to form a double crucible together with the rhenium crucible;
and (3) using the double crucible as a growth device, and performing crystal growth by adopting a melt method to obtain the rare earth sesquioxide crystal.
2. The method for growing rare earth sesquioxide crystals based on the double-crucible method as set forth in claim 1, wherein a rhenium support is used in the double crucible to separate the rhenium crucible from the tungsten crucible;
preferably, the upper edge of the tungsten crucible in the double crucible is higher than the upper edge of the rhenium crucible;
preferably, the wall thickness of the rhenium crucible is smaller than that of the tungsten crucible;
preferably, the rhenium crucible and the tungsten crucible are both cylindrical, and the diameter difference between the rhenium crucible and the tungsten crucible is more than 10 mm.
3. The method for growing a rare earth sesquioxide crystal according to the double-crucible method as set forth in claim 1, wherein the rare earth sesquioxide crystal is (Ln)xRe1-x)2O3Crystal, x is not less than 0<0.5; re ═ Y, Sc, Lu or Gd, Ln ═ Yb, Ce, Tb, Nd, Dy, Ho, Er, Tm or Pr;
preferably, the source isThe material is Re2O3And Ln2O3And (3) powder.
4. The double-crucible-based method for growing rare earth sesquioxide crystals according to claim 1, characterized in that protective gas is used for protection during the crystal growth process by the melt method;
preferably, the protective gas is a flowable single or mixed reducing gas; more preferably, the reducing gas is H2+Ar。
5. The double-crucible-based method for growing rare earth sesquioxide crystals according to claim 1, wherein the melt process crystal growth process comprises: melting, adding seed crystals, reducing diameter, shouldering, growing in an equal diameter manner, and cooling and removing after the growth is finished to obtain rare earth sesquioxide crystals;
preferably, when the crystal is grown by a heat exchange method or a temperature gradient method, the seeding step is omitted.
6. The method for growing rare earth sesquioxide crystals based on the double crucible method according to claim 5, characterized in that, in the process of crystal growth by the melt method, the raw materials are put into a double crucible, heated and melted, overheated by 10-30 ℃, kept at a constant temperature to stabilize the melt state, and then cooled to the temperature of the seed crystal;
preferably, Re is used2O3Taking the crystal as a seed crystal, descending the seed crystal to the surface of the melt and reducing the diameter of the seed crystal, shouldering when the diameter of the seed crystal is reduced to 2-3mm, and then starting isodiametric growth; when the Czochralski method is adopted for growth, the pulling speed is 0.5-5 mm.h-1。
7. The device for growing the rare earth sesquioxide crystal is characterized by comprising a growth furnace body, wherein the growth furnace body is provided with a furnace chamber, a rhenium crucible is arranged in the furnace chamber, and a tungsten crucible is sleeved outside the rhenium crucible.
8. The apparatus for growing rare earth sesquioxide crystals as set forth in claim 7, characterized in that a rhenium holder is provided at the bottom of the rhenium crucible;
preferably, the bottom of the tungsten crucible is provided with a tungsten bracket.
9. The apparatus for growing a rare earth sesquioxide crystal according to claim 7, characterized in that the tungsten crucible has a cylindrical structure or a cylindrical structure without a bottom surface;
preferably, the upper edge of the tungsten crucible is higher than the upper edge of the rhenium crucible;
preferably, the wall thickness of the rhenium crucible is smaller than that of the tungsten crucible;
preferably, the difference between the diameters of the rhenium crucible and the tungsten crucible is larger than 10 mm.
10. The apparatus for growing rare earth sesquioxide crystals as set forth in claim 7, characterized in that a rhenium crucible cover is provided on top of the rhenium crucible;
preferably, a rhenium mould is vertically arranged in the rhenium crucible and on the bottom surface of the rhenium crucible;
preferably, the bottom of the rhenium crucible is provided with a heat exchanger;
preferably, the periphery, the upper surface and the bottom surface of the growth furnace body are provided with heat preservation layers; preferably, the heat-insulating layer is a zirconia heat-insulating brick or a zirconia fiber cotton;
preferably, quartz tubes are arranged on the outer side of the heat preservation layer on the periphery of the growth furnace body, and induction heating coils are arranged on the periphery of the quartz tubes.
CN202011179598.7A 2020-10-29 2020-10-29 Method and device for growing rare earth sesquioxide crystal based on double-crucible method Pending CN112281214A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011179598.7A CN112281214A (en) 2020-10-29 2020-10-29 Method and device for growing rare earth sesquioxide crystal based on double-crucible method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011179598.7A CN112281214A (en) 2020-10-29 2020-10-29 Method and device for growing rare earth sesquioxide crystal based on double-crucible method

Publications (1)

Publication Number Publication Date
CN112281214A true CN112281214A (en) 2021-01-29

Family

ID=74373893

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011179598.7A Pending CN112281214A (en) 2020-10-29 2020-10-29 Method and device for growing rare earth sesquioxide crystal based on double-crucible method

Country Status (1)

Country Link
CN (1) CN112281214A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN202347126U (en) * 2011-10-14 2012-07-25 重庆四联光电科技有限公司 Double-crucible induction heating furnace
CN202643904U (en) * 2012-04-01 2013-01-02 北京华进创威电子有限公司 Double-crucible induction heating physical vapor phase transmission device for monocrystalline growth
US20140174341A1 (en) * 2011-08-05 2014-06-26 Plansee Se Crucible for growing crystals
CN105671629A (en) * 2016-04-06 2016-06-15 中国科学院上海光学精密机械研究所 Edge-defined film-fed growth method of rare-earth sesquioxide laser crystals

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140174341A1 (en) * 2011-08-05 2014-06-26 Plansee Se Crucible for growing crystals
CN202347126U (en) * 2011-10-14 2012-07-25 重庆四联光电科技有限公司 Double-crucible induction heating furnace
CN202643904U (en) * 2012-04-01 2013-01-02 北京华进创威电子有限公司 Double-crucible induction heating physical vapor phase transmission device for monocrystalline growth
CN105671629A (en) * 2016-04-06 2016-06-15 中国科学院上海光学精密机械研究所 Edge-defined film-fed growth method of rare-earth sesquioxide laser crystals

Similar Documents

Publication Publication Date Title
AU2006282917B2 (en) System and method for crystal growing
CN101323978B (en) Large size sapphire crystal preparing technology and growing apparatus thereof
CN108048907B (en) Preparation method of large-size and high-performance lanthanum hexaboride single crystal
EP0785298B1 (en) Rapid cooling of cz silicon crystal growth system
CN101580961A (en) Method for growing crystal by reducing atmosphere Kyropoulos method
CN107935572A (en) A kind of ceramic material with special micro-structure and preparation method thereof
CN109082707B (en) Rare earth sesquioxide crystal growth device and method based on temperature gradient method
CN113061982A (en) Continuous direct-pulling single crystal furnace and method capable of controlling content of monocrystalline silicon oxygen
CN201058893Y (en) Device for growing gallium-doped silicon monocrystal by czochralski method
CN104313693A (en) Yttrium aluminum garnet laser crystal doped growth device, crystal growth furnace and preparation method thereof
CN112501690A (en) Growth method of sapphire single crystal
CN110484965B (en) Gallium oxide crystal and growth method and growth device thereof
CN111041558B (en) Rare earth sesquioxide laser crystal growth method
CN105950878B (en) A kind of effective apparatus and method for removing impurity in uranium metal
CN104805499A (en) N type polycrystalline ingot casting equipment and process for preparing N type polycrystalline ingot
CN105133019A (en) Multi-chamber gallium arsenide single crystal growth furnace and method
CN112281214A (en) Method and device for growing rare earth sesquioxide crystal based on double-crucible method
CN209039630U (en) The monocrystal growing furnace of the high-purity germanium single crystal of Grown by CZ Method
CN113930843B (en) Method for growing crystal based on horizontal directional solidification method
CN104357904B (en) A kind of large scale titanium gem crystal growing method
CN101144179B (en) Device for single-crystal growth by physical gas phase transmission precipitation method
CN106048728B (en) A kind of method of growing high quality silicon carbide whisker
CN116145258A (en) Method for growing SiC crystal by low-temperature solution method
CN108866627A (en) A kind of neodymium erbium is co-doped with GYAG laser crystal and preparation method thereof
KR20100071526A (en) Silicon single crystal cooler and silicon single crystal growth apparatus having the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination