CN106757317A - Rare earth crystal growth equipment, rare earth crystal growth technique and application - Google Patents
Rare earth crystal growth equipment, rare earth crystal growth technique and application Download PDFInfo
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- CN106757317A CN106757317A CN201611059073.3A CN201611059073A CN106757317A CN 106757317 A CN106757317 A CN 106757317A CN 201611059073 A CN201611059073 A CN 201611059073A CN 106757317 A CN106757317 A CN 106757317A
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- rare earth
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
- C30B15/22—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal
- C30B15/26—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal using television detectors; using photo or X-ray detectors
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/28—Complex oxides with formula A3Me5O12 wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. garnets
-
- 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
- C30B29/34—Silicates
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- 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 provides a kind of rare earth crystal growth equipment, the rare earth growth apparatus include：Crystal growing furnace；The crystal growing furnace is internally provided with heating element heater；The burner hearth top of the crystal growing furnace is provided with observation form；The top of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with Non-contact Infrared Temperature Measurement device.Compared with prior art, the present invention sets Non-contact Infrared Temperature Measurement device on the observation form top on the top of crystal growing furnace, realize axially and radially temperature measuring and calculating at melt/solid interface, thermal field structure according to needed for the thermograde design rare earth crystal growth for measuring, using the chemical bonding theory of crystalline growth, make pulling growth systems thermodynamics and dynamics Controlling meet Optimum Matching, shorten rare earth crystal growth duration, the Energy Efficiency Ratio of crystal growth is improved, crystal yield rate is improved.
Description
Technical field
The present invention relates to crystalline material technical field, and in particular to by rare earth crystal growth equipment, rare earth crystal growth work
Skill and application.
Background technology
Rare earth functional crystal material can be carried as the important medium of the conversions such as light, sound, electricity for various important Primary Components
For high-quality operation material.Rare earth scintillating crystals have high density, High Light Output, the characteristic of fast decay, meet high-energy physics,
Basic demand of the application fields such as nuclear medicine to scintillator, rare earth photoelectric crystal material can realize electricity, the interaction of light and
Conversion, is widely used in the fields such as communication, aerospace, medical science, geology, meteorology, architecture, military technology.
The crystal growing furnace of French Cyberstar companies production is acknowledged as with best combination property.The country is directed to
Silicon single crystal and sapphire single-crystal have produced special crystal growth equipment.And it is directed to the special crystal of rare earth functional crystal material
Growing system is not yet developed.Rare earth oxide crystalline melting point (more than 1700 DEG C) high is wanted, it is necessary to meet its thermodynamics
Grown under the conditions of the thermal field asked.For existing crystal pull growth apparatus, substantial amounts of early stage exploration need to be carried out, improve thermal field knot
Structure, optimizes the thermograde of rare earth oxide crystal growth, due to its very long process so that rare earth oxide crystalline material
The suitable height of early investment cost.Existing general crystal pull growth apparatus are needed badly into that be designed to rare earth oxide crystal is special
Growth apparatus.
In rare earth crystal growing process, the axially and radially temperature built depending on thermodynamically demand of thermal field structure
Gradient.At present, Frequency Induction Heating has that melting efficiency is high, furnace temperature is easy to control, good energy-conserving effect, compact conformation, overload capacity
Strong the features such as, is widely used in crystal pull growth furnace.However, being merely able to provide EF power in growth course, lack straight
See temperature to show, be unfavorable for the acquisition of thermograde, it is impossible to for the design/adjustment of thermal field structure provides temperature foundation directly perceived.By
1700 DEG C are usually above in the fusing point of rare earth oxide crystal, the temperature in the temperature range for commonly using thermocouple indicates exception tired
It is difficult.Additionally, the temperature survey of crystal growth mainly uses contact temperature-measuring mode at present.Contact temperature-measuring is generally using conventional warm
Galvanic couple is fixed in the insulation material outside crystal growing crucible that (connected mode is mainly and avoids contact with melt and bring crystal dirty
Dye), the temperature of measurement is not real melt temperature, and position is fixed, it is impossible to measures multi-point temp, i.e., cannot obtain temperature ladder
Degree.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide rare earth crystal growth equipment, rare earth crystal growth
Technique and application, the growth apparatus can realize the thermograde measuring and calculating at melt/solid interface.
The invention provides a kind of rare earth crystal growth equipment, including：
Crystal growing furnace；
The crystal growing furnace is internally provided with heating element heater；
The burner hearth top of the crystal growing furnace is provided with observation form；
The top of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with non-contact infrared survey
Warm device.
Preferably, a diameter of 50~80mm of the observation form.
Preferably, the Non-contact Infrared Temperature Measurement device includes multidirectional adjusting bracket and is arranged in multidirectional adjusting bracket
Double color infrared ray element.
Preferably, the burner hearth top of the crystal growing furnace it is outside, described observation form periphery be provided with circulation it is cold
But water system；
The top of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with image observation element.
Preferably, the sidewall of the furnace body of the crystal growing furnace by stove to including the first insulation material for setting gradually outside stove
Layer, the second adiabator layer and the 3rd adiabator layer；First adiabator layer is zirconium oxide insulation material；Described second
Adiabator layer is formed by zirconium oxide with aluminum oxide；3rd adiabator layer is zirconium oxide insulation material.
Preferably, the density of first adiabator layer is 5.2~3.8g/cm3；Second adiabator layer it is close
It is 3.5~2.3g/cm to spend3；The density of the 3rd adiabator layer is 1.8~0.6g/cm3。
Preferably, the thickness of first adiabator layer is 1~3.5cm；
The thickness of second adiabator layer is 1~4cm；
The thickness of the 3rd adiabator layer is 0.5~1.5cm.
Preferably, the heating element heater is iraurite product and Cu induction coils；The size of the iraurite product be φ 70~
140mm, deep 50~150mm；The size of the Cu induction coils is 2~3 times of iraurite product size.
Present invention also offers a kind of rare earth crystal growth technique, including：
A) after high-purity rare-earth raw material is mixed, mixed material is obtained；
B) under vacuum or protective atmosphere, after the mixed material that above-mentioned steps are obtained is through oversintering, polycrystal material is obtained
Block；
C) under vacuum or protective atmosphere, the polycrystal material block that above-mentioned steps are obtained is in claim 1~8 any one
After being melted in described rare earth crystal growth equipment, after carrying out crystal growth under the guiding of seed crystal using czochralski method, obtain dilute
Native crystal.
Present invention also offers above-mentioned rare earth crystal growth equipment in growth of yttrium-aluminum Garnet crystal and/or the positive silicon of rare earth
Application in hydrochlorate crystalloid.
The invention provides a kind of rare earth crystal growth equipment, the rare earth growth apparatus include：Crystal growing furnace；The crystalline substance
Body growth furnace is internally provided with heating element heater；The burner hearth top of the crystal growing furnace is provided with observation form；The crystal
The top of outside, the described observation form on the burner hearth top of growth furnace is provided with Non-contact Infrared Temperature Measurement device.With existing skill
Art is compared, and the present invention sets Non-contact Infrared Temperature Measurement device on the observation form top on the top of crystal growing furnace, is realized molten
Axially and radially temperature measuring and calculating at body/solid interface, the thermal field according to needed for the thermograde design rare earth crystal growth for measuring
Structure, using the chemical bonding theory of crystalline growth, makes pulling growth systems thermodynamics and dynamics Controlling meet Optimum Matching,
Shorten rare earth crystal growth duration, improve the Energy Efficiency Ratio of crystal growth, improve crystal yield rate.
Brief description of the drawings
The structural representation of the rare earth crystal growth equipment that Fig. 1 is provided for the present invention；
The structural representation of the rare earth crystal growth equipment that Fig. 2 is provided for the present invention；
The structural representation of the recirculating cooling water system that Fig. 3 is provided for the present invention；
The structural representation of the crystal growing furnace that Fig. 4 is provided for the present invention.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
Referring to Fig. 1, Fig. 2, Fig. 3 and Fig. 4, the structural representation of the rare earth crystal growth equipment that Fig. 1 and Fig. 2 is provided for the present invention
Figure；Fig. 3 is the structural representation of recirculating cooling water system；Fig. 4 is the structural representation of crystal growing furnace.
The invention provides a kind of rare earth crystal growth equipment, including：Crystal growing furnace；The inside of the crystal growing furnace
It is provided with heating element heater；The burner hearth top of the crystal growing furnace is provided with observation form；The burner hearth top of the crystal growing furnace
The top of outside, the described observation form at end is provided with Non-contact Infrared Temperature Measurement device.
The present invention provide rare earth crystal growth equipment can intuitively obtain the true temperature of crystal growth, Gu realize melt/
Thermograde measuring and calculating at body interface, growing high quality rare earth optical crystal material improves rare earth added value.
According to the present invention, the crystal growing furnace is internally provided with heating element heater；The heating element heater is this area skill
Heating element heater known to art personnel, has no special limitation, heretofore described heating element heater be preferably iraurite product with
Cu induction coils；The iraurite product is preferably dimensioned to be 70~140mm of φ, deep 50~150mm；The chi of the Cu induction coils
Very little be preferably iraurite product size 2~3 times.
The sidewall of the furnace body of the crystal growing furnace by stove to the first adiabator layer for preferably including outside stove to set gradually,
Second adiabator layer and the 3rd adiabator layer；First adiabator layer is zirconium oxide insulation material；Described second protects
Adiabator layer is formed by zirconium oxide with aluminum oxide；3rd adiabator layer is zirconium oxide insulation material.Wherein, described first
The density of adiabator layer is preferably 5.2~3.8g/cm3, more preferably 5~4g/cm3, it is further preferably 4.6~4g/cm3, it is optimal
Elect 4.2g/cm as3；The thickness of first heat-insulation layer is preferably 1~3.5cm, preferably 2~3.5cm, further preferably for 2~
3cm, most preferably 2.5cm；The density of second adiabator layer is preferably 3.5~2.3g/cm3, more preferably 3.3~
2.8g/cm3, it is further preferably 3.2~3g/cm3, most preferably 3.0g/cm3；The thickness of second heat-insulation layer is preferably 1~
4cm, preferably 2~3.5cm, are further preferably 2.5~3cm, most preferably 3cm；The density of the 3rd adiabator layer is preferred
It is 1.8~0.6g/cm3, more preferably 1.4~0.6g/cm3, it is further preferably 1.0~0.6g/cm3, most preferably 0.8g/cm3；
The thickness of the 3rd heat-insulation layer is preferably 0.5~1.5cm, preferably 0.8~1.2cm, is further preferably 1.0cm.
The present invention builds the temperature field structure and its supporting heating unit suitable for rare earth oxide in crystal growth burner hearth
Part, for rare earth oxide crystal growth provides suitable axially and radially thermograde, realizes φ 30~80mm yttrium-aluminium-garnets
Crystalloid (RE:Y3Al5O12, RE=Ce, Nd, Sm, Eu, Ho, Tm, Er, Yb) and rare earth orthosilicate (Ce:RE2SiO5, RE=
La,Gd,Y)。
The burner hearth top of the crystal growing furnace is provided with observation form；The observation form is preferably wide-angle observation and regards
Window；The diameter of the observation form is preferably 50~80mm.
The top of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with non-contact infrared survey
Warm device.In the present invention, the Non-contact Infrared Temperature Measurement device preferably includes multidirectional adjusting bracket and is arranged on multidirectional tune
Double color infrared ray element on section support.Multidirectional adjusting bracket can be such that double color infrared ray element realizes both horizontally and vertically
180 ° of rotations, realize Multi-point focusing, obtain multi-point temp, calculate axially and radially thermograde.
The double color infrared ray element is preferably digitlization double color infrared ray element and realizes melt liquid level temperature digital
Change display function, the influence of quartz window is corrected using double color infrared ray, acquisition approaches melt true temperature numerical value, and temperature is rung
Should be less than 1ms.Can realize that bath surface radial symmetry gradient is estimated by adjusting temperature measurer facula position；According to rare-earth oxidation
Thermograde needed for thing crystal growth, design meets the thermal field structure of thermograde needed for rare earth crystal growth, using crystal
Growth theory, it is determined that suitable crystal growth parameters, special growth apparatus are escalated into by general crystal growth equipment, shortens dilute
Native crystal growth duration, improves the Energy Efficiency Ratio of crystal growth system.
According to the present invention, the periphery of outside, the described observation form on the burner hearth top of the crystal growing furnace preferably also sets
It is equipped with recirculating cooling water system；The top of outside, the described observation form on the burner hearth top of the crystal growing furnace preferably also sets
It is equipped with image observation element.
The periphery of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with circulating cooling water system
System, can take away the heat that the transmission of burner hearth top is thought in crystal growing process, be provided to install image observation element outside observation form
Suitable working environment.
The top of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with image observation element；
Described image observation element is image observation element well known to those skilled in the art, has no special limitation, the present invention
In preferably include video camera and video camera support；The video camera can by image support rotate, more preferably can 360 ° rotation, fill
Divide the advantage using the wide viewing angle of upper viewing window, 122 °~154 ° wide viewing angles observations can be realized to burner hearth internal environment；It is described
Video camera is preferably connected with computer end, so as to realize image remote monitoring function.
In the present invention, described image observation element preferably also includes optical filter；The optical filter is arranged at the shooting
The front end of instrument.Avoid causing the image cannot to observe melt temperature is excessively bright higher than 1800 DEG C of high lights for bringing.
The present invention sets recirculating cooling water system outside the observation form on the top of crystal growing furnace, can take away crystal life
The heat transmitted to burner hearth top in growth process, suitable building ring is provided to install image observation element outside observation form
Border, and passing through image observation element can realize the remote observation of crystal pull stove.
In the present invention, because Non-contact Infrared Temperature Measurement device and image observation element are all to observe form as detection
Window, preferably couples double color infrared ray element with video camera, makes both public same focal lengths, improves space availability ratio.
The present invention sets Non-contact Infrared Temperature Measurement device on the observation form top on the top of crystal growing furnace, realizes molten
Axially and radially temperature measuring and calculating at body/solid interface, the thermal field according to needed for the thermograde design rare earth crystal growth for measuring
Structure, using the chemical bonding theory of crystalline growth, makes pulling growth systems thermodynamics and dynamics Controlling meet Optimum Matching,
Shorten rare earth crystal growth duration, improve the Energy Efficiency Ratio of crystal growth, improve crystal yield rate.
Present invention also offers a kind of technique for applying above-mentioned rare earth crystal growth equipment to carry out rare earth crystal growth, bag
Include：A) after high-purity rare-earth raw material is mixed, mixed material is obtained；B) under vacuum or protective atmosphere, by above-mentioned steps
After the mixed material for obtaining is through oversintering, polycrystal material block is obtained；C) under vacuum or protective atmosphere, above-mentioned steps are obtained
After polycrystal material block melts in above-mentioned rare earth crystal growth equipment, crystal growth is carried out under the guiding of seed crystal using czochralski method
Afterwards, rare earth crystal is obtained.
The all raw materials of the present invention, originate to it and are not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
The all raw materials of the present invention, its purity is higher than 0.9999 (4N).
Wherein, the high-purity rare-earth raw material be the high pure raw material that can obtain rare earth crystal well known to those skilled in the art i.e.
Can, special limitation is had no, preferably can growth of yttrium-aluminum Garnet crystal and/or rare earth orthosilicate crystalloid in the present invention
High-purity rare-earth raw material.
The present invention is mixed high pure raw material according to setting ratio, obtains mixed material.The present invention is to the mixing
Condition is not particularly limited, with the mixing condition of such reaction well known to those skilled in the art, those skilled in the art
Can be adjusted according to practical condition, raw material condition, the present invention is preferably uniform mixing, the time of the mixing is preferred
It is 24~120h, more preferably 40~120h, more preferably 60~120h, most preferably 80~120h.The present invention is to described mixed
The mode of conjunction is not particularly limited, with hybrid mode well known to those skilled in the art, present invention preferably employs blender mixing.
The present invention is not particularly limited to other properties of the mixed material, is flashed with the rare earth for preparing well known to those skilled in the art
The property of the mixed material of crystal, the granularity of mixed material of the present invention is preferably 0.05~30 μm, more preferably 0.1
~25 μm, most preferably more preferably 1~15 μm, 2~8 μm.
It is of the invention subsequent under vacuum or protective atmosphere, after the mixed material that above-mentioned steps are obtained is through oversintering, obtain
To polycrystal material block.
The present invention is not particularly limited to the pressure of the vacuum, with the true of sintering process well known to those skilled in the art
Pneumatics power, the pressure of vacuum of the present invention is preferably less than equal to 10Pa, more preferably less than equal to 7Pa, more preferably
It is less than or equal to 5Pa, most preferably 3~5Pa；The present invention is not particularly limited to the protective atmosphere, with art technology
For the protective atmosphere of sintering rare-earth crystal known to personnel, protective atmosphere of the present invention is preferably nitrogen, lazy
One or more in property gas and reducibility gas, more preferably nitrogen and reducibility gas, most preferably nitrogen and hydrogen.
The present invention is not particularly limited to the actual conditions of the sintering, with sintering condition well known to those skilled in the art
, the temperature of sintering of the present invention is preferably 900~1300 DEG C, more preferably 950~1250 DEG C, more preferably 1000~
1200 DEG C, most preferably 1050~1150 DEG C.The time of sintering of the present invention is preferably 12~20h, more preferably 13~
22h, more preferably 14~22h, most preferably 15~20h.The present invention is not particularly limited to the equipment of the sintering, with ability
Preferably be put into high-purity crucible the mixed material in sintering furnace by agglomerating plant known to field technique personnel, the present invention
Sintering.
The present invention after mixed material further preferably is first passed through into cake of press, obtains raw material cake to reach more preferable sintering effect, then
It is sintered.The present invention is not particularly limited to the specific steps and technological parameter of the cake of press, ripe with those skilled in the art
The specific steps and technological parameter of pressed compact before the sintering known, those skilled in the art can be according to practical condition, original
Material composition and properties of product requirement are selected and adjusted, and the pressure of cake of press of the present invention is preferably 20~70MPa, more excellent
Elect 30~60MPa, most preferably 40~50MPa as.
Of the invention last under vacuum or protective atmosphere, the polycrystal material block that above-mentioned steps are obtained is in above-mentioned rare earth crystal
After growth apparatus fusing, after crystal growth is carried out under the guiding of czochralski method seed crystal, rare earth crystal is obtained.
The present invention is not particularly limited to the pressure of the vacuum, with the true of sintering process well known to those skilled in the art
Pneumatics power, the pressure of vacuum of the present invention is preferably less than equal to 10Pa, more preferably less than equal to 7Pa, more preferably
It is less than or equal to 5Pa, most preferably 1~3Pa；The present invention is not particularly limited to the protective atmosphere, with art technology
For the protective atmosphere of sintering rare-earth crystal known to personnel, protective atmosphere of the present invention is preferably nitrogen, lazy
One or more in property gas and reducibility gas, more preferably nitrogen and reducibility gas, most preferably nitrogen and hydrogen.
Into temperature rise period, the fusing of polycrystal material BOB(beginning of block).Test material block, melt temperature, thermometric are interval up to 900~2500
℃.The rare earth crystal growth equipment provided using the present invention can realize electromotion focusing, and measured melt liquid level area is smaller than
The spot size of temperature measurer；The digital display of measurement temperature, temperature-responsive is less than 1ms.By adjusting temperature measurer facula position energy
Enough realize that bath surface radial symmetry gradient is estimated.The melt of yttrium-aluminium-garnet class and rare earth orthosilicate crystalloid includes difference
Fluid is constituted, and after crystalline substance material is completely melt, feature liquid fluid line occurs.Melt center and distance are measured using double color infrared temperature measuring instrument
The temperature of the melt temperature of melt center x position, x is preferably 10,20,30,40,50,60,70,80,90,100mm measuring and calculating radially
Thermograde.Inertia/reproducibility the gas of melt center and vertical range melt center y location is measured using double color infrared temperature measuring instrument
The temperature of body, y is preferably 10,20,30,40,50,60mm, calculates axial-temperature gradient.Adjustment EF power, treats melt center
When temperature is higher than 5~50 DEG C of yttrium-aluminium-garnet crystalloid and rare earth orthosilicate crystalline melting point, you can seed crystal is contacted into liquid level,
Carry out seeding operation.
The present invention is not particularly limited to the seed crystal, with well known to those skilled in the art brilliant for preparing rare earth flicker
The seed crystal of body.
The present invention is not particularly limited to the temperature-rise period of the intensification polycrystal material block, with well known to those skilled in the art
Temperature-rise period.Seeding operation of the present invention is preferably carried out when there is feature liquid fluid line (liquid fluid line).Art technology
Personnel are it is understood that liquid fluid line refers to all tangent with rate vector curve on every bit in fluid liquid.Institute of the present invention
State occur feature liquid fluid line in macroscopical presentation be preferably, polycrystal material block liquid phase is changed into from solid phase after when ripple occurs in liquid phase surface
When, as there is feature liquid fluid line.
The present invention carries out seeding operation after there is feature liquid fluid line using seed crystal, then carries out crystal using czochralski method
Growth, the growth rate and the speed of rotation being calculated according to crystal theoretical realizes crystal growth, obtains rare earth crystal.The present invention
The czochralski method is not particularly limited, with the czochralski method for preparing rare earth crystal well known to those skilled in the art；This hair
The bright technological parameter to the czochralski method is not particularly limited, and those skilled in the art can be according to practical condition, raw material
Composition and properties of product requirement are selected and adjusted.
After seeding terminates, the growth of the growth rate and speed of rotation crystal that obtain is calculated according to crystal theoretical, preferably in fact
The growth of existing yttrium-aluminium-garnet crystalloid and/or rare earth orthosilicate crystalloid；In the present invention, the speed of the crystal growth
Preferably 2.5~8.0mm/h, more preferably 4~7.5mm/h, more preferably 5.1~7.0mm/h, most preferably 5.5~
6.5mm/h；The Crystal Rotation speed is preferably 6~30rpm, more preferably more preferably 8~25rpm, 10~22rpm, most
Preferably 10~18rpm.The temperature of crystal/melt interface, calculates thermograde in test crystal growing process.
According to measuring and calculating in crystal (yttrium-aluminium-garnet class and rare earth orthosilicate crystalloid) growth course axially and radially
Thermograde, so that the suitable insulation material of thermal conductivity factor selection and its geometry, size can be obtained by insulation material,
Build upper and lower thermal field structure；Can also be from the chemical bonding theory of crystalline growth, with reference in rare earth scintillating crystals growth course
Interface bonding structure, determine dominant growth direction, with reference to rare earth crystal thermal field structure using corresponding crystal orientation seed crystal
And the growth parameter(s) for growing in the direction is calculated and optimizes, fast-growth yttrium-aluminium-garnet class and rare earth orthosilicate are brilliant
Body.
Present invention also offers a kind of above-mentioned rare earth crystal growth equipment in growth of yttrium-aluminum Garnet crystal and/or rare earth
Application in orthosilicate crystalloid.
Multipoint temperature measuring is realized using external Non-contact Infrared Temperature Measurement device, realizes axially calculating with footpath phase temperature；
Thermal field structure and its supporting heating element heater according to needed for the thermograde design rare earth crystal growth for measuring, using crystalline growth
Chemical bonding theory, make pulling growth systems thermodynamics and dynamics Controlling meet Optimum Matching, crystal growth personnel need not
Early stage is designed, and yttrium-aluminium-garnet class and rare earth orthosilicate crystal growth are carried out by directly feeding intake.
In order to further illustrate the present invention, with reference to the rare earth crystal growth equipment, dilute that embodiment is provided the present invention
Native crystal growth technique and application are described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Rare earth crystal growth equipment is provided：Crystal growing furnace；The crystal growing furnace is internally provided with heating element heater, plus
Thermal element is preferably iraurite product and Cu induction coils；The iraurite product is preferably dimensioned to be φ 125mm, depth 125mm；It is described
Cu induction coils are preferably dimensioned to be 2~3 times of iraurite product size；The sidewall of the furnace body of the crystal growing furnace by stove to stove
Outer the first adiabator layer, the second adiabator layer and the 3rd adiabator layer for preferably including to set gradually；Described first protects
Adiabator layer is zirconium oxide insulation material；Second adiabator layer is formed by zirconium oxide with aluminum oxide；3rd insulation
Material layer is zirconium oxide insulation material；The density of first adiabator layer is preferably 4.2g/cm3；First heat-insulation layer
Thickness be 2.5cm；The density of second adiabator layer is preferably 3.0g/cm3；The thickness of second heat-insulation layer is
3.0cm；The density of the 3rd adiabator layer is preferably 0.8g/cm3；The thickness of the 3rd heat-insulation layer is 1.0cm；It is described
The burner hearth top of crystal growing furnace is provided with observation form, a diameter of 50mm of the observation form；The crystal growing furnace
The periphery of outside, the described observation form on burner hearth top is provided with recirculating cooling water system；The burner hearth top of the crystal growing furnace
The top of outside, the described observation form at end is provided with Non-contact Infrared Temperature Measurement device, Non-contact Infrared Temperature Measurement device bag
Multidirectional adjusting bracket is included with the double color infrared ray element being arranged in multidirectional adjusting bracket；Double color infrared ray element can pass through
Multidirectional adjusting bracket realizes both horizontally and vertically 180 ° of rotations.
Y by purity higher than 99.995%2O3、Al2O3Powder, according to Y2O3:Al2O3=3:5 proportioning weighings, suppress and burn
Form round pie Y3Al5O12Polycrystal raw material.The tired closed assembly of 5000g polycrystal raw materials is entered the Ir crucibles in above-mentioned crystal growth burner hearth
It is interior, in the seed crystal in front loaded [111] direction of seed rod.Adjustment crystal growing furnace top double color infrared ray original paper position and angle
Degree, focuses in bath surface center.Burner hearth is filled with high-purity N after vacuumizing2Gas is used as protection gas, intensification melt (polycrystal material
Block).Calculated using the chemical bonding theory of crystalline growth and determine dominant growth direction [111], calculate Y3Al5O12Along [111] side
To pulling growth 2.5~6.0mm/h of speed, 8~18rpm of the speed of rotation.After crystalline substance material is completely melt, there is feature liquid stream
Line.Adjustment EF power, body core temperature fusion is higher than Y3Al5O12During 3~5 DEG C of fusing point, measured using double color infrared temperature measuring instrument
Melt center and apart from melt center x=5, the melt temperature of 10,20mm positions, respectively 1833.5,1834.3,1835.2,
1837.4 DEG C, 0.16,0.18,0.22 DEG C/mm of measuring and calculating radial symmetry gradient.Using double color infrared temperature measuring instrument measurement melt center and
Vertical range melt center y=5, the inert gas temperature of 10,20,30mm positions, respectively 1830.4,1825.7,1812.4,
1796.5 DEG C, measuring and calculating axial-temperature gradient is -0.62, -0.94, -1.33, -1.59 DEG C/mm.Seed crystal is contacted into liquid level, is drawn
Crystalline substance operation.When slightly having growth during seed crystal contact melt liquid level, it was demonstrated that growth temperature gradient is suitable.After " necking down " operation, crystal enters
Enter growth phase, the growth parameter(s) calculated according to the chemical bonding theory of crystalline growth is grown, obtain isometrical φ 78mm, weight
The Y of 3.05kg3Al5O12Crystal.
Growth Y3Al5O12Crystalline size：Isometrical size φ 78mm, crystal total length 230mm, gross weight 3.05kg.Without cracking,
Crystal mass is intact.
Embodiment 2
Rare earth crystal growth equipment in embodiment 1 is provided.
Y by purity higher than 99.995%2O3、Al2O3Powder, according to Nd2O3:Y2O3:Al2O3=0.06:2.94:5 proportionings
Weighing, suppresses and sinters into round pie Nd:Y3Al5O12Polycrystal raw material.The tired closed assembly of 1000g polycrystal raw materials is entered into above-mentioned crystal growth
In Ir crucibles in burner hearth, in the seed crystal in front loaded [111] direction of seed rod.Adjustment crystal growing furnace top dual-color red exterior measuring
Warm original paper position and angle, focus in bath surface center.Burner hearth is filled with high-purity N after vacuumizing2Gas heats up as protection gas
Melt (polycrystal material block).Calculated using the chemical bonding theory of crystalline growth and determine dominant growth direction [111], calculated
Y3Al5O12Along the pulling growth 2.0~5.0mm/h of speed, 8~18rpm of the speed of rotation in [111] direction.It is completely melt in crystalline substance material
Afterwards, there is feature liquid fluid line.Adjustment EF power, body core temperature fusion is higher than Nd:Y3Al5O12During 3~5 DEG C of fusing point, utilize
Double color infrared temperature measuring instrument measures melt center and apart from melt center x=5, the melt temperature of 10,20mm positions, respectively
1827.2,1828.3,1829.8,1834.2 DEG C, 0.22,0.30,0.44 DEG C/mm of measuring and calculating radial symmetry gradient.Using dual-color red
Outer temperature measurer measures melt center and vertical range melt center y=5, the inert gas temperature of 10,20,30mm positions, difference
Be 1824.3,1819.1,1802.5,1780.7 DEG C, measuring and calculating axial-temperature gradient be -0.58, -1.04, -1.66, -2.18 DEG C/
mm.Seed crystal is contacted into liquid level, seeding operation is carried out.When slightly having growth during seed crystal contact melt liquid level, it was demonstrated that growth temperature gradient
Properly.After " necking down " operation, crystal enters growth phase, and the growth parameter(s) calculated according to the chemical bonding theory of crystalline growth is entered
Row growth, obtains isometrical φ 40mm, the Nd of weight 520g:Y3Al5O12Crystal.
Growth Nd:Y3Al5O12Crystalline size：Isometrical size φ 40mm, crystal total length 90mm, gross weight 0.52kg.Nothing is opened
Split, crystal mass is intact.Go out to realize that laser is exported in 1062nm.
Embodiment 3
Rare earth crystal growth equipment in embodiment 1 is provided.
As procedure described above, the Lu by purity higher than 99.995%2O3、Y2O3、SiO2Powder, according to Lu2O3:Y2O3:SiO2
=0.95:0.05:1 proportioning weighing, suppresses and sinters into round pie (Lu0.95Y0.05)2SiO5Polycrystal raw material.4400g polycrystalline is former
The tired closed assembly of material enters in the Ir crucibles in above-mentioned crystal growth burner hearth, in the seed crystal in front loaded [010] direction of seed rod.Adjustment is brilliant
Body growth furnace top high temperature video camera observation position and angle, focus in bath surface center.Burner hearth is filled with height after vacuumizing
Pure H2+ Ar is used as protection gas, intensification melt (polycrystal material block).Determination advantage is calculated using the chemical bonding theory of crystalline growth to give birth to
Length direction [010], calculates (Lu0.95Y0.05)2SiO5Along the pulling growth 3.5~6.5mm/h of speed in [010] direction, the speed of rotation
10~25rpm.Adjustment EF power, body core temperature fusion is higher than (Lu0.95Y0.05)2SiO5During 5~10 DEG C of fusing point, using double
Color infrared radiation thermometer measures melt center and apart from melt center x=5, the melt temperature of 10,20mm positions, respectively
2018.6,2019.8,2023.4,2036.8 DEG C, 0.44,0.72,1.34 DEG C/mm of measuring and calculating radial symmetry gradient.Using dual-color red
Outer temperature measurer measures melt center and vertical range melt center y=5, the inert gas temperature of 10,20,30mm positions, difference
Be 2014.7,2008.5,1989.0,1961.7 DEG C, measuring and calculating axial-temperature gradient be -0.78, -1.24, -1.95, -2.73 DEG C/
mm.Seed crystal is contacted into liquid level, seeding operation is carried out.When slightly having growth during seed crystal contact melt liquid level, it was demonstrated that growth temperature gradient
Properly.After " necking down " operation, crystal enters growth phase, and the growth parameter(s) calculated according to the chemical bonding theory of crystalline growth is entered
Row growth, obtains isometrical φ the 50mm, (Lu of weight 2150g0.95Y0.05)2SiO5Crystal.
Growth (Lu0.95Y0.05)2SiO5Crystalline size：Isometrical size φ 50mm, crystal total length 135mm, gross weight
2.15kg.Without cracking, crystal mass is intact.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (10)
1. a kind of rare earth crystal growth equipment, it is characterised in that including：
Crystal growing furnace；
The crystal growing furnace is internally provided with heating element heater；
The burner hearth top of the crystal growing furnace is provided with observation form；
The top of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with Non-contact Infrared Temperature Measurement dress
Put.
2. rare earth crystal growth equipment according to claim 1, it is characterised in that a diameter of the 50 of the observation form~
80mm。
3. rare earth crystal growth equipment according to claim 1, it is characterised in that the Non-contact Infrared Temperature Measurement device
Including multidirectional adjusting bracket and the double color infrared ray element being arranged in multidirectional adjusting bracket.
4. rare earth crystal growth equipment according to claim 1, it is characterised in that the burner hearth top of the crystal growing furnace
It is outside, described observation form periphery be provided with recirculating cooling water system；
The top of outside, the described observation form on the burner hearth top of the crystal growing furnace is provided with image observation element.
5. rare earth crystal growth equipment according to claim 1, it is characterised in that the sidewall of the furnace body of the crystal growing furnace
By in stove to including the first adiabator layer, the second adiabator layer and the 3rd adiabator layer that set gradually outside stove；It is described
First adiabator layer is zirconium oxide insulation material；Second adiabator layer is formed by zirconium oxide with aluminum oxide；Described
Three adiabator layers are zirconium oxide insulation material.
6. rare earth crystal growth equipment according to claim 5, it is characterised in that the density of first adiabator layer
It is 5.2~3.8g/cm3；The density of second adiabator layer is 3.5~2.3g/cm3；3rd adiabator layer it is close
It is 1.8~0.6g/cm to spend3。
7. rare earth crystal growth equipment according to claim 5, it is characterised in that the thickness of first adiabator layer
It is 1~3.5cm；
The thickness of second adiabator layer is 1~4cm；
The thickness of the 3rd adiabator layer is 0.5~1.5cm.
8. rare earth crystal growth equipment according to claim 1, it is characterised in that the heating element heater be iraurite product with
Cu induction coils；The size of the iraurite product is 70~140mm of φ, deep 50~150mm；The size of the Cu induction coils is
2~3 times of iraurite product size.
9. a kind of rare earth crystal growth technique, it is characterised in that including：
A) after high-purity rare-earth raw material is mixed, mixed material is obtained；
B) under vacuum or protective atmosphere, after the mixed material that above-mentioned steps are obtained is through oversintering, polycrystal material block is obtained；
C) under vacuum or protective atmosphere, the polycrystal material block that above-mentioned steps are obtained is described in claim 1~8 any one
Rare earth crystal growth equipment in melt after, after carrying out crystal growth under the guiding of seed crystal using czochralski method, obtain rare earth brilliant
Body.
10. the rare earth crystal growth equipment described in claim 1~8 any one in growth of yttrium-aluminum Garnet crystal and/or
Application in rare earth orthosilicate crystalloid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107488874A (en) * | 2017-09-04 | 2017-12-19 | 中国科学院长春应用化学研究所 | A kind of design method of temperature field structure for rare earth crystal growth technique and the growth technique of low-cost rare earth crystal |
| CN110453276A (en) * | 2019-07-31 | 2019-11-15 | 赣州虔东激光科技有限公司 | A kind of device producing laser crystal base |
| CN110528065A (en) * | 2019-09-30 | 2019-12-03 | 萧县威辰机电工程设备有限公司 | A kind of monocrystalline silicon growing furnace that security performance is high |
| CN114754586A (en) * | 2022-05-12 | 2022-07-15 | 眉山博雅新材料股份有限公司 | High-temperature furnace |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721586A (en) * | 2005-05-13 | 2006-01-18 | 中国科学院上海硅酸盐研究所 | A kind of fuse-elements crystal real-time viewing system |
| CN201850329U (en) * | 2010-11-08 | 2011-06-01 | 鸿福晶体科技(安徽)有限公司 | Single crystal growth monitor of jewels |
| CN102337592A (en) * | 2011-07-01 | 2012-02-01 | 中国电子科技集团公司第二研究所 | Sic crystal growth furnace temperature measuring window |
| CN103132135A (en) * | 2012-12-13 | 2013-06-05 | 苏州工业园区杰士通真空技术有限公司 | High-efficient novel sapphire crystal growth system |
| CN103558129A (en) * | 2013-11-22 | 2014-02-05 | 王学重 | Probe type online three-dimensional imaging detection system and probe type online three-dimensional imaging detection method |
-
2016
- 2016-11-25 CN CN201611059073.3A patent/CN106757317A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721586A (en) * | 2005-05-13 | 2006-01-18 | 中国科学院上海硅酸盐研究所 | A kind of fuse-elements crystal real-time viewing system |
| CN201850329U (en) * | 2010-11-08 | 2011-06-01 | 鸿福晶体科技(安徽)有限公司 | Single crystal growth monitor of jewels |
| CN102337592A (en) * | 2011-07-01 | 2012-02-01 | 中国电子科技集团公司第二研究所 | Sic crystal growth furnace temperature measuring window |
| CN103132135A (en) * | 2012-12-13 | 2013-06-05 | 苏州工业园区杰士通真空技术有限公司 | High-efficient novel sapphire crystal growth system |
| CN103558129A (en) * | 2013-11-22 | 2014-02-05 | 王学重 | Probe type online three-dimensional imaging detection system and probe type online three-dimensional imaging detection method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107488874A (en) * | 2017-09-04 | 2017-12-19 | 中国科学院长春应用化学研究所 | A kind of design method of temperature field structure for rare earth crystal growth technique and the growth technique of low-cost rare earth crystal |
| CN110453276A (en) * | 2019-07-31 | 2019-11-15 | 赣州虔东激光科技有限公司 | A kind of device producing laser crystal base |
| CN110528065A (en) * | 2019-09-30 | 2019-12-03 | 萧县威辰机电工程设备有限公司 | A kind of monocrystalline silicon growing furnace that security performance is high |
| CN114754586A (en) * | 2022-05-12 | 2022-07-15 | 眉山博雅新材料股份有限公司 | High-temperature furnace |
| CN114754586B (en) * | 2022-05-12 | 2023-02-17 | 眉山博雅新材料股份有限公司 | High-temperature furnace |
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