CN107177884A - The growing method and device of a kind of fluoride single crystal - Google Patents
The growing method and device of a kind of fluoride single crystal Download PDFInfo
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- CN107177884A CN107177884A CN201710442067.4A CN201710442067A CN107177884A CN 107177884 A CN107177884 A CN 107177884A CN 201710442067 A CN201710442067 A CN 201710442067A CN 107177884 A CN107177884 A CN 107177884A
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- alundum tube
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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
- 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
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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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
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- Crystallography & Structural Chemistry (AREA)
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of growing method of fluoride single crystal and device, belong to the field of single crystal growth of crystal of fluoride.Crucible is used for graphite crucible with cover, the water removal fluorization agent of selection is NH4HF2, by raw material and fluorization agent mixed grinding, raw mixture is obtained, water removal fluorination is carried out；Then heating obtains liquation, then crucible inner melt is down to behind crystalline temperature position completely, stands, and then cooling obtains the fluoride single crystal.The present invention carries out crystal growth using closed vacuum water removal from fluorination Bridgman-Stockbarger method, and adjusts the parameters such as the temperature in growth course, so as to obtain meeting the high-quality large scale LiLnF of the Centimeter Level of real requirement4（Ln=Y, Gd, Lu) monocrystalline, size is about 10 × 50mm of Φ, and in ultraviolet-visible region transmitance up to more than 90%.The technology has simple to operate, economic, the advantage such as safe and environment-friendly.
Description
Technical field
The present invention relates to technical field of single crystal growth, more particularly, to the growing method and device of a kind of fluoride single crystal.
Background technology
Fluoride LiLnF4(Ln=Y, Gd, Lu) monocrystalline is a kind of excellent laser crystal material in a low voice of physical and chemical performance,
With chemical stability is good, fusing point is relatively low, high-concentration dopant is still transparent, spontaneous radiation fluorescence lifetime length, refractive index are by temperature
The advantages of influence is smaller.Therefore, in optical field, such fluoride laser material has particularly significant research with applying valency
Value.In addition, LiLnF4Monocrystalline from VUV to infrared wavelength range in still there is higher clarity, in light laser pumping source and
Under conditions of low phonon energy, the limitation with compared with low-refraction improves the probability of activity ionizing radiation transition.Including fluorine
Similar crystal series including compound monocrystalline, is significantly as the optical application of operation of laser sources material.
In a series of growing methods of crystal of fluoride, such as czochralski method, epitaxy, Bridgman-Stockbarger method, zone-melting process, wherein
The key of fluoride combination crystal growth is how to solve O present in raw material and growing environment2With H2The oxygen sources such as O participate in fluorination
The problem of reaction.O is occurred in that for example, working as in environment of crystal growth2With H2The remnants of the oxygen sources such as O, when growth temperature reaches 650 DEG C
During the above, such oxygen source reacts with the fluoride in growing environment, has ultimately resulted in the generation of oxyfluoride impurity component,
Even form polycrystalline.Therefore, obtain high-quality crystal of fluoride and be always treated as a very scabrous problem.
In current LiLnF4In the growth technique of crystal, use widest method for Bridgman-Stockbarger method, this method is used
Platinum crucible, its is expensive, and this kind of crucible is first use in addition, is re-worked, taken time and effort using complete needs every time.
Before crystal growth, it is necessary to raw material is removed water and is fluorinated, conventional method is under the high temperature conditions, leads to HF gases, and HF gases are severe toxicity
, there is potential safety hazard in gas, the boiler tube for fluorination of ventilating in addition is corrosion resistant platinum pipe, expensive.Filled using platinum crucible
, it is necessary to be sealed with oxyhydrogen flame to platinum crucible after material, operation is more difficult and in the process raw material can not be avoided to inhale again
Water.Water removal and growth are on different devices, cumbersome in addition.Can therefore invent a kind of reduce cost and improves security again
It is free from environmental pollution, and more simple method, and the method that the crystal mass needed for optical property can be met are operated, turn into
Current people process difficulties urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to provide a kind of growing method of fluoride single crystal and device, the growing method is used
Vacuum tightness Bridgman-Stockbarger method, and by regulating and controlling water removal fluorination program, so as to obtain meeting the Centimeter Level of real requirement
LiLnF4Monocrystalline, the growing method is simple to operate, economical and practical and efficient.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of growing method of fluoride single crystal, the chemical formula of the fluoride is LiLnF4, wherein Ln=Y, Gd or Lu are described
The growth of fluoride single crystal specifically includes following steps：
1）It is 99.99% LiF, LnF using purity3With fluorization agent NH4HF2As raw material, load after ground 15 ~ 30 minutes
Graphite crucible；
2）By step 1）In obtained mixed material be placed on high-temperature region in crystal growing apparatus, carry out water removal fluorination；
3）Melting is heated to the raw mixture after water removal fluorination, liquation is obtained；Crystal growing apparatus is determined with temperature thermocouple
The temperature of middle diverse location, determines the crystallization temperature identical position with liquation in the crystal growing apparatus, referred to as crystallizes
Point position；First cause liquation to drop to more than the crystalline temperature position at 2 ~ 5cm by way of decline, set afterwards under liquation
The speed of drop is 0.3 ~ 0.4mm/h, and is allowed to, uniformly across crystalline temperature position, stand, afterwards cool, obtain the fluoride
Monocrystalline.
As Ln=Y, fluoride is LiYF4, then step 1）In raw materials used LiF, YF3And NH4HF2Mol ratio be
1.04:1:0.1；As Ln=Gd, fluoride is LiGdF4, then step 1）In raw materials used LiF, GdF3And NH4HF2Mol ratio
For 1.85:1:0.2；As Ln=Lu, fluoride is LiLuF4, then step 1）In raw materials used LiF, LuF3And NH4HF2Mole
Than for 1:1:0.2.
Step 2）Described in water removal fluorination process be：Alundum tube is evacuated, the air pressure in pipe is reached 10-2Pa,
High-temperature region temperature rises to 100 ~ 150 DEG C, and subsequent constant temperature and pressure is removed water for 12 ~ 36 hours；Hereafter 325 ~ 375 DEG C are warming up to again,
Constant temperature is fluorinated for 6 ~ 10 hours；After water removal fluorination terminates, argon gas is passed through to an atmospheric pressure.
The step 3）Heating melting steps be specially：The raw mixture removed water after fluorination is still placed on crystalline substance
In high-temperature region in body grower, afterwards heating cause the crystal growing apparatus in high-temperature region and low-temperature space reach it is pre-
If temperature, insulation melting obtains liquation；The preset temperature of the high-temperature region is 900 ~ 1000 DEG C, the default temperature of the low-temperature space
Spend for 300 ~ 450 DEG C；Thermograde in the crystal growing apparatus is 25 ~ 30 DEG C/cm.
The step 3）In, temperature-fall period is：High-temperature region and low-temperature space are cooled with 15 ~ 25 DEG C/h speed.
Above-mentioned growing method is carried out in crystal growing apparatus, and the crystal growing apparatus includes：Body of heater, alundum tube, use
In the furnace body support and the burner hearth in body of heater of support body of heater；The burner hearth includes the high-temperature region positioned at burner hearth upper end with
The low-temperature space at end；The fixed graphite crucible equipped with raw material in the alundum tube, and make it that graphite crucible can be in burner hearth with corundum
Pipe is up and down reciprocatingly lifted.
Lowering or hoisting gear is provided with the furnace body support, to control the lifting for the alundum tube being located in burner hearth, and then is controlled
Hot charge to be added is moved back and forth between the high-temperature region and the low-temperature space；The lowering or hoisting gear includes：Transverse arm, crystalline substance is lifted to turn
Motor, line slideway and precision ball screw；The lifting transverse arm is arranged on furnace body support and for lifting alundum tube, with
Realize that alundum tube pumps；The brilliant rotating motor, is fixed on lifting transverse arm center, for rotating alundum tube, to cause
Melt substance in graphite crucible is quickly uniformed；The line slideway, is connected with lifting transverse arm, with the fixed lifting transverse arm
And it is vertically moved back and forth track motion；The precision ball screw, is connected with lifting transverse arm, and passes through the accurate rolling
The rotation of ballscrew lifts transverse arm up and down motion to drive；Described line slideway is set with precision ball screw parallel side-by-side
In furnace body support, and positioned at lifting transverse arm two ends.
The alundum tube is connected with vacuum mechanical pump, in the case where air intake valve and outlet valve are simultaneously closed off so that
Vacuum in alundum tube reaches 10-2Pa；The alundum tube is also connected with argon bottle, to keep anhydrous and oxygen-free in alundum tube
Atmosphere；The crystal growing apparatus also includes exhaust gas processing device, i.e., equipped with Ca (OH)2The conical flask of the aqueous solution, for locating
Reason contains fluoride.
The crystal growing apparatus also includes the heater for being arranged on burner hearth outer circumferential side；The heater includes being located at height
Warm area and the heating wire positioned at low-temperature space；Temperature regulating device is provided with high-temperature region and low-temperature space, the temperature regulating device is S type controls
Warm galvanic couple.
The crystal growing apparatus also includes the S type temperature thermocouples being arranged in burner hearth, and the temperature thermocouple is fixed
On the brilliant rotating motor being connected with lowering or hoisting gear, and moved with the lifting of alundum tube, to determine the temperature of diverse location；
The crystal growing apparatus also includes being located above burner hearth being used for sealed thermal insulation layer, and the thermal insulation layer is silicate fiber plate.
The beneficial effects of the present invention are：
（1）The present invention prepares LiLnF using vacuum tightness flux Bridgman method4(Ln=Y, Gd, Lu) monocrystalline, using close
Close alundum tube and provide anhydrous and oxygen-free environment for crystal growth；Using the graphite crucible of capping, prevent that the volatilization of raw material is serious；Add
After fluorization agent, water removal fluorination can be carried out at a temperature of low voltage constant；Whole process is continuously finished in same boiler tube, and is led to
The parameters such as the temperature crossed in adjustment growth course, so as to obtain meeting the high-quality large scale of Centimeter Level of real requirement
LiLnF4(Ln=Y, Gd, Lu) monocrystalline, size is about 10 × 50mm of Φ, and ultraviolet-visible region transmitance up to 90% with
On；The method for monocrystal growth is practical, simple to operate, economical and efficient, and cost is low and environment-friendly；
（2）Crystal growing apparatus provided by the present invention, structure is novel, simple, safe and reliable, not only goes for LiLnF4
The growth of (Ln=Y, Gd, Lu) monocrystalline, but also one class is oxidizable, volatile compounds crystal available for growth, with wide
General application value.
Brief description of the drawings
Fig. 1 is the profile of the crystal growing apparatus of vacuum tightness Bridgman-Stockbarger method used herein；In figure：1. hair
Heated filament, 2. bodies of heater, 3. S type temperature-control heat couples, 4. alundum tubes, 5. S type temperature thermocouples, 6. thermal insulation layers, 7. vacuum pressures
Power table, 8. vacuum mechanical pumps, 9. Ca (OH)2Solution, 10. line slideways, 11. lifting transverse arms, 12. air intake valves, 13.
Brilliant rotating motor, 14. furnace body supports, 15. precision ball screws, 16. outlet valves, 17. argon bottles.
Fig. 2 is the profile of the graphite crucible of the present invention；In figure：18. graphite crucible body, 19. graphite crucible lids.
Embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail.But skilled in the art realises that,
Protection scope of the present invention is not limited only to following examples.According to present disclosure, those skilled in the art will recognize that
To in the case where not departing from the technical characteristic and scope given by technical solution of the present invention, embodiment described above is made perhaps
Change and modifications belongs to protection scope of the present invention more.
As described above, the invention provides a kind of crystal growing apparatus, it can be used for vacuum tightness Bridgman-Stockbarge method for growing
LiLnF4(Ln=Y, Gd, Lu) monocrystalline.As shown in figure 1, the grower includes body of heater 2 and the body of heater for supporting body of heater 2
Support 14.There is burner hearth, burner hearth includes the low-temperature space of high-temperature region at its upper end and lower end in body of heater 2.
Wherein, lowering or hoisting gear is provided with furnace body support 14, can be controlled by lowering or hoisting gear firm in burner hearth
The lifting of beautiful pipe 4, and then control to move back and forth between high-temperature region and low-temperature space of the hot charge to be added in burner hearth.
Specifically, as shown in figure 1, lowering or hoisting gear includes the precision ball screw 15 being arranged in furnace body support 14, lifting
Transverse arm 11 and the brilliant rotating motor 13 for being fixed on the center of lifting transverse arm 11.Specifically, brilliant rotating motor 13 can be arranged on alundum tube 4
Bottom, and in the furnace body support 14.
Lowering or hoisting gear also includes being disposed longitudinally on line slideway 10 in furnace body support 14, by lifting transverse arm 11 along straight
Line guide rail 10 moves to the bottom of furnace body support 14 and then drives alundum tube 4 to shift to low-temperature space from high-temperature region in burner hearth.Straight line
Guide rail 10 is arranged in furnace body support 14 with the parallel side-by-side of precision ball screw 15, and is located at the two of lifting transverse arm 11 respectively
End.Wherein, the connection of precision ball screw 15 lifting transverse arm 11, lifting transverse arm is driven about 11 by rotating precision ball screw 15
Reciprocal lifting.Lifting transverse arm 11 is used to lift alundum tube 4, to realize pumping for alundum tube 4.
Brilliant rotating motor 13 is connected with the alundum tube 4 in burner hearth, for rotating alundum tube 4, to cause in graphite crucible
Melt substance is quickly uniformed.Alundum tube 4 is used for the fixed graphite crucible equipped with raw material, and make it that graphite crucible can be in burner hearth
Up and down reciprocatingly lifted with alundum tube.
The operation principle of the lowering or hoisting gear is that lifting transverse arm 11 is driven by setting the rotation of precision ball screw 15, is made
Transverse arm 11, which must be lifted, to be pumped according to certain speed, and then enable high-temperature region of the graphite crucible in burner hearth
Moved back and forth between low-temperature space.Line slideway 10 is connected by the present invention with lifting transverse arm 11, to fix lifting transverse arm 11 and make
It vertically moves back and forth track motion, so as to ensure that graphite crucible can be moved along fixation locus in burner hearth.
The crystal growing apparatus of the present invention also includes mechanical pump 8, for being connected with alundum tube 4, air intake valve 12 and is going out
In the case that air valve 16 is simultaneously closed off, it may be such that the vacuum in alundum tube reaches 10-2Pa, the alundum tube also with argon bottle
17 connections, to cause the atmosphere that anhydrous and oxygen-free is kept in alundum tube, and then effectively can carry out water removal fluorination treatment to raw material；This
Outside, the crystal growing apparatus also includes exhaust gas processing device i.e. equipped with Ca (OH)2The conical flask 9 of the aqueous solution, contains for handling
Fluoride etc. endangers gas.
Graphite crucible as shown in Figure 2 is employed in the present invention, the graphite crucible includes graphite crucible body 18 and graphite earthenware
Crucible lid 19.Hot charge to be added is put into the graphite crucible body 18 of the graphite crucible, graphite crucible lid 19 is tightened, afterwards by institute
State graphite crucible to be put into alundum tube 4 and fix, then control precision ball screw 15 to rotate by computer program, Jin Ercao
Control the lifting transverse arm 11 being connected with precision ball screw 15 to move upwards, graphite crucible is moved to high-temperature region.The present invention is adopted
With graphite crucible with cover, even if Fluoride for Raw Material compound there is severe corrosive will not also cause the rupture of graphite crucible body 18, in addition
Graphite crucible is cheap, and cost is relatively low.
According to the present invention, the crystal growing apparatus also includes the heater for being arranged on the outer circumferential side of burner hearth；The heating
Device is to be located at high-temperature region and the heating wire 1 positioned at low-temperature space.In addition, being provided with temperature control dress in high-temperature region and low-temperature space
Put, the temperature regulating device is temperature-control heat couple, preferably temperature regulating device is S types temperature-control heat couple 3.When treating in graphite crucible
Heat raw material to reach behind high-temperature region, it is heated by being heated at high temperature silk, slow heating so that high-temperature region and low-temperature space
Temperature reaches respective preset temperature, and insulation causes raw material homogenization, obtains liquation.
The crystal growing apparatus of the present invention also includes the temperature thermocouple 5 being arranged in burner hearth, for determining the life
With the crystallization temperature identical position of liquation, referred to as crystalline temperature position in growth device.Preferably, temperature thermocouple 5 be fixed on
On the brilliant rotating motor 13 that lowering or hoisting gear is connected, and moved with the lifting of alundum tube 4, to determine diverse location in burner hearth
Temperature.The crystalline temperature position that the present invention determines melt is in order to find the position of crystal growth began, so as to set corundum
The decrease speed of pipe 4.Determine behind the crystalline temperature position, so that liquation is uniformly across institute by way of declining alundum tube 4
State crystalline temperature position.Preferably so that liquation with 0.3 ~ 0.4mm/h speed at the uniform velocity by crystalline temperature position, stand afterwards.
The crystal growing apparatus of the present invention also includes being used for the thermal insulation layer 6 of sealing thermal insulation above body of heater 2 and burner hearth.It is logical
Setting thermal insulation layer 6 is crossed to ensure that the temperature in burner hearth is constant.Preferably, the thermal insulation layer 6 can be silicate fiber plate.
Present invention also offers a kind of LiLnF4The growing method of (Ln=Y, Gd, Lu) monocrystalline, it is to use close crucible
High-quality large-sized LiLnF of descent method for growing Centimeter Level4(Ln=Y, Gd, Lu) monocrystalline.This method include raw material prepare,
The step such as vacuum tightness water removal fluorination and degrowth, preferably includes following steps：
1）Using LiF, LnF3(Ln=Y, Gd, Lu) and fluorization agent NH4HF2As raw material, the purity of raw material is up to
99.99%, obtain reaction raw materials after being adequately mixed grinding.
According to the present invention, for LiYF4, raw material Li F, YF3And NH4HF2Mol ratio be preferably 1.04:1:0.1.For
LiGdF4, raw material Li F, GdF3And NH4HF mol ratio is preferably 1.85:1:0.2.For LiLuF4, raw material Li F, LuF3With
NH4HF mol ratio is preferably 1: 1:0.2.The present invention controls the mol ratio of raw material within the above range, primarily to making
The polycrystal material of higher purity can more fully be reacted and obtain by obtaining raw material, by the above-mentioned model of the doping specific gravity control of fluorization agent
In enclosing, primarily to alloing raw material more fully to remove water fluorination.Specifically, can be first by raw material Li F, LnF3(Ln=Y,
Gd, Lu) and fluorization agent NH4HF2Weighed according to molar ratio, and be placed in mortar be fully ground after 15 ~ 30 minutes load
Graphite crucible.The weighing of the invention preferably in the glove box full of argon gas, grinding and charging.
2）Vaccum dewatering fluorination is carried out to the raw material in step 1.
The step of carrying out vaccum dewatering fluorination to raw mixture is that ground raw mixture is loaded to special stone
In black crucible, glove box is removed afterwards, graphite crucible is loaded into alundum tube, opens vacuum mechanical pump so that the gas in alundum tube
Press as 10-2Handkerchief.Temperature for removing water is 100 ~ 150 DEG C, and more preferably 120 DEG C, sintering time is 12 ~ 36 hours, further excellent
Elect as 24 hours.It is 325 ~ 375 DEG C to be fluorinated temperature, and more preferably 350 DEG C, sintering time is 6 ~ 10 hours, further excellent
Elect as 8 hours；By sintering temperature control in above-mentioned scope, mainly in view of causing raw material more fully to react and burning
The H in raw material is removed during knot completely2O in O and atmosphere2。
3）Raw mixture high-temperature heating melting after vaccum dewatering is fluorinated, under finding behind crystallization temperature point position
It is born length, cools afterwards, obtain the LiLnF4(Ln=Y, Gd, Lu) monocrystalline.
The step 3）High-temperature heating melting step also include：
31）The raw mixture after vaccum dewatering is fluorinated fixes its position in the growth dress with high-temperature region and low-temperature space
In the high-temperature region put, afterwards heating cause the grower in high-temperature region and low-temperature space reach preset temperature, be incubated
Melting, obtains liquation.
The preset temperature of the high-temperature region is 900 ~ 1000 DEG C, more preferably 960 DEG C.The default temperature of the low-temperature space
Spend for 300 ~ 450 DEG C, more preferably 400 DEG C.The thermograde is (25 ~ 30) DEG C/cm；Preferably 27 DEG C/cm.This
Invention by the temperature control of high-temperature region within the above range, optimum temperature gradation, electric furnace heating wire mainly in view of crystal growth
Service life and security, more economical safety within this range.
In order that crystal grows under suitable speed, prevent that crystal growth is too fast and becomes polycrystalline, it is necessary to step 3）
In liquation cooled, the step 3）In cooling step include：
32）Searching and the crystallization temperature identical position of liquation in the grower, referred to as crystalline temperature position, under
The mode of drop causes liquation to drop to more than the crystalline temperature position at 2 ~ 5cm, set afterwards the speed of liquation decline as 0.3 ~
0.4mm/h, and be allowed to uniformly across the crystalline temperature position；
33）The high-temperature region and the low-temperature space are cooled, preferably high-temperature region and low-temperature space are with 15 ~ 25 DEG C/h speed
Cooling, room temperature is more preferably down to 20 DEG C/h speed, obtain high-quality, Centimeter Level the large scale LiLnF4 (Ln=Y,
Gd, Lu) monocrystalline.
As described above, the present invention is to determine the crystalline temperature position by the temperature thermocouple 5 being arranged in brilliant rotating motor 13
Put, as alundum tube declines, just stop after crystalline temperature position is descended through.The step 32）In, liquation is with 0.3 ~ 0.4mm/
H speed at the uniform velocity by crystalline temperature position, is stood afterwards, and melt is fully crystallized, and growth is completed, and using this method, is finally given
High-quality large-sized LiLnF of Centimeter Level4(Ln=Y, Gd, Lu) monocrystalline.
Embodiment 1
1）Employ the LiF of purity 99.99%, YF3With fluorization agent NH4HF2It is used as raw material.Wherein, raw material Li F, YF3And NH4HF2
Mol ratio be 1.04:1:0.1.By LiF, YF after weighing3And NH4HF2Mixing is placed in mortar to be fully ground after 20 minutes and filled
In graphite crucible.The weighing in the glove box full of argon gas of this step, grinding and charging.
2）Again by step 1）The uniform raw mixture of middle gained removes glove box, and graphite crucible is loaded into alundum tube,
Rise alundum tube pressure pin causes fixed graphite crucible to reach the high-temperature region of grower as shown in Figure 1.Open vacuum machine
Pump so that the air pressure in alundum tube is 10-2Handkerchief.Height warm area temperature is risen to 120 DEG C, constant temperature and pressure is sintered 24 hours.Enter one
Step rise temperature is sintered 8 hours to 350 DEG C.Sintering is passed through argon gas to an atmospheric pressure after finishing.
3）To burner hearth heat temperature raising, high-temperature region is set to reach 960 DEG C of preset temperature, low-temperature space reaches 400 DEG C of preset temperature, temperature
Degree gradient is 27 DEG C/cm.Insulation 24 hours are stood afterwards so that the liquation of material formation homogenization to be heated.Using being arranged on
Temperature thermocouple in alundum tube pressure pin determines crystalline temperature position corresponding with liquation in burner hearth, starts and declines motor so that
Crucible pressure pin is allowed to be cooled uniformly across crystalline temperature position with the slow uniform descent of 0.3mm/h speed, when graphite earthenware
After crucible is by crystalline temperature position, i.e., behind the crystalline temperature position that graphite crucible passes through low-temperature space, stop declining.Then by high-temperature region and
Low-temperature space is down to room temperature with 20 DEG C/h rate of temperature fall, finally takes out crystal, obtains the Centimeter Level that size is 10 × 50mm of Φ
High-quality large-sized LiYF4Monocrystalline.
Determine the Centimeter Level LiYF obtained in embodiment 14The transmitance of monocrystalline：
1）LiYF4Monocrystalline cutting and polishing：By the LiYF of gained4Monocrystalline cuts into size about 3 × 4 × 5mm3, then each face is carried out
Polishing.
2）Diameter about 2mm circular port is dug out on a black-film, then polished LiYF4Monocrystalline adheres to hole
On, monocrystalline is blocked aperture, then using this black-film measurement transmitance with monocrystalline, during measurement, laser is passed right through aperture.
LiYF in embodiment 1 is determined using this method4The UV, visible light light transmission rate of monocrystalline is up to more than 90%.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of growing method of fluoride single crystal, it is characterised in that：The chemical formula of the fluoride is LiLnF4, wherein Ln=Y,
Gd or Lu, the growth of the fluoride single crystal specifically includes following steps：
1）It is 99.99% LiF, LnF using purity3With fluorization agent NH4HF2As raw material, load after ground 15 ~ 30 minutes
Graphite crucible；
2）By step 1）In obtained mixed material be placed on high-temperature region in crystal growing apparatus, carry out water removal fluorination；
3）Melting is heated to the raw mixture after water removal fluorination, liquation is obtained；Crystal growing apparatus is determined with temperature thermocouple
The temperature of middle diverse location, determines the crystallization temperature identical position with liquation in the crystal growing apparatus, referred to as crystallizes
Point position；First cause liquation to drop to more than the crystalline temperature position at 2 ~ 5cm by way of decline, set afterwards under liquation
The speed of drop is 0.3 ~ 0.4mm/h, and is allowed to, uniformly across crystalline temperature position, stand, afterwards cool, obtain the fluoride
Monocrystalline.
2. growing method according to claim 1, it is characterised in that：As Ln=Y, fluoride is LiYF4, then step 1）In
Raw materials used LiF, YF3And NH4HF2Mol ratio be 1.04:1:0.1；As Ln=Gd, fluoride is LiGdF4, then step 1）
In raw materials used LiF, GdF3And NH4HF2Mol ratio be 1.85:1:0.2；As Ln=Lu, fluoride is LiLuF4, then step
1）In raw materials used LiF, LuF3And NH4HF2Mol ratio be 1:1:0.2.
3. growing method according to claim 1, it is characterised in that：Step 2）Described in water removal fluorination process be：It is right
Alundum tube is evacuated, and the air pressure in pipe is reached 10-2Pa, high-temperature region temperature rises to 100 ~ 150 DEG C, and subsequent constant temperature and pressure 12 ~
Removed water within 36 hours；Hereafter 325 ~ 375 DEG C are warming up to again, and constant temperature is fluorinated for 6 ~ 10 hours；After water removal fluorination terminates, it is passed through
Argon gas is to an atmospheric pressure.
4. growing method according to claim 1, it is characterised in that：The step 3）Heating melting steps be specially：
The raw mixture removed water after fluorination is still placed in the high-temperature region in crystal growing apparatus, heating afterwards causes described
High-temperature region and low-temperature space in crystal growing apparatus reach preset temperature, and insulation melting obtains liquation；The high-temperature region it is pre-
If temperature is 900 ~ 1000 DEG C, the preset temperature of the low-temperature space is 300 ~ 450 DEG C；Temperature ladder in the crystal growing apparatus
Spend for 25 ~ 30 DEG C/cm.
5. growing method according to claim 1, it is characterised in that：The step 3）In, temperature-fall period is：High-temperature region and
Low-temperature space is cooled with 15 ~ 25 DEG C/h speed.
6. the growing method according to claim any one of 1-5, it is characterised in that：The growing method is filled in crystal growth
Middle progress is put, the crystal growing apparatus includes：Body of heater, alundum tube, the furnace body support for supporting body of heater and positioned at body of heater
Interior burner hearth；The burner hearth includes the low-temperature space of the high-temperature region and lower end positioned at burner hearth upper end；Fixation is equipped with the alundum tube
The graphite crucible of raw material, and graphite crucible can up and down reciprocatingly be lifted with alundum tube in burner hearth.
7. growing method according to claim 6, it is characterised in that：Lowering or hoisting gear is provided with the furnace body support, with
Control is located at the lifting of the alundum tube in burner hearth, and then controls hot charge to be added past between the high-temperature region and the low-temperature space
Multiple motion；The lowering or hoisting gear includes：Lift transverse arm, brilliant rotating motor, line slideway and precision ball screw；The lifting is horizontal
Arm is arranged on furnace body support and for lifting alundum tube, to realize that alundum tube pumps；The brilliant rotating motor, it is fixed
In lifting transverse arm center, for rotating alundum tube, to cause the melt substance in graphite crucible quickly to uniform；The straight line is led
Rail, is connected with lifting transverse arm, to fix the lifting transverse arm and it is vertically moved back and forth track motion；The precise ball
Leading screw, is connected with lifting transverse arm, and drives lifting transverse arm to move up and down by the rotation of the precision ball screw；Described
Line slideway is arranged in furnace body support with precision ball screw parallel side-by-side, and positioned at lifting transverse arm two ends.
8. growing method according to claim 6, it is characterised in that：The alundum tube is connected with vacuum mechanical pump, is being entered
In the case that air valve and outlet valve are simultaneously closed off so that the vacuum in alundum tube reaches 10-2Pa；The alundum tube also with
Argon bottle is connected, to cause the atmosphere that anhydrous and oxygen-free is kept in alundum tube；The crystal growing apparatus also includes vent gas treatment and filled
Put, i.e., equipped with Ca (OH)2The conical flask of the aqueous solution, contains fluoride for handling.
9. growing method according to claim 6, it is characterised in that：The crystal growing apparatus also includes being arranged on burner hearth
The heater of outer circumferential side；The heater includes being located at high-temperature region and the heating wire positioned at low-temperature space；In high-temperature region and low temperature
Area is provided with temperature regulating device, and the temperature regulating device is S type temperature-control heat couples.
10. growing method according to claim 6, it is characterised in that：The crystal growing apparatus also includes being arranged on stove
S type temperature thermocouples in thorax, the temperature thermocouple is fixed on the brilliant rotating motor being connected with lowering or hoisting gear, and with firm
The lifting of beautiful pipe and move, to determine the temperature of diverse location；The crystal growing apparatus also includes being located above burner hearth and is used for
Sealed thermal insulation layer, the thermal insulation layer is silicate fiber plate.
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| CN107557861A (en) * | 2017-10-21 | 2018-01-09 | 福州大学 | A kind of growing method and its process units suitable for BPOC monocrystalline |
| TWI648525B (en) * | 2017-12-18 | 2019-01-21 | 國家中山科學研究院 | Device for measuring thermal field distribution inside crucible |
| CN109797428A (en) * | 2019-02-12 | 2019-05-24 | 南京同溧晶体材料研究院有限公司 | A kind of heat-exchanging method grows rare earth ion doped crystal of fluoride porous graphite crucible and its growing method |
| CN112522789A (en) * | 2020-11-30 | 2021-03-19 | 中国科学院福建物质结构研究所 | Monoclinic phase Ga2S3Method and apparatus for vapor phase growth of crystal |
| CN112663135A (en) * | 2020-11-30 | 2021-04-16 | 中国科学院福建物质结构研究所 | Monoclinic phase Ga2S3Method and apparatus for physical vapor phase growth of single crystal |
| CN112663133A (en) * | 2021-01-25 | 2021-04-16 | 延安星特亮科创有限公司 | Bridgman method crystal growth crucible |
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| CN113293429A (en) * | 2021-05-31 | 2021-08-24 | 福州大学 | Monoclinic phase Ga2S3Method for producing single crystal |
| CN114622279A (en) * | 2022-03-18 | 2022-06-14 | 四川奇峰景行光学科技有限公司 | Fluoride polycrystalline raw material treatment device and method |
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| CN107557861B (en) * | 2017-10-21 | 2019-05-10 | 福州大学 | A kind of growing method and its process units suitable for BPOC monocrystalline |
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| TWI648525B (en) * | 2017-12-18 | 2019-01-21 | 國家中山科學研究院 | Device for measuring thermal field distribution inside crucible |
| CN109797428B (en) * | 2019-02-12 | 2023-04-14 | 南京同溧晶体材料研究院有限公司 | Growth method for growing rare earth ion doped fluoride crystal by heat exchange method |
| CN109797428A (en) * | 2019-02-12 | 2019-05-24 | 南京同溧晶体材料研究院有限公司 | A kind of heat-exchanging method grows rare earth ion doped crystal of fluoride porous graphite crucible and its growing method |
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| CN112663135B (en) * | 2020-11-30 | 2023-09-08 | 中国科学院福建物质结构研究所 | Monoclinic phase Ga 2 S 3 Method and apparatus for physical vapor growth of single crystal |
| CN112663133A (en) * | 2021-01-25 | 2021-04-16 | 延安星特亮科创有限公司 | Bridgman method crystal growth crucible |
| CN113035480A (en) * | 2021-02-26 | 2021-06-25 | 中国科学院江西稀土研究院 | Magnetic refrigeration material and preparation method and application thereof |
| CN113035480B (en) * | 2021-02-26 | 2022-02-11 | 中国科学院江西稀土研究院 | Magnetic refrigeration material and preparation method and application thereof |
| CN113293429A (en) * | 2021-05-31 | 2021-08-24 | 福州大学 | Monoclinic phase Ga2S3Method for producing single crystal |
| CN114622279A (en) * | 2022-03-18 | 2022-06-14 | 四川奇峰景行光学科技有限公司 | Fluoride polycrystalline raw material treatment device and method |
| CN116395673A (en) * | 2023-03-07 | 2023-07-07 | 青岛昊鑫新能源科技有限公司 | Carbon nanotube production reactor |
| CN116395673B (en) * | 2023-03-07 | 2023-09-15 | 青岛昊鑫新能源科技有限公司 | Carbon nanotube production reactor |
| CN116988155A (en) * | 2023-07-31 | 2023-11-03 | 上海芯飞睿科技有限公司 | Fluoride crystal and preparation method thereof |
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