CN107177884B - A kind of growing method and device of fluoride single crystal - Google Patents
A kind of growing method and device of fluoride single crystal Download PDFInfo
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- CN107177884B CN107177884B CN201710442067.4A CN201710442067A CN107177884B CN 107177884 B CN107177884 B CN 107177884B CN 201710442067 A CN201710442067 A CN 201710442067A CN 107177884 B CN107177884 B CN 107177884B
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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 devices, belong to the field of single crystal growth of crystal of fluoride.Use crucible for graphite crucible with cover, the water removal fluorization agent selected is NH4HF2, by raw material and fluorization agent mixed grinding, raw mixture is obtained, carries out water removal fluorination；Then heating obtains melt, then after crucible inner melt is down to crystalline temperature position completely, stands, and then cooling obtains the fluoride single crystal.The present invention carries out crystal growth from fluorination Bridgman-Stockbarger method using closed vacuum water removal, and adjusts the parameters such as the temperature in growth course, to obtain the high quality large scale LiLnF for the Centimeter Level that can meet real requirement4(Ln=Y, Gd, Lu) monocrystalline, size are about 10 × 50mm of Φ, and in ultraviolet-visible region transmitance up to 90% or more.The technology has easy to operate, economic, the advantages such as safe and environmental-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 technique
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 lower, high-concentration dopant is still transparent, spontaneous radiation fluorescence lifetime is long, refractive index is by temperature
Influence the advantages that smaller.Therefore, in optical field, such fluoride laser material has particularly significant research and the valence of applying
Value.In addition, LiLnF4Monocrystalline from vacuum ultraviolet to infrared wavelength range in still there is higher clarity, in light laser pumping source and
Under conditions of low phonon energy, there is the limitation compared with low-refraction, improve the probability of activity ionizing radiation transition.Including fluorine
Similar crystal series including compound monocrystalline, the optical application as operation of laser sources substance is significantly.
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.For example, when there is O in environment of crystal growth2With H2The remnants of the oxygen sources such as O, when growth temperature reaches 650 DEG C
When above, such oxygen source reacts with the fluoride in growing environment, has eventually led to the generation of oxyfluoride impurity component,
Even form polycrystalline.Therefore, it obtains high quality crystal of fluoride and is always treated as a very scabrous problem.
In current LiLnF4In the growth technique of crystal, use widest method for Bridgman-Stockbarger method, this method uses
Platinum crucible, it is expensive, and furthermore this kind of crucible is first use, has used needs to re-work every time, has taken time and effort.?
Before crystal growth, it is necessary to remove water and be fluorinated to raw material, conventional method is under the high temperature conditions, to lead to HF gas, and HF gas is severe toxicity
Gas, there are security risks, and fluorinated boiler tube of furthermore ventilating is corrosion resistant platinum pipe, expensive.It is filled using platinum crucible
It after material, needs to seal platinum crucible with oxyhydrogen flame, operation is more difficult and raw material can not be avoided to inhale again in the process
Water.In addition it removes water and grows on different devices, it is cumbersome.Can therefore invent a kind of reduce cost and improves safety again
It is free from environmental pollution, and more simple method is operated, and the method for crystal quality needed for being able to satisfy optical property, become
Current people process difficulties urgently to be resolved.
Summary of the invention
The purpose of the present invention is to provide the growing method and device of a kind of fluoride single crystal, which is used
Vacuum tightness Bridgman-Stockbarger method, and by regulation water removal fluorination program, to obtain the Centimeter Level for meeting real requirement
LiLnF4Monocrystalline, the growing method is easy to operate, economical and practical and efficient.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of growing method of fluoride single crystal, the chemical formula of the fluoride are LiLnF4, wherein Ln=Y, Gd or Lu,
The growth of the fluoride single crystal specifically includes the following steps:
1) using purity is 99.99% LiF, LnF3With fluorization agent NH4HF2As raw material, after ground 15 ~ 30 minutes
It is packed into graphite crucible；
2) mixed raw material obtained in step 1) is placed on the high-temperature region in crystal growing apparatus, carries out water removal fluorination；
3) to the raw mixture heating melting after water removal fluorination, melt is obtained；Crystal growth is measured with temperature thermocouple
The temperature of different location in device determines position identical with the crystallization temperature of melt in the crystal growing apparatus, referred to as
Crystalline temperature position；Drop to melt at 2 ~ 5cm of the crystalline temperature position or more, setting is molten later
The speed of liquid decline is 0.3 ~ 0.4mm/h, and is allowed to stand uniformly across crystalline temperature position, cool down later, obtain the fluorine
Compound monocrystalline.
As Ln=Y, fluoride LiYF4, then raw materials used LiF, YF in step 1)3And NH4HF2Molar ratio be
1.04:1:0.1；As Ln=Gd, fluoride LiGdF4, then raw materials used LiF, GdF in step 1)3And NH4HF2Molar ratio
For 1.85:1:0.2；As Ln=Lu, fluoride LiLuF4, then raw materials used LiF, LuF in step 1)3And NH4HF2Mole
Than for 1:1:0.2.
Water removal fluorination process described in step 2 are as follows: alundum tube is evacuated, the air pressure in pipe is made to reach 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 it is warming up to 325 ~ 375 DEG C again,
It is fluorinated within constant temperature 6 ~ 10 hours；After water removal fluorination, argon gas is passed through to an atmospheric pressure.
The heating melting steps of the step 3) specifically: the raw mixture after water removal fluorination is still placed on crystalline substance
In high-temperature region in body grower, heating is so that high-temperature region and low-temperature space in the crystal growing apparatus reach pre- later
If temperature, heat preservation melting obtains melt；The preset temperature of the high-temperature region is 900 ~ 1000 DEG C, the default temperature of the low-temperature space
Degree is 300 ~ 450 DEG C；Temperature gradient in the crystal growing apparatus is 25 ~ 30 DEG C/cm.
In the step 3), temperature-fall period are as follows: high-temperature region and low-temperature space are cooled down with the rate of 15 ~ 25 DEG C/h.
Above-mentioned growing method carries out in crystal growing apparatus, and the crystal growing apparatus includes: furnace body, alundum tube, use
In the furnace body support of support furnace body and positioned at the intracorporal burner hearth of furnace；The burner hearth includes the high-temperature region positioned at burner hearth upper end under
The low-temperature space at end；The fixed graphite crucible that raw material is housed in the alundum tube, and make graphite crucible can be in burner hearth with corundum
Pipe is up and down reciprocatingly gone up and down.
It is provided with lifting device on 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 moves back and forth between the high-temperature region and the low-temperature space；The lifting device includes: lifting transverse arm, brilliant turn
Motor, linear guide 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 crystalline substance rotating motor is fixed on lifting transverse arm center, for rotating alundum tube, so that
Melt substance in graphite crucible quickly uniforms；The linear guide is connect, with the fixation lifting transverse arm with lifting transverse arm
And it is made vertically to move back and forth track movement；The precision ball screw is connect with lifting transverse arm, and passes through the accurate rolling
The rotation of ballscrew goes up and down transverse arm up and down motion to drive；The linear guide is arranged with precision ball screw parallel side-by-side
In furnace body support, and it is located at lifting transverse arm both ends.
The alundum tube is connect with vacuum mechanical pump, in the case where air intake valve and outlet valve simultaneously close off, so that
Vacuum degree in alundum tube reaches 10-2Pa；The alundum tube is also connect with argon bottle, so that keeping anhydrous and oxygen-free in alundum tube
Atmosphere；The crystal growing apparatus further includes exhaust gas processing device, that is, Ca (OH) is housed2The conical flask of aqueous solution, for locating
Reason contains fluoride.
The crystal growing apparatus further includes the heating device that burner hearth peripheral side is arranged in；The heating device includes being located at height
Warm area and heating wire positioned at low-temperature space；It is provided with temperature regulating device in high-temperature region and low-temperature space, the temperature regulating device is the control of S type
Warm galvanic couple.
The crystal growing apparatus further includes the S type temperature thermocouple being arranged in burner hearth, and the temperature thermocouple is fixed
It is moved on the brilliant rotating motor being connected with lifting device, and with the lifting of alundum tube, to measure the temperature of different location；
The crystal growing apparatus further includes the thermal insulation layer above burner hearth for sealing, and the thermal insulation layer is silicate fiber plate.
The beneficial effects of the present invention are:
(1) present invention prepares LiLnF using vacuum tightness flux Bridgman method4(Ln=Y, Gd, Lu) monocrystalline, is adopted
Anhydrous and oxygen-free environment is provided with closed alundum tube for crystal growth；Using the graphite crucible of capping, prevent the volatilization of raw material serious；
After fluorization agent is added, water removal fluorination can be carried out at a temperature of low voltage constant；Whole process is continuously finished in same boiler tube,
And by adjusting parameters such as temperature in growth course, to obtain the big ruler of Centimeter Level high quality that can meet real requirement
Very little LiLnF4(Ln=Y, Gd, Lu) monocrystalline, size are about 10 × 50mm of Φ, and in ultraviolet-visible region transmitance up to 90%
More than；The method for monocrystal growth is practical, easy to operate, economical and efficient, at low cost and environmental-friendly；
(2) crystal growing apparatus provided by the present invention, it is structure novel, simple, securely and reliably, not only it can be adapted for
LiLnF4The growth of (Ln=Y, Gd, Lu) monocrystalline, and can also be used in a kind of oxidizable, volatile compounds crystal of growth,
It is with a wide range of applications.
Detailed description of the invention
Fig. 1 is the sectional view of the crystal growing apparatus of vacuum tightness Bridgman-Stockbarger method used herein；In figure: 1. hairs
Heated filament, 2. furnace bodies, 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. linear guides, 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 sectional view of graphite crucible of the invention；In figure: 18. graphite crucible bodies, 19. graphite crucible lids.
Specific 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 embodiment.According to the present disclosure, those skilled in the art will recognize that
To in the case where not departing from technical characteristic given by technical solution of the present invention and range, embodiment described above is made perhaps
More change and modification belong to protection scope of the present invention.
As described above, can be used for vacuum tightness Bridgman-Stockbarge method for growing the present invention provides a kind of crystal growing apparatus
LiLnF4(Ln=Y, Gd, Lu) monocrystalline.As shown in Figure 1, the grower includes furnace body 2 and the furnace body for being used to support furnace body 2
Bracket 14.There is burner hearth, burner hearth includes the low-temperature space of high-temperature region and lower end at its upper end in furnace body 2.
Wherein, it is provided with lifting device on furnace body support 14, can be controlled by lifting device rigid in burner hearth
The lifting of beautiful pipe 4, and then control hot charge to be added in the high-temperature region in burner hearth and moved back and forth between low-temperature space.
Specifically, as shown in Figure 1, lifting device 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 11 center of lifting transverse arm.Specifically, brilliant rotating motor 13 can be set in alundum tube 4
Bottom end, and be located at furnace body support 14 in.
Lifting device further includes the linear guide 10 being disposed longitudinally in furnace body support 14, by lifting transverse arm 11 along straight
Line guide rail 10 is mobile to the bottom of furnace body support 14 and then alundum tube 4 is driven 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 15 parallel side-by-side of precision ball screw, and is located at the two of lifting transverse arm 11
End.Wherein, the connection of precision ball screw 15 lifting transverse arm 11 drives about 11 transverse arm of lifting by rotation precision ball screw 15
Reciprocal lifting.Lifting transverse arm 11 is for lifting alundum tube 4, to realize pumping for alundum tube 4.
Brilliant rotating motor 13 is connected with the alundum tube 4 being located in burner hearth, for rotating alundum tube 4, so that in graphite crucible
Melt substance quickly uniforms.Alundum tube 4 makes graphite crucible can be in burner hearth for the fixed graphite crucible that raw material is housed
It is up and down reciprocatingly gone up and down with alundum tube.
The working principle of the lifting device 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 gone up and down, to pump according to certain speed, so that graphite crucible can be in the high-temperature region in burner hearth
It is moved back and forth between low-temperature space.Linear guide 10 is connect by the present invention with lifting transverse arm 11, with fixed lifting transverse arm 11 and is made
It vertically moves back and forth track movement, to ensure that graphite crucible can move in burner hearth along fixation locus.
Crystal growing apparatus of the invention further includes mechanical pump 8, for connecting with alundum tube 4, in air intake valve 12 and is gone out
In the case that air valve 16 simultaneously closes off, the vacuum degree in alundum tube may make to reach 10-2Pa, the alundum tube also with argon bottle
17 connections, so that keeping the atmosphere of anhydrous and oxygen-free in alundum tube, and then effectively can carry out water removal fluorination treatment to raw material；This
Outside, which further includes that exhaust gas processing device is equipped with Ca (OH)2The conical flask 9 of aqueous solution contains for handling
Fluoride etc. endangers gas.
Graphite crucible as shown in Figure 2 is used in the present invention, which 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, later by institute
It states graphite crucible to be put into alundum tube 4 and fix, the rotation of precision ball screw 15, Jin Ercao is then controlled by computer program
It controls the lifting transverse arm 11 being connect with precision ball screw 15 to move upwards, graphite crucible is moved to high-temperature region.The present invention adopts
With graphite crucible with cover, the rupture of graphite crucible body 18 will not be caused Fluoride for Raw Material compound has strong corrosive, furthermore
Graphite crucible is cheap, and cost is relatively low.
According to the present invention, which further includes the heating device that the peripheral side of burner hearth is arranged in；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
It sets, the temperature regulating device is temperature-control heat couple, and preferably temperature regulating device is S type temperature-control heat couple 3.When be located at graphite crucible in
It heats after raw material reaches high-temperature region, it is heated by being heated at high temperature silk, is slowly heated up, so that high-temperature region and low-temperature space
Temperature reaches respective preset temperature, and heat preservation obtains melt so that raw material homogenization.
Crystal growing apparatus of the invention further includes the temperature thermocouple 5 being arranged in burner hearth, for determining the life
Position identical with the crystallization temperature of melt in growth device, referred to as crystalline temperature position.Preferably, temperature thermocouple 5 be fixed on
It on the brilliant rotating motor 13 that lifting device is connected, and is moved with the lifting of alundum tube 4, to measure different location in burner hearth
Temperature.The crystalline temperature position of present invention measurement melt is the position in order to find crystal growth began, so as to set corundum
The decrease speed of pipe 4.After determining the crystalline temperature position, make melt uniformly across institute by way of declining alundum tube 4
State crystalline temperature position.Preferably so that melt at the uniform velocity passes through crystalline temperature position with the speed of 0.3 ~ 0.4mm/h, stand later.
Crystal growing apparatus of the invention further includes the thermal insulation layer 6 that sealing thermal insulation is used for above furnace body 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, which can be silicate fiber plate.
The present invention also provides a kind of LiLnF4The growing method of (Ln=Y, Gd, Lu) monocrystalline is using close crucible
The large-sized LiLnF of the high quality of descent method for growing Centimeter Level4(Ln=Y, Gd, Lu) monocrystalline.This method include raw material preparation,
Vacuum tightness water removal fluorination and degrowth, preferably include following steps:
1) LiF, LnF are used3(Ln=Y, Gd, Lu) and fluorization agent NH4HF2As raw material, the purity of raw material is up to
99.99%, reaction raw materials are obtained after being adequately mixed grinding.
According to the present invention, for LiYF4, raw material Li F, YF3And NH4HF2Molar ratio be preferably 1.04:1:0.1.For
LiGdF4, raw material Li F, GdF3And NH4The molar ratio of HF is preferably 1.85:1:0.2.For LiLuF4, raw material Li F, LuF3With
The molar ratio of NH4HF is preferably 1:1:0.2.The present invention controls the molar 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 raw material is allow 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 15 ~ 30 minutes after be packed into
Graphite crucible.The present invention preferably weighing 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 packed into special stone
In black crucible, glove box is removed later, and graphite crucible is packed into alundum tube, vacuum mechanical pump is opened, so that the gas in alundum tube
Pressure is 10-2Pa.Temperature for removing water is 100 ~ 150 DEG C, and further preferably 120 DEG C, sintering time is 12 ~ 36 hours, further excellent
It is selected as 24 hours.Being fluorinated temperature is 325 ~ 375 DEG C, and further preferably 350 DEG C, sintering time is 6 ~ 10 hours, further excellent
It is selected as 8 hours；By sintering temperature control in above-mentioned range, mainly in view of so that raw material is more sufficiently reacted and burnt
The H in raw material is completely removed during knot2O in O and atmosphere2。
3) raw mixture after being fluorinated vaccum dewatering is heated at high temperature melting, under finding behind crystallization temperature point position
It is born length, cools down later, obtain the LiLnF4(Ln=Y, Gd, Lu) monocrystalline.
The high-temperature heating of the step 3) melts step further include:
31) raw mixture after being fluorinated vaccum dewatering fixes its position in the life with high-temperature region and low-temperature space
In high-temperature region in growth device, heating later so that high-temperature region and low-temperature space in the grower reach preset temperature,
Heat preservation melting, obtains melt.
The preset temperature of the high-temperature region is 900 ~ 1000 DEG C, further preferably 960 DEG C.The default temperature of the low-temperature space
Degree is 300 ~ 450 DEG C, further preferably 400 DEG C.The temperature gradient is (25 ~ 30) DEG C/cm；Preferably 27 DEG C/cm.This
The temperature control of high-temperature region within the above range, is mainly considered optimum temperature gradation, the electric furnace heating wire of crystal growth by invention
Service life and safety, more economical safety within this range.
In order to grow crystal under suitable speed, prevents crystal growth too fast and become polycrystalline, need to step 3)
In melt cool down, the cooling step in the step 3) includes:
32) position identical with the crystallization temperature of melt, referred to as crystalline temperature position are found in the grower, are led to
Cross decline mode melt is dropped to 2 ~ 5cm of the crystalline temperature position or more at, set later melt decline speed as
0.3 ~ 0.4mm/h, and be allowed to uniformly across the crystalline temperature position；
33) cool down to the high-temperature region and the low-temperature space, preferably high-temperature region and low-temperature space are with 15 ~ 25 DEG C/h's
Rate cooling, room temperature is more preferably down to the rate of 20 DEG C/h, obtain the high quality, Centimeter Level large scale LiLnF4 (Ln=
Y, Gd, Lu) monocrystalline.
As described above, the present invention is to determine the crystallization point by the temperature thermocouple 5 being arranged in brilliant rotating motor 13
It sets, as alundum tube declines, just stops after descending through crystalline temperature position.In the step 32), melt is with 0.3 ~ 0.4mm/
The speed of h at the uniform velocity passes through crystalline temperature position, stands later, and melt is fully crystallized, and growth is completed, and using this method, finally obtains
The large-sized LiLnF of high quality of Centimeter Level4(Ln=Y, Gd, Lu) monocrystalline.
Embodiment 1
1) LiF, YF of purity 99.99% are used3With fluorization agent NH4HF2As raw material.Wherein, raw material Li F, YF3With
NH4HF2Molar ratio be 1.04:1:0.1.By LiF, YF after weighing3And NH4HF2Mixing, which is placed in mortar, is fully ground 20 points
Loaded in graphite crucible after clock.The weighing in the glove box full of argon gas of this step, grinding and charging.
2) uniform raw mixture obtained in step 1) is removed into glove box again, graphite crucible is packed into alundum tube,
Increase the high-temperature region that alundum tube pressure pin makes fixed graphite crucible reach grower as shown in Figure 1.Open vacuum machine
Pump, so that the air pressure in alundum tube is 10-2Pa.Height warm area temperature is risen to 120 DEG C, constant temperature and pressure is sintered 24 hours.Into one
Step increases temperature to 350 DEG C, is sintered 8 hours.Argon gas is passed through after sintering to an atmospheric pressure.
3) to burner hearth heat temperature raising, high-temperature region is made 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.Heat preservation 24 hours are stood later, so that substance to be heated forms the melt of homogenization.Existed using setting
Crystalline temperature corresponding with melt position in temperature thermocouple measurement burner hearth in alundum tube pressure pin, starting decline motor, so that
Crucible pressure pin is allowed to cool down uniformly across crystalline temperature position with the slow uniform descent of 0.3mm/h speed, when graphite earthenware
After crucible passes through crystalline temperature position, i.e., behind the crystalline temperature position that graphite crucible passes through low-temperature space, stop decline.Then by high-temperature region and
Low-temperature space is down to room temperature with the rate of temperature fall of 20 DEG C/h, finally takes out crystal, obtains the Centimeter Level having a size of 10 × 50mm of Φ
The large-sized LiYF of high quality4Monocrystalline.
The Centimeter Level LiYF obtained in measurement embodiment 14The transmitance of monocrystalline:
1) LiYF4Monocrystalline cutting and polishing: by resulting LiYF4Monocrystalline is cut into size about 3 × 4 × 5mm3, then to each face
It is polished.
2) round hole that diameter about 2mm is dug out on a black-film, then polished LiYF4Monocrystalline adheres to hole
On, so that monocrystalline is blocked aperture, then measure transmitance using this black-film with monocrystalline, when measurement, laser is made to pass right through aperture.
Using the LiYF in this method measurement embodiment 14The UV, visible light light transmission rate of monocrystalline is up to 90% or more.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
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 the following steps:
1) using purity is 99.99% LiF, LnF3With fluorization agent NH4HF2As raw material, it is packed into after ground 15 ~ 30 minutes
Graphite crucible；As Ln=Y, fluoride LiYF4, then raw materials used LiF, YF in step 1)3And NH4HF2Molar ratio be
1.04:1:0.1；As Ln=Gd, fluoride LiGdF4, then raw materials used LiF, GdF in step 1)3And NH4HF2Molar ratio
For 1.85:1:0.2；As Ln=Lu, fluoride LiLuF4, then raw materials used LiF, LuF in step 1)3And NH4HF2Mole
Than for 1:1:0.2；
2) mixed raw material obtained in step 1) is placed on the high-temperature region in crystal growing apparatus, carries out water removal fluorination；
3) to the raw mixture heating melting after water removal fluorination, melt is obtained；Crystal growing apparatus is measured with temperature thermocouple
The temperature of middle different location is determined position identical with the crystallization temperature of melt in the crystal growing apparatus, is referred to as crystallized
Point position；It drops to melt at 2 ~ 5cm of the crystalline temperature position or more, sets under melt later
The speed of drop is 0.3 ~ 0.4mm/h, and is allowed to stand uniformly across crystalline temperature position, cool down later, obtain the fluoride
Monocrystalline；
Above-mentioned steps 2) described in water removal fluorination process are as follows: alundum tube is evacuated, the air pressure in pipe is made to reach 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 it is warming up to 325 ~ 375 DEG C again,
It is fluorinated within constant temperature 6 ~ 10 hours；After water removal fluorination, argon gas is passed through to an atmospheric pressure；
Above-mentioned steps 3) heating melting steps specifically: it is raw that the raw mixture after water removal fluorination is still placed on crystal
In high-temperature region in growth device, heating later is so that high-temperature region and low-temperature space in the crystal growing apparatus reach default temperature
Degree, heat preservation melting, obtains melt；The preset temperature of the high-temperature region is 900 ~ 1000 DEG C, and the preset temperature of the low-temperature space is
300~450℃；Temperature gradient in the crystal growing apparatus is 25 ~ 30 DEG C/cm；
The growing method carries out in crystal growing apparatus, and the crystal growing apparatus includes: furnace body, alundum tube, for branch
It supports the furnace body support of furnace body and is located at the intracorporal burner hearth of furnace；The burner hearth includes positioned at the high-temperature region and lower end of burner hearth upper end
Low-temperature space；The fixed graphite crucible that raw material is housed in the alundum tube, and make graphite crucible can be in burner hearth on alundum tube
Lower reciprocal lifting.
2. growing method according to claim 1, it is characterised in that: in the step 3), temperature-fall period are as follows: high-temperature region and
Low-temperature space is cooled down with the rate of 15 ~ 25 DEG C/h.
3. growing method according to claim 1, it is characterised in that: it is provided with lifting device on the furnace body support, with
Control is located at the lifting of the alundum tube in burner hearth, and then it is past between the high-temperature region and the low-temperature space to control hot charge to be added
Multiple movement；The lifting device includes: lifting transverse arm, brilliant rotating motor, linear guide 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 crystalline substance rotating motor, it is fixed
In lifting transverse arm center, for rotating alundum tube, so that the melt substance in graphite crucible quickly uniforms；The straight line is led
Rail is connect with lifting transverse arm, with the fixation lifting transverse arm and it is made vertically to move back and forth track movement；The precise ball
Lead screw is connect with lifting transverse arm, and drives lifting transverse arm to move up and down by the rotation of the precision ball screw；Described
Linear guide is arranged in furnace body support with precision ball screw parallel side-by-side, and is located at lifting transverse arm both ends.
4. growing method according to claim 1, it is characterised in that: the alundum tube is connect with vacuum mechanical pump, into
In the case that air valve and outlet valve simultaneously close off, so that the vacuum degree in alundum tube reaches 10-2Pa；The alundum tube also with
Argon bottle connection, so that keeping the atmosphere of anhydrous and oxygen-free in alundum tube；The crystal growing apparatus further includes vent gas treatment dress
It sets, that is, Ca (OH) is housed2The conical flask of aqueous solution contains fluoride for handling.
5. growing method according to claim 1, it is characterised in that: the crystal growing apparatus further includes being arranged in burner hearth
The heating device of peripheral side；The heating device 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 couple.
6. growing method according to claim 1, it is characterised in that: the crystal growing apparatus further includes being arranged in burner hearth
Interior S type temperature thermocouple, the temperature thermocouple are fixed on the brilliant rotating motor being connected with lifting device, and with corundum
The lifting of pipe and move, to measure the temperature of different location；The crystal growing apparatus further includes being located above burner hearth for close
The thermal insulation layer of envelope, the thermal insulation layer are silicate fiber plate.
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN113293429B (en) * | 2021-05-31 | 2022-08-30 | 福州大学 | Preparation method of monoclinic phase Ga2S3 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 |
| 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 |
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| CN103147119B (en) * | 2013-03-21 | 2015-09-16 | 北京雷生强式科技有限责任公司 | A kind of preparation method of magnesium fluoride crystal and growth apparatus |
| CN105734668B (en) * | 2016-03-28 | 2018-09-28 | 中国科学院福建物质结构研究所 | A kind of Ba3P3O10The growing method of Cl monocrystalline |
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