[go: up one dir, main page]

CN116988155A - Fluoride crystal and preparation method thereof - Google Patents

Fluoride crystal and preparation method thereof Download PDF

Info

Publication number
CN116988155A
CN116988155A CN202310948790.5A CN202310948790A CN116988155A CN 116988155 A CN116988155 A CN 116988155A CN 202310948790 A CN202310948790 A CN 202310948790A CN 116988155 A CN116988155 A CN 116988155A
Authority
CN
China
Prior art keywords
crucible
temperature
hearth
corundum tube
tube
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
CN202310948790.5A
Other languages
Chinese (zh)
Inventor
董永军
华伟
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.)
Shanghai Xinfeirui Technology Co ltd
Original Assignee
Shanghai Xinfeirui Technology Co ltd
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 Shanghai Xinfeirui Technology Co ltd filed Critical Shanghai Xinfeirui Technology Co ltd
Priority to CN202310948790.5A priority Critical patent/CN116988155A/en
Publication of CN116988155A publication Critical patent/CN116988155A/en
Pending legal-status Critical Current

Links

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
    • C30B29/12—Halides
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/007—Mechanisms for moving either the charge or the heater
    • 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
    • C30B27/00—Single-crystal growth under a protective fluid

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 discloses a preparation method of fluoride crystals, which comprises the following specific steps: s1, weighing compound raw materials, and preparing polycrystalline powder by adopting a solid phase method; s2, placing the polycrystalline powder into a crucible, placing a fluoride crystal rod at the bottom of the crucible to serve as seed crystals, placing the crucible into a sealed corundum tube, and placing the corundum tube into a temperature field of a crystal growth furnace; s3, heating the hearth, vacuumizing the corundum tube, slowly filling inert mixed gas into the tube, and keeping micro-positive pressure in the tube and keeping flowing; s4, continuously heating until the raw materials in the crucible are sufficiently melted; s5, keeping the corundum tube and crucible structure still, slowly lifting the hearth structure of the furnace body upwards, keeping the temperature gradient of a hearth crystallization area unchanged, starting crystallization along with the upward movement of the hearth, stopping lifting when the crystallization height reaches a set value, and stopping introducing gas; s6, taking out the crucible after cooling to room temperature to obtain the blocky crystal.

Description

Fluoride crystal and preparation method thereof
Technical Field
The invention relates to the field of optical crystals, in particular to a fluoride crystal and a preparation method thereof.
Background
In recent decades, with the rapid development of optical communication technology, especially the rising of terahertz communication, the application range of magneto-optical materials is further expanded, and meanwhile, the research of novel magneto-optical materials is promoted, so that the development of magneto-optical devices to low-loss, high-sensitivity and miniaturized directions is promoted. Meanwhile, as the high-power all-solid-state laser has wide application prospects in the civil and military fields of isotope separation, laser processing, photoelectric countermeasure, laser ignition nuclear fusion and the like, the high-power, broadband and high-reliability laser light source is rapidly developed and gradually applied. As the laser output power is continuously increased (kw, mw, gimmick, tewa, etc.), the light transmission aperture of the system needs to be continuously increased to reduce parasitic effects (self-focusing, thermal lens effects, etc.), avoiding laser damage and thermal damage. These two trends are placing increasing demands on new high Verdet constant magneto-optical materials and large size magneto-optical materials.
With the development of crystal growth theory and the progress of preparation technology, the research of magneto-optical crystals has made more breakthroughs in recent decades. The magneto-optical crystals such as Yttrium Iron Garnet (YIG), terbium Aluminum Garnet (TAG), rare earth orthoferrite, rare earth molybdate and rare earth tungstate have higher Verdet constant, and show unique magneto-optical performance advantages and wide application prospects. Therefore, research on crystal growth technology, material properties and device development with magneto-optical crystals as cores has led to great interest. The preparation and performance research of large-size magneto-optical crystals are also important research contents and development directions in the field of magneto-optical crystals, wherein the large-size Tb 3 Ga 5 O 12 The (TGG) crystals exhibit excellent properties in this direction. However, the development of larger aperture faraday isolators based on TGG is often limited by the available TGG crystal size and thermal effects of the larger faraday rotator, which is considered to be a potential bottleneck for high power laser technology. In 2016, stevens et al, from synops, inc. Lu Man, no Luo Pu, reported the optical and magneto-optical properties of KTF crystals, indicating that "KTF has higher laser power and smaller focal length shift and depolarization than TGG under similar experimental conditions," indicating that it is a promising candidate for high power laser applications. Therefore, how to grow KTF crystals with high crystallinity and good optical performance is a problem to be solved.
The prior art provides a method for growing fluoride crystals by using the Bridgman method, which can lead the purity of the grown crystals to be higher and obtain large-size crystals and high-quality crystals; the process is simple and easy to control; the growth speed is high, and a large number of crystals can be prepared in a few hours.
However, in the process of implementing the technical scheme of the embodiment of the application, the inventor discovers that the above technology has at least the following technical problems:
during the crystal growth process, the crucible is moved to generate vibration during the movement process, the vibration has great influence on the crystal quality, and the raw material is inevitably contacted with air during the crystal growth process, so that the obtained crystal contains impurities.
Disclosure of Invention
The fluoride crystal and the crystal growth method thereof solve the problem that the optical performance of the prepared crystal is poor due to crucible vibration in the process of preparing the fluoride crystal in the prior art by adopting a method of moving a fixed crucible to a temperature field, and the problems that impurities are contained in the grown crystal due to contact with air in the crystal growth process are solved by putting raw materials into the crucible and vacuumizing the crucible in a middle corundum tube.
Embodiments of the present application provide a fluoride crystal comprising KTb 3 F 10 、KGd 3 F 10 、KHo 3 F 10 、KEr 3 F 10 、KY 3 F 10 。
The embodiment of the application also provides a crystal growth method of fluoride crystals, which effectively solves the problems, and comprises the following steps:
providing a compound raw material for preparing the fluoride crystal according to the chemical formula of the fluoride crystal, and placing the compound raw material in a reaction tank to prepare high-purity polycrystalline powder of the fluoride crystal;
placing the fluoride crystal polycrystalline powder into a crucible, wherein the crucible is made of graphite or platinum. A crystal bar of the fluoride crystal is placed at the bottom of the crucible to serve as seed crystal;
placing the crucible in a closed corundum tube, wherein one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can vacuumize the corundum tube;
placing the corundum tube in a crystal growth furnace, wherein the crystal growth furnace is set to be a multi-temperature zone, the multi-temperature zone is a longitudinal temperature gradient, the gradient can be changed by adjusting the power of a heater at different positions, and the gradient adjusting range is 10-60 ℃/cm;
after the corundum tube is installed, heating a hearth, vacuumizing the corundum tube, keeping the temperature constant for 2 hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling mixed gas into the corundum tube, wherein the mixed gas is Ar: cf4=9:1 gas mixture, after which a slight positive pressure (0.01-0.03 KPa) was maintained in the tube and flow was maintained.
Continuously heating to a melting point, keeping the temperature for 2-10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3-3mm/h, the heating system of a hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is kept at 20-50 ℃/cm, and as the hearth moves upwards, the melt is gradually crystallized upwards from a seed crystal area at the bottom, and stopping lifting and introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10-35 ℃/h, and cooling to room temperature. And taking out the crucible to obtain the fluoride crystal blocky crystal.
One or more technical solutions provided in the embodiments of the present application at least have the following technical effects or advantages:
1. because the crucible is placed in the sealed corundum tube, the problem that the obtained crystal contains impurities due to contact with air in the crystal growth process is effectively solved, and the advantages of more excellent optical performance and less impurities of the fluoride crystal grown by the method are further realized.
2. Since Ar is used: the mixed gas with CF4=9:1 is used as the protective gas, so that the problem of fluoride ion loss in the crystal growth process is effectively solved, the raw material utilization rate is improved, and the waste of raw materials is reduced.
3. The method is characterized in that a corundum tube and a crucible are kept motionless in the crystal growth process, a hearth structure of a furnace body is slowly lifted upwards, a temperature field structure is moved, different positions of the crucible sequentially pass through crystallization gradient regions of the temperature field, so that the influence of vibration generated during the movement of the crucible on crystallization quality is effectively solved, the temperature field gradient of different regions in the temperature field is different due to the limitation of the structure, the movement of the crucible can cause crystallization to be influenced by gradient difference, the effect of less crystals influenced by gradient change in the crystal growth process is further realized, and the optical performance of the obtained fluoride crystal is further improved.
Drawings
FIG. 1 is an XRD pattern of terbium potassium fluoride crystals according to one embodiment of the present application.
Detailed Description
The embodiment of the application solves the problem that impurities appear in the prepared crystal caused by the reaction of fluoride, air and moisture when the fluoride crystal grows due to contact with air in the prior art by providing the fluoride crystal and the method for growing the fluoride crystal; and vibration generated by moving the crucible in the prior art affects the quality of crystallization, thereby reducing the optical performance of the grown fluoride crystal; and because of the limitation of the structure of the temperature field in the prior art, the temperature field gradients in different areas inside the temperature field are different, and the movement of the crucible can cause the crystallization to be influenced by the gradient difference.
The technical scheme in the embodiment of the application aims to solve the problems, and the overall thought is as follows:
through placing the crucible of placing ternary fluoride raw materials into sealed corundum pipe, the crystal bar of required preparation's crystal is placed to the crucible bottom as the seed crystal, and the material of crucible is platinum or graphite, and corundum pipe one end has to fill the relief vent, can be to corundum pipe evacuation and fill the gassing operation, and after the corundum pipe installation was accomplished, evacuation to the corundum pipe for fluoride raw materials is isolated with the air, avoids fluoride and air reaction to appear impurity.
Heating the hearth when vacuumizing, keeping the temperature at 350 ℃ for two hours, and stopping vacuumizing and filling mixed gas into the pipe, wherein the mixed gas is Ar: CF (compact flash) 4 Is 9:1, and then keeping the micro positive pressure in the pipe to be 0.01-0.03KPa and keeping flowing. The flowing CF4 gas can effectively prevent the loss of fluoride ions in the raw material and the melt.
Continuously heating to a melting point, keeping the temperature constant for two hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3-3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is kept at 20-50 ℃/cm, and as the hearth moves upwards, the melt is gradually crystallized upwards from a bottom seed crystal area, the lifting is stopped when the crystallization height reaches a set value, and the gas is stopped. And (3) slowly cooling, wherein the cooling rate is 10-35 ℃/h, and taking out the crucible after cooling to room temperature to obtain the blocky fluoride crystal. The crucible and corundum tube structure are kept motionless, so that the influence of vibration generated when the crucible is moved on the quality of crystals is effectively avoided, and the influence of differences in temperature field gradients in different areas in the temperature field on the crystals is avoided.
In order to better understand the above technical solutions, the following detailed description will refer to the accompanying drawings and specific embodiments.
Example 1
KF and TbF will be used 3 Ternary fluorination by solid phase methodThe terbium potassium polycrystal raw material is put into a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed into a sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from a bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Example two
KF and YF will be used 3 By solid phase methodThe obtained ternary KY 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from a bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 Impurities in the crystal were measured The XRD pattern obtained was similar to that of figure one.
Example III
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from a bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoidingKEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example IV
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from a bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the cruciblePair KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example five
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from a bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature, Obtaining KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example six
KF and TbF will be used 3 The ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and one end of the corundum tube is provided with a charging and discharging port, so that the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the lifting of the hearth until the crystallization height reaches a set valueAnd stopping lifting the hearth and stopping introducing gas. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Example seven
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature for 6 hours, keeping the corundum tube and the crucible structure still after the raw materials in the crucible are sufficiently melted, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt seeds from the bottom along with the lifting of the hearth And (3) starting crystallization in the crystal area, gradually crystallizing upwards, stopping lifting the hearth when the crystallization height reaches a set value, and stopping introducing gas. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example eight
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
After the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to the melting point, keeping the temperature for 6 hours, keeping the corundum tube and the crucible structure still after the raw materials in the crucible are sufficiently melted, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and liftingThe process keeps the heating system of the furnace temperature field stable, the temperature gradient of the crystallization area of the furnace is kept unchanged, the gradient is maintained at 20 ℃/cm, the melt is gradually crystallized upwards from the bottom seed crystal area along with the upward movement of the furnace, the furnace is stopped being lifted when the crystallization height reaches a set value, and the gas is stopped being introduced. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example nine
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to the melting pointAfter the raw materials in the crucible are fully melted, keeping the corundum tube and the crucible structure motionless, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the lifting of the hearth, and the lifting of the hearth is stopped when the crystallization height reaches a set value, and the gas is stopped. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples ten
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
After the corundum tube is installed, the furnace chamber is heated, and the corundum tube is heatedVacuumizing, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from a bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example eleven
KF and TbF will be used 3 The ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and one end of the corundum tube is provided with a charging and discharging port, so that the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from the bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Example twelve
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from the bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example thirteen
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from the bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples fourteen
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, and the crucible is placed in a dense stateIn the sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, so that the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from the bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example fifteen
KF and GdF will be used 3 Obtained by solid phase methodTo ternary KGd 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 0.3mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 20 ℃/cm, and the melt starts to crystallize upwards gradually from the bottom seed crystal area along with the lifting of the hearth, and stops lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The crystal growth process has a problem of chemical reaction with oxygen and water in the air,KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples sixteen
KF and TbF will be used 3 The ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and one end of the corundum tube is provided with a charging and discharging port, so that the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Example seventeen
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal quality is achieved by using a crucibleThe crucible is placed into a sealed corundum tube and vacuumized, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example eighteen
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples nineteenth
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h The temperature is raised to room temperature, and the crucible is taken out to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example twenty
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
After the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to the melting point, keeping the temperature for 10 hours, keeping the corundum tube and the crucible structure still after the raw materials in the crucible are sufficiently melted, slowly lifting the hearth structure of the furnace body upwards at the lifting speed of 2mm/h, keeping the heating system of the hearth temperature field stable in the lifting process, and keeping the temperature gradient of the hearth crystallization zone unchangedThe gradient is maintained at 35 ℃/cm, and as the hearth moves upwards, the melt is gradually crystallized upwards from the seed crystal area at the bottom, and when the crystallization height reaches a set value, the hearth is stopped being lifted, and the gas is stopped being introduced. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example twenty-one
KF and TbF will be used 3 The ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and one end of the corundum tube is provided with a charging and discharging port, so that the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to the melting point, keeping the temperature for 6 hours, keeping the corundum tube and the crucible structure still after the raw materials in the crucible are sufficiently melted, and slowly lifting the hearth of the furnace body upwards The structure, the rising speed is 2mm/h, the heating system of the furnace temperature field is kept stable in the rising process, the temperature gradient of the crystallization area of the furnace is kept unchanged, the gradient is kept at 35 ℃/cm, along with the upward movement of the furnace, the melt is gradually crystallized upwards from the bottom seed crystal area, the furnace is stopped being lifted when the crystallization height reaches a set value, and the gas is stopped being introduced. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Examples twenty two
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
The temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to the melting point, keeping the temperature for 6 hours, after the raw materials in the crucible are fully melted,the corundum tube and crucible structure is kept motionless, the hearth structure of the furnace body is slowly lifted upwards, the lifting speed is 2mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is kept at 35 ℃/cm, the melt is gradually crystallized upwards from the bottom seed crystal area along with the lifting of the hearth, the lifting of the hearth is stopped when the crystallization height reaches a set value, and the gas is stopped. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples twenty-three
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples twenty-four
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
the corundum tube is installedAnd then heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples twenty-five
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
After the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples twenty-six
KF and TbF will be used 3 Placing ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method into a platinum crucible, placing a KTF crystal bar at the bottom of the crucible as seed crystal, placing the crucible into a sealed corundum tube, and carrying out vacuumizing and deflating operations on the inside of the corundum tube by arranging a charging and deflating port at one end of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from the bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Examples twenty-seven
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided withThe air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from the bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples twenty-eight
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Polycrystalline sourcePlacing the materials into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from the bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples twenty-nine
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from the bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 Overgrowth of crystalThe chemical reaction between the process and oxygen and water in the air is reduced KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example thirty
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 2mm/h, and the lifting process keeps the heating system of the hearth temperature field stable, so that the temperature gradient of the hearth crystallization area is kept unchanged, the gradient is maintained at 35 ℃/cm, and the melt is gradually crystallized upwards from the bottom seed crystal area along with the upward movement of the hearth, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example thirty-one
KF and TbF will be used 3 The ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and one end of the corundum tube is provided with a charging and discharging port, so that the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Example thirty-two
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example thirty-three
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature for 10 hours, keeping the corundum tube and the crucible structure still after the raw materials in the crucible are sufficiently melted, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is kept at 50 ℃/cm, and the melt is gradually crystallized upwards from a bottom seed crystal area along with the lifting of the hearthStopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example thirty-four
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to the melting point, keeping the temperature for 10 hours, keeping the corundum tube and the crucible structure still after the raw materials in the crucible are sufficiently melted, slowly lifting the hearth structure of the furnace body upwards at the lifting speed of 3mm/h, and keeping the hearth temperature field in the lifting process The heating system is stable, the temperature gradient of the crystallization area of the hearth is kept unchanged, the gradient is maintained at 50 ℃/cm, the melt is gradually crystallized upwards from the seed crystal area at the bottom along with the upward movement of the hearth, and when the crystallization height reaches a set value, the hearth is stopped being lifted, and the gas is stopped being introduced. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example thirty-five
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
The temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas=9:1, after which the intra-tube micro positive pressure (0.01-0.032KPa) and flow is maintained. Continuously heating to a melting point, keeping the temperature constant for 10 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Example thirty-six
KF and TbF will be used 3 The ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and one end of the corundum tube is provided with a charging and discharging port, so that the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, and keeping the temperature for two hours when the temperature is increased to 350 DEG C After that, the evacuation was stopped and Ar was slowly charged into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Example thirty-seven
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, the temperature of the hearth is raised, and the furnace is just heatedThe jade pipe is vacuumized, when the temperature is increased to 350 ℃, the temperature is kept constant for two hours, then the vacuumization is stopped, and Ar is slowly filled into the pipe: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KY 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples thirty-eight
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples thirty-nine
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples forty
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 A crystal bar is used as seed crystal, and the crucible is placed in a dense stateIn the sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
After the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 6 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples forty-one
KF and TbF will be used 3 The ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and one end of the corundum tube is provided with a charging and discharging port, so that the inside of the corundum tube can be vacuumized and discharged. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. And (3) slowly cooling, wherein the cooling rate is 10 ℃/h, and taking out the crucible after cooling to room temperature to obtain the KTF massive crystal.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
the method has the advantages that the influence of crucible vibration on the crystallization quality of KTF crystals is avoided, the crucible is placed in a sealed corundum tube and vacuumized, the effect of isolating air is achieved, the problem that the terbium fluoride potassium crystal growth process chemically reacts with oxygen and water in the air is effectively avoided, impurities in the KTF crystals are reduced, and an XRD pattern shown in a graph I is obtained through testing.
Examples forty-two
KF and YF will be used 3 Ternary KY obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a platinum crucible, and placing KY at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KY 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid KY caused by crucible vibration 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KY 3 F 10 The crystal growth process chemically reacts with oxygen and water in the airThe problem of response is that KY is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples forty-three
KF and ErF will be used 3 Ternary KEr obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a graphite crucible, and placing KEr at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KEr 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KEr 3 F 10 The influence of crystal quality is achieved by placing a crucibleThe sealed corundum tube is vacuumized, thereby playing the role of isolating air and effectively avoiding KEr 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KEr 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples forty-four
KF and HoF will be used 3 Ternary KHo obtained by solid phase method 3 F 10 Placing polycrystalline raw material into a platinum crucible, and placing KHo at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in the sealed corundum tube, one end of the corundum tube is provided with a charging and discharging port, and the inside of the corundum tube can be vacuumized and deflated. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is maintained at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and stopping lifting the hearth and stopping introducing gas when the crystallization height reaches a set value. Slowly cooling at a cooling rate of 10deg.C/h, cooling to room temperature, and taking out the crucible to obtain KHo 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoid the vibration of the crucible to KHo 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, thereby playing the role of isolating air and effectively avoiding KHo 3 F 10 The chemical reaction between the crystal growth process and oxygen and water in the air reduces KHo 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Examples forty-five
KF and GdF will be used 3 Ternary KGd obtained by adopting solid phase method 3 F 10 Putting the polycrystalline raw material into a graphite crucible, and placing KGd at the bottom of the crucible 3 F 10 The crystal bar is used as seed crystal, the crucible is placed in a sealed corundum tube, one end of the corundum tube is provided with an air charging and discharging port, and the air charging and discharging port can be used for vacuumizing and discharging the inside of the corundum tube. Placing the corundum tube in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom to form a longitudinal temperature gradient, and the temperature gradient is set to be 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to a melting point, keeping the temperature constant for 2 hours, after the raw materials in the crucible are sufficiently melted, keeping the corundum tube and the crucible structure still, slowly lifting the hearth structure of the furnace body upwards, wherein the lifting speed is 3mm/h, the heating system of the hearth temperature field is kept stable in the lifting process, the temperature gradient of a hearth crystallization area is kept unchanged, the gradient is kept at 50 ℃/cm, and as the hearth moves upwards, the melt starts to crystallize upwards gradually from a bottom seed crystal area, and when the crystallization height reaches a set value, the lifting of the hearth is stopped, and the ventilation is stopped And (5) introducing gas. Slowly cooling to a cooling rate of 10 ℃/h, taking out the crucible after cooling to room temperature to obtain KGd 3 F 10 Bulk crystals.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
avoiding the vibration of the crucible to KGd 3 F 10 The influence of crystal crystallization quality is achieved by placing the crucible in a sealed corundum tube and vacuumizing, so that the effect of isolating air is achieved, and KGd is effectively avoided 3 F 10 The problem of chemical reaction between the crystal growth process and oxygen and water in the air is solved, and KGd is reduced 3 F 10 The XRD patterns of impurities in the crystals obtained by testing are similar to those of the first figure.
Comparative example
A ternary terbium potassium fluoride polycrystal raw material obtained by adopting a solid phase method by using KF and TbF3 is placed in a platinum crucible, a KTF crystal bar is placed at the bottom of the crucible to serve as seed crystal, the crucible is placed in a sealed corundum tube, and the rigid crucible is placed in a temperature field of a crystal growth furnace;
the temperature field structure is set as a multi-temperature area, the temperature of the multi-temperature area structure is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, and the gradient range is set to 10-60 ℃/cm by adjusting the power of heaters at different positions;
after the corundum tube is installed, heating the hearth, vacuumizing the corundum tube, keeping the temperature constant for two hours when the temperature is increased to 350 ℃, stopping vacuumizing, and slowly filling Ar into the tube: CF (compact flash) 4 Mixed gas =9:1, then keep micro positive pressure (0.01-0.032 KPa) in tube and keep flowing. Continuously heating to 1100 ℃, keeping the temperature for 10 hours, slowly rising the crucible structure after the raw materials in the crucible are sufficiently melted, keeping the rising speed at 0.3mm/h, keeping the heating system of the furnace temperature field stable in the rising process, keeping the temperature gradient of the crystallization area of the furnace unchanged, keeping the gradient at 50 ℃/cm, gradually crystallizing upwards from the seed crystal area at the bottom along with the rising of the furnace, stopping lifting the furnace, and stopping introducing gas when the crystallization height reaches a set value. Start to slowly cool down, and cool down quicklyAnd (3) taking out the crucible after the temperature is reduced to the room temperature at the rate of 35 ℃/h, and obtaining the KTF massive crystal.
According to the technical scheme provided by the embodiment of the application, the KTF crystal obtained by the method is low in crystallinity and easy to crush, contains more impurities, and the XRD pattern obtained by testing is quite different from the first pattern.
Table 1 is given the ratios of the parameters of the fluoride crystals prepared in the examples above
As can be seen from Table I, the fluoride crystals prepared in the examples of the present application have significantly reduced impurities and significantly improved crystallinity.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (10)

1. A fluoride crystal, characterized in that the crystal comprises KTb 3 F 10 、KGd 3 F 10 、KHo 3 F 10 、KEr 3 F 10 、KY 3 F 10 。
2. The preparation method of the fluoride crystal is characterized by comprising the following specific steps:
s1: weighing compound raw materials, and preparing polycrystalline powder by adopting a solid phase method;
s2: placing the polycrystalline powder into a crucible, placing a fluoride crystal rod at the bottom of the crucible as seed crystal, placing the crucible into a sealed corundum tube, placing the corundum tube into a temperature field of a crystal growth furnace, and arranging an air charging and discharging port at one end of the corundum tube, wherein the air charging and discharging port can vacuumize the corundum tube;
s3: heating a hearth of the crystal growth furnace, vacuumizing a corundum tube, keeping the temperature constant for 2 hours when the temperature is increased to 350 ℃, stopping vacuumizing, slowly filling inert mixed gas into the tube, keeping micro-positive pressure in the tube, and keeping flowing;
s4: continuously heating to the melting point, and keeping the temperature for 2-10 hours until the raw materials in the crucible are sufficiently melted;
S5: maintaining the corundum tube and crucible structure stationary, slowly lifting the hearth structure of the furnace body upwards, maintaining the heating system of the hearth temperature field stable in the lifting process, maintaining the temperature gradient of the hearth crystallization zone unchanged, gradually crystallizing upwards from the bottom seed crystal zone along with the upward movement of the hearth, stopping lifting when the crystallization height reaches a set value, and stopping introducing gas;
s6: and (5) slowly cooling, and taking out the crucible after cooling to room temperature to obtain the blocky crystal.
3. The method for preparing a fluoride crystal according to claim 2, wherein the polycrystalline powder in step S2 is ternary fluoride polycrystalline powder, and specifically comprises: KTb 3 F 10 、KGd 3 F 10 、KHo 3 F 10 、KEr 3 F 10 、KY 3 F 10 。
4. The method of claim 2, wherein the crucible in step S2 is made of platinum or graphite.
5. The method for preparing fluoride crystal according to claim 2, wherein the specific structure of the temperature field in the step S2 is a multi-temperature zone, the temperature is gradually reduced from top to bottom, a longitudinal temperature gradient is formed, the gradient can be changed by adjusting the power of the heater at different positions, and the gradient adjusting range is 10-60 ℃/cm.
6. The method for preparing a fluoride crystal according to claim 2, wherein the mixed gas in step S3 is specifically Ar: CF (compact flash) 4 Mixed gas of =9:1.
7. The method for producing a fluoride crystal according to claim 2, wherein the micro positive pressure in step S3 is specifically 0.01 to 0.03Kpa.
8. The method for preparing fluoride crystals of claim 2, wherein the specific speed of lifting the hearth structure in step S5 is 0.3-3mm/h.
9. The method for producing a fluoride crystal according to claim 2, wherein the temperature gradient in the furnace crystallization zone in step S5 is specifically 20 to 50 ℃/cm.
10. The method for producing a fluoride crystal according to claim 2, wherein the rate of cooling to room temperature in step S6 is 10 to 35 ℃/h.
CN202310948790.5A 2023-07-31 2023-07-31 Fluoride crystal and preparation method thereof Pending CN116988155A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310948790.5A CN116988155A (en) 2023-07-31 2023-07-31 Fluoride crystal and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310948790.5A CN116988155A (en) 2023-07-31 2023-07-31 Fluoride crystal and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116988155A true CN116988155A (en) 2023-11-03

Family

ID=88520921

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310948790.5A Pending CN116988155A (en) 2023-07-31 2023-07-31 Fluoride crystal and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116988155A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117684264A (en) * 2023-12-11 2024-03-12 安徽科瑞思创晶体材料有限责任公司 Terbium fluoride potassium crystal material and growth method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103060891A (en) * 2013-01-31 2013-04-24 长春理工大学 Device and method for directionally growing fluoride single crystal via lifting small-gradient thermal field
CN107177884A (en) * 2017-06-13 2017-09-19 福州大学 The growing method and device of a kind of fluoride single crystal
US10718963B1 (en) * 2016-11-16 2020-07-21 Electro-Optics Technology, Inc. High power faraday isolators and rotators using potassium terbium fluoride crystals
CN111621849A (en) * 2020-05-25 2020-09-04 北京雷生强式科技有限责任公司 Magneto-optical crystal, magneto-optical device and preparation method
CN112080798A (en) * 2020-09-27 2020-12-15 上海应用技术大学 A kind of near-zero thermal quenching fluoride fluorescent single crystal material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103060891A (en) * 2013-01-31 2013-04-24 长春理工大学 Device and method for directionally growing fluoride single crystal via lifting small-gradient thermal field
US10718963B1 (en) * 2016-11-16 2020-07-21 Electro-Optics Technology, Inc. High power faraday isolators and rotators using potassium terbium fluoride crystals
CN107177884A (en) * 2017-06-13 2017-09-19 福州大学 The growing method and device of a kind of fluoride single crystal
CN111621849A (en) * 2020-05-25 2020-09-04 北京雷生强式科技有限责任公司 Magneto-optical crystal, magneto-optical device and preparation method
CN112080798A (en) * 2020-09-27 2020-12-15 上海应用技术大学 A kind of near-zero thermal quenching fluoride fluorescent single crystal material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KARIMOV, D. N.等: "Growth of KR3F10 (R = Tb-Er) Compounds by the Vertical Directional Crystallization Method. III: Melting Character and Nonstoichiometry of Cubic KHo3F10 and KEr3F10Single Crystals", CRYSTALLOGRAPHY REPORTS, 19 July 2023 (2023-07-19), pages 147 - 153 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117684264A (en) * 2023-12-11 2024-03-12 安徽科瑞思创晶体材料有限责任公司 Terbium fluoride potassium crystal material and growth method thereof

Similar Documents

Publication Publication Date Title
EP2484815B1 (en) METHOD FOR PRODUCING SiC SINGLE CRYSTAL
CN101970728B (en) Single-crystal manufacturing apparatus and method for manufacturing single crystal
CN116988155A (en) Fluoride crystal and preparation method thereof
CN101348939B (en) Growth method for improving utilization rate of gallium arsenide single crystal
CN103911667B (en) A kind of method for monocrystal growth of contact without sidewall of crucible based on necking down type crucible
US4141777A (en) Method of preparing doped single crystals of cadmium telluride
CN117867649B (en) Method for purifying selenium, germanium, gallium, and barium polycrystalline materials and growing high-transmittance crystals by horizontal gradient crystallization
CN117867637B (en) Method for preparing high-purity selenium germanium gallium barium polycrystal material for single crystal growth in one step by utilizing inclined single-temperature zone synthesis furnace
CN110067024A (en) Photoelectric functional crystal M3RE(PO4)3And preparation method thereof
CN103305911B (en) Large size Re:YAP series laser crystal horizontal orientation solidifies preparation method
CN114808134A (en) Preparation process of tellurium-zinc-cadmium single crystal wafer
CN108193270B (en) A kind of preparation method of ternary chalcopyrite semiconductor crystal arsenic germanium cadmium
CN115504480B (en) Compound zinc barium borate and zinc barium borate birefringent crystal, and preparation method and application thereof
CN116988154A (en) Ternary fluoride polycrystalline powder and preparation method thereof
CN209941144U (en) Graphite crucible for growing rare earth ion doped fluoride crystal by heat exchange method
CN105133004A (en) USb2 monocrystal fluxing agent growth method and product prepared in same
CN109797428B (en) Growth method for growing rare earth ion doped fluoride crystal by heat exchange method
JP3207983B2 (en) Method for producing single crystals of I-III-VI2 group compounds
ITMI992423A1 (en) INDIO PHOSPHIDE DIRECT SYNTHESIS PROCEDURE
Kuriyama Bridgman growth of lithium indium alloy single crystals
CN111549376A (en) Cerium-doped lanthanum bromide scintillation crystal and growth method thereof
CN119121391B (en) Method for preparing tellurium-indium-lead polycrystal material for single crystal growth by horizontal gradient crystallization method
CN106012016B (en) A kind of adjustable up-conversion luminescence non-plumbum ferroelectric monocrystal of electricity and preparation method thereof
CN112725881B (en) High-purity aluminum oxide crystal multi-stage continuous melting device and method for preparing sapphire
CN119121407A (en) A method for reducing the influence of gravity to grow low optical absorption and high uniformity indium lead telluride single crystals

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