CN107841789A - Yttrium aluminate visible waveband laser crystal that a kind of dysprosium terbium is co-doped with and preparation method thereof - Google Patents
Yttrium aluminate visible waveband laser crystal that a kind of dysprosium terbium is co-doped with and preparation method thereof Download PDFInfo
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- CN107841789A CN107841789A CN201710851986.7A CN201710851986A CN107841789A CN 107841789 A CN107841789 A CN 107841789A CN 201710851986 A CN201710851986 A CN 201710851986A CN 107841789 A CN107841789 A CN 107841789A
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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
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/24—Complex oxides with formula AMeO3, wherein A is a rare earth metal and Me is Fe, Ga, Sc, Cr, Co or Al, e.g. ortho ferrites
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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
Abstract
The present invention relates to the yttrium aluminate visible waveband laser crystal that a kind of dysprosium terbium is co-doped with, the molecular formula of the crystal is Dy, Tb:YAlO3(Dy,Tb:YAP), orthorhombic crystal, cell parameter are belonged toWithThermal conductivity is 11Wm‑1K‑1.Use purity 4N Y2O3, Al2O3, Dy2O3And Tb4O7As raw material, by being sufficiently mixed, briquetting, the technological process such as high temperature pre-sintering pre-processes to raw material, carries out crystal growth by czochralski method Frequency Induction Heating, growth atmosphere uses High Purity Nitrogen.Compared with prior art, crystalline material of the present invention can realize efficient visible waveband gold-tinted output, and applied to laser projection, the field such as laser display and undersea detection, present invention repeatability is high, largely reduces power consumption, reduces cost.
Description
Technical field
The present invention relates to a kind of visible waveband laser crystal and preparation method thereof, aluminic acid that more particularly to a kind of dysprosium terbium is co-doped with
Yttrium crystal and preparation method thereof, belong to fluorescent material technical field.
Background technology
The information that the mankind are obtained largely derives from visible ray.The Nobel prize for physics of 2014 is granted by high efficiency blue
LED inventor, remind us how important the pursuit to visible ray solid state light emitter is.However, in visible light lasers spectrum still
So there is blank to be difficult to fill up:Accurate wavelength needed for broad tuning, special applications and always unintelligible yellow (560-
590nm wave bands) light beam.Visible laser is in wearable device, colored display, visible ray optical communication, laser printing, high density
The field such as optical storage of data and biomedicine possesses huge application prospect and economic value.
Pr3+It is current visible waveband development active ions the most ripe, has laser output power and efficiency height etc. excellent
Point, there is laser output report in blue, green, orange, red and dark red optical band.But Pr3+A shortcoming be directly to launch
Gold-tinted.Gold-tinted laser has huge application prospect in fields such as astronomical, communication, biotechnology and medical treatment.Such as, launch wavelength position
In the beacon laser device (Sodium Guide Star Technology) of receiving of 560-590nm yellow bands be that ground optics is looked in the distance
The key equipment of mirror.578nm is the frequency marking (the 1S0-3P0 transition of corresponding Yb atoms) of atom light clock.It is but practical at present
Solid-state laser technical scheme is the GaAs diode-end-pumpeds (Nd using 808nm:YAG) crystal obtain 1064nm and
1319nm tunable seed source, then realize that 589nm laser exports by nonlinear crystal (LBO) and frequency, technology path complexity,
Cost is high.Thus InGaN diode-end-pumpeds are directly realized by 560-590nm gold-tinteds output Worth Expecting.
In recent years, dysprosium ion (Dy3+) yellow band laser is as one of focus of academia.External scientist is right
Mix Dy3+The laser activity of crystal yellow band has carried out Primary Study.Dy3+Generally use launch wavelength is near 450nm
InGaN diodes correspond to two excited levels as pumping source, gold-tinted laser4F9/2Arrive6H13/2Between transition, such as Fig. 1 institutes
Show.In view of Dy3+Absorption and emission cross section it is relatively small, the problems such as laser lower level life-span is larger.Thus, to produce effectively
Gold-tinted laser, it is necessary to try to carry out the population that disappears to laser lower level.The method of the effective population that disappears is typically to draw in crystal
Enter and deactivate ion, such as Tb3+。Tb3+Into after crystal, energy transfer process be present：Dy3+:6H13/2+Tb3+:7F6→Dy3+:6H15/2+Tb3+:7F4.As a result Dy3+Energy level6H13/2Population is reduced, and the laser lower level life-span significantly reduces.Such as in LiLuF4
In crystal, with Tb3+Incorporation, the laser lower level life-span is reduced to 58 μ s from 294 μ s, and the upper laser level life-span keeps substantially
It is constant, it is changed into 1328 μ s from 1344 μ s.2012, S.R.Bowman et al. reported InGaN laser pumpings Dy first:YAG
Crystal, mean power 150mW pulse gold-tinted output, slope efficiency 12% are obtained at 583nm.2014,
G.Bolognesi et al. is using InGaN blue light LD pumpings Dy, Tb:LiLuF4Crystal realizes 578nm, 55mW, 13.4% company
Continuous laser output.In summary, existing these mix Dy at present3+Laser crystal still suffers from many deficiencies, constrains blue light LD pumps
The practical application of the visible yellow band solid state laser in Pu and exploitation.
Dysprosium terbium is co-doped with having very high requirement to host material, and crystal needs have excellent optics, thermodynamics, mechanicalness
Energy, chemical stability and low phonon energy, low phonon energy can largely reduce the nonradiative relaxation of Doped ions,
Improve ionoluminescence efficiency.YAP matrix belongs to rhombic system, density 5.35g/cm3, phonon energy 570cm-1, and in physics
It is closely similar with wide variety of YAG host materials in terms of engineering properties, thus be high power, big energy solids laser
Good selection.From accompanying drawing 3 and the absorption of accompanying drawing 4 and fluorescence spectrum, it can be seen that crystal is in 450nm InGaN diode pumpings
There is stronger absworption peak in the transmitting boundary of source, in yellow band emission peak maximum intensity, be advantageously implemented the efficient laser fortune of gold-tinted
Turn.But YAP crystal has high-temperature phase-transitional, easily ftracture.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of luminous efficiency height, no
Yttrium aluminate visible waveband laser crystal that rare earth ion dysprosium terbium easy to crack is co-doped with and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：The yttrium aluminate visible waveband that a kind of dysprosium terbium is co-doped with swashs
Luminescent crystal, it is characterised in that the molecular formula of the crystal is Dy, Tb:YAlO3(Dy,Tb:YAP), orthorhombic crystal, structure cell ginseng are belonged to
NumberWithThermal conductivity is 11Wm-1K-1。
The molecular formula of the crystal is Dyx,Tby:Y(1-x-y)AlO3, wherein x is Dy atomic percent 4at.%, y Tb
Atomic percent 1%~2.5%.
A kind of preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium is co-doped with, it is characterised in that using czochralski method,
Comprise the following steps：
(1) purity is 4N Dy2O3, Tb4O7, Al2O3And Y2O3Raw material is according to formula molecular formula Dyx,Tby:Y(1-x-y)AlO3,
Wherein x is Dy atomic percent, is 4at.%, and y is Tb atomic percent, is 1%~2.5%, carries out raw material and weighs, ball
Grinding machine mixes, and dries, and is then pressed into a shape material embryo, high temperature sintering using hydraulic press, and taking-up is put into Iridium Crucible, loads intermediate frequency
It is ready for growing in sensing heating lifting furnace；
(2) crucible is put into oxidation zircon sand by the thermal field of YAP crystal growths using zircon sand and zirconium oxide insulating brick is aoxidized,
Top uses individual layer or double-deck zirconium oxide insulating brick, and heat insulation effect is strengthened in insulating brick bottom outer using the covering of zirconium oxide fine sand,
Diaphragm uses sapphire sheet, and seed crystal ensures seed crystal center, crucible center, hub of a spool using b to YAP monocrystalline, loading furnace process
In consistent, after the completion of shove charge, retained foreign body in dust catcher cleaning loss of sheet；
(3) start mechanical pump, treat vacuum ＜ 10Pa in stove, be filled with inert gas as protective gas, prevent Iridium Crucible
Oxidation, is then warming up to 1900 DEG C for 4 hours, constant temperature is completely melt for about 1 hour to raw material, according to roasting seed crystal, is sowed, necking down, is put
Shoulder, it is isometrical, receive thin crystal growth flow and grown, descended in the early stage the seed crystal stage, keep liquid level dimpling, can be effectively ensured
Crystal enters from impurity；
(4) cooled after the completion of crystal growth using multi-stage procedure, obtain Dy, Tb:YAP monocrystalline.
The time of step (1) the ball mill mixing is 24 hours, and the drying is in 80 DEG C of drying box constant temperature 12 hours
It is in 1200 DEG C of Muffle furnace high temperature sintering 24 hours to remove wherein moisture and alcohol, the high temperature sintering.
B described in step (2) to the size of YAP seed crystals be 5 × 5 × 60mm；
Described guarantee seed crystal center, crucible center, hub of a spool are in and unanimously refer to rotary pulling bar, the seed crystal amplitude of oscillation
No more than 1mm.
Inert gas described in step (3) refers to high pure nitrogen or argon gas；
The described inert gas amount of pouring is air pressure in stove is reached an atmospheric pressure.
Pulling rate is 1~4mm/h in crystal growing process described in step (3), and rotating speed is 15~20rpm.
Necking down described in step (3) refers to necking down to about 2~4mm；
It is described isometrical to refer to diameter 40mm；
Described receipts carefully refer to that single crystal diameter is slowly attenuated by heating about 5mm or directly quickly pulls.
Multi-stage procedure described in step (4), which carries out cooling, to be cooled by following procedure：
1) 15 DEG C/h, cool 10h, 1900 DEG C -1780 DEG C；
2) 20 DEG C/h, cool 10h, 1780 DEG C -1580 DEG C；
3) 30 DEG C/h, cool 20h, 1580 DEG C -980 DEG C；
4) 35 DEG C/h, cool 15h, 980 DEG C -455 DEG C；
5) 45 DEG C/h, cool 10h, 455 DEG C-room temperature；
Temperature-fall period amounts to 65 hours, and rate of temperature fall is 15~55 DEG C/h, in the process, if last stage rate of temperature fall
It is too fast, crystallographic cracking can be caused, the post drop stage can accelerate rate of temperature fall, save the energy, reduce cost.
One preferred scheme of Czochralski grown of the present invention is：Step (2) zirconium oxide insulating brick is using double-deck；Step (3)
Necking down is to diameter about 2mm；Step (3) the receipts thin stage, which uses, pulls mode so that has grown crystal and has been separated with liquid level.
Compared with prior art, the advantage of the invention is that：
1st, Dy, Tb prepared by the present invention:YAP monocrystalline directly can directly be excited generation gold-tinted, phase by semiconductor diode
Compared with singly mixing Dy before:YAP has higher luminous efficiency.
2nd, instant invention overcomes dysprosium terbium in YAP monocrystalline to be co-doped with problem of Cracking, and prepared monocrystalline has extraordinary optics matter
Amount.
3rd, the present invention pulls technique and make it that scheme repeatability is high, efficiently solves Dy and Tb ions and is co-doped with YAP crystal
Problem of Cracking, multi-stage procedure cooling more effectively realize the reduction of power consumption.
Brief description of the drawings
Accompanying drawing 1 is Dy and Tb the ion energy transport mechanism that the technical scheme of the embodiment of the present invention 2 prepares sample；
Accompanying drawing 2 is the X-ray powder diffraction pattern that the technical scheme of the embodiment of the present invention 2 prepares sample；
Accompanying drawing 3 is the room temperature absorption coefficient spectrogram that the technical scheme of the embodiment of the present invention 2 prepares sample；
Accompanying drawing 4 is the Room temperature PL spectrum figure that the technical scheme of the embodiment of the present invention 2 prepares sample；
Accompanying drawing 5 is that the technical scheme of the embodiment of the present invention 2 prepares sample in the case where 450nm light excites, corresponding to 574nm emission peaks
Fluorescence lifetime spectrogram.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：Frequency Induction Heating Czochralski grown Dy0.04,Tb0.01:Y0.95AlO3
Dy, Tb are grown using Frequency Induction Heating method:YAP crystal, the direction of growth grows along b axles, 60 × 55mm's of φ
A shape pre-sintering raw material 454.8g is put into Iridium Crucible, shove charge vacuum is evacuated to 3Pa, is filled with high pure nitrogen as protection gas
Atmosphere, 1900 DEG C are warming up to 400~500 DEG C/h heating rate, constant temperature 1-2 hours to raw material are completely melt, using b to pure
YAP monocrystalline is that seed crystal is grown, growth rate 1mm/h, rotating speed 18rpm, in early growth period, control Raised key axis growth, necking down
Start shouldering after to about 3mm, isodiametric growth, when diameter portion length reaches 50mm, start ending to diameter 2mm, stop simultaneously
Only lifting and rotating speed, obtain the Dy, Tb of a b axle direction of growth:YAP crystal, it is cracking.
Embodiment 2：
Dy is grown using Frequency Induction Heating method0.04,Tb0.01:Y0.95AlO3Crystal, the direction of growth grows along b axles, in φ
A shape pretreated feedstock 454.8g is put into 60 × 55mm Iridium Crucible, shove charge vacuum is evacuated to 3Pa, is filled with high pure nitrogen and does
For protective atmosphere, with 400~500 DEG C/h heating rate to 1900 DEG C, constant temperature 1-2 hours to raw material are completely melt, using b to
Pure YAP monocrystalline is that seed crystal is grown, growth rate 1mm/h, rotating speed 18rpm, in early growth period, control Raised key axis growth, contracting
Neck is to shouldering is started after about 3mm, and isodiametric growth, when diameter portion length reaches 50mm, Rapid lifting crystal departs from liquid level, obtains
Obtain the Dy, Tb of a b axle direction of growth:YAP crystal, not cracking and scattering particles, optical quality are good.
Referring to accompanying drawing 1, the Dy in the present invention3+And Tb3+Ion energy transport mechanism, Tb3+Ion is realized to Dy3+Ion has
The population that disappears of effect, its corresponding energy transfer process are：Dy3+:6H13/2+Tb3+:7F6→Dy3+:6H15/2+Tb3+:7F4.So that Dy3+
Energy level6H13/2Population is reduced, and the laser lower level life-span significantly reduces.
Referring to accompanying drawing 2, it is the Dy, Tb grown according to this embodiment scheme:YAP crystal prototype X-ray powder diffraction figures
Spectrum, test result show that prepared material is phase pure material, occur without miscellaneous peak.
Referring to accompanying drawing 3, it is the Dy, Tb grown according to this embodiment scheme:YAP crystal prototype absorption coefficient collection of illustrative plates, its
Middle absworption peak just coincide with semiconductor diode InGaN launch wavelengths at 450nm, is especially suitable for pump-coupling.
Referring to accompanying drawing 4, it is the Dy, Tb grown according to this embodiment scheme:YAP crystal prototype launching light spectrograms, wherein
Yellow emission peak intensity highest, illustrate that material is very beneficial for gold-tinted output.
Referring to accompanying drawing 5, it is the Dy, Tb grown according to this embodiment scheme:YAP crystal prototype fluorescence lifetime spectrograms, swash
Hair wavelength is 450nm, Detection wavelength 574nm, and it is 126 μ s that fitting, which obtains the life-span, and it is anti-that the relatively long life-span is advantageous to population
Turn, be advantageous to the output of gold-tinted；And Dy, Tb:Energy level under YAP samples6H13/2Life-span compares Dy:Energy level under YAP6H13/2Life-span
It is obvious to reduce.
Embodiment 3：
Dy is grown using Frequency Induction Heating method0.04,Tb0.015:Y0.945AlO3Crystal, the direction of growth grows along b axles, in φ
A shape pretreated feedstock 454.8g is put into 60 × 55mm Iridium Crucible, shove charge vacuum is evacuated to 3Pa, is filled with high pure nitrogen and does
For protective atmosphere, with 400~500 DEG C/h heating rate to 1900 DEG C, constant temperature 1-2 hours to raw material are completely melt, using b to
Pure YAP monocrystalline is that seed crystal is grown, growth rate 1mm/h, rotating speed 18rpm, in early growth period, control Raised key axis growth, contracting
Neck is to shouldering is started after about 2.5mm, and isodiametric growth, when diameter portion length reaches 50mm, Rapid lifting crystal departs from liquid level,
Obtain the Dy, Tb of a b axle direction of growth:YAP crystal, not cracking and scattering particles, optical quality are good.
Its main structural behaviour, absorption spectrum, luminescent spectrum and attenuation curve are similar to Example 2.
Embodiment 4：
Dy is grown using Frequency Induction Heating method0.04,Tb0.02:Y0.94AlO3Crystal, the direction of growth grows along b axles, in φ
A shape pretreated feedstock 454.8g is put into 60 × 55mm Iridium Crucible, shove charge vacuum is evacuated to 3Pa, is filled with high pure nitrogen and does
For protective atmosphere, with 400~500 DEG C/h heating rate to 1900 DEG C, constant temperature 1-2 hours to raw material are completely melt, using b to
Pure YAP monocrystalline is that seed crystal is grown, growth rate 1.5mm/h, rotating speed 19rpm, and in early growth period, control Raised key axis grows,
Necking down is to shouldering is started after about 2mm, and isodiametric growth, when diameter portion length reaches 60mm, Rapid lifting crystal departs from liquid level,
Obtain the Dy, Tb of a b axle direction of growth:YAP crystal, not cracking and scattering particles, optical quality are good.
Its main structural behaviour, absorption spectrum, luminescent spectrum and attenuation curve are similar to Example 2.
Embodiment 5：
Dy is grown using Frequency Induction Heating method0.04,Tb0.025:Y0.935AlO3Crystal, the direction of growth grows along b axles, in φ
A shape pretreated feedstock 454.8g is put into 60 × 55mm Iridium Crucible, shove charge vacuum is evacuated to 3Pa, is filled with high pure nitrogen and does
For protective atmosphere, with 400~500 DEG C/h heating rate to 1900 DEG C, constant temperature 1-2 hours to raw material are completely melt, using b to
Pure YAP monocrystalline is that seed crystal is grown, growth rate 2mm/h, rotating speed 19rpm, in early growth period, control Raised key axis growth, contracting
Neck is to shouldering is started after about 2mm, and isodiametric growth, when diameter portion length reaches 55mm, Rapid lifting crystal departs from liquid level, obtains
Obtain the Dy, Tb of a b axle direction of growth:YAP crystal, not cracking and scattering particles, optical quality are good.
Its main structural behaviour, absorption spectrum, luminescent spectrum and attenuation curve are similar to Example 2.
Embodiment 6：
The yttrium aluminate laser crystal preparation method that a kind of dysprosium terbium is co-doped with, using czochralski method, comprises the following steps：
(1) purity is 4N Dy2O3, Tb4O7, Al2O3And Y2O3Raw material is according to formula molecular formula Dyx,Tby:Y(1-x-y)AlO3,
The atomic percent 4at.%, y that wherein x is Dy are Tb atomic percent 1%, carry out raw material and weigh, ball mill mixing 24 is small
When, 80 DEG C of drying box constant temperature 12 hours removes wherein moisture and alcohol, is then pressed into a shape material embryo using hydraulic press, is put into horse
Not 1200 DEG C of stove high temperature sintering 24 hours, taking-up are put into Iridium Crucible, are fitted into Frequency Induction Heating lifting furnace and are ready for giving birth to
It is long；
(2) crucible is put into oxidation zircon sand by the thermal field of YAP crystal growths using zircon sand and zirconium oxide insulating brick is aoxidized,
Top uses mono-layer oxidized zirconium insulating brick, and heat insulation effect, diaphragm are strengthened in insulating brick bottom outer using the covering of zirconium oxide fine sand
Using sapphire sheet, seed crystal is 5 × 5 × 60mm to YAP monocrystalline, its size using b, and loading furnace process will ensure seed crystal center, earthenware
Crucible center, hub of a spool is in consistent (i.e. rotary pulling bar, the seed crystal amplitude of oscillation are no more than 1mm), after the completion of shove charge, dust catcher cleaning
Retained foreign body in loss of sheet；
(3) start mechanical pump, treat vacuum ＜ 10Pa in stove, be filled with high pure nitrogen as protective gas, prevent Iridium Crucible
Oxidation, is then warming up to 1900 DEG C for 4 hours, constant temperature is completely melt that according to roasting seed crystal, sow, necking down is to about for about 1 hour to raw material
2mm, shouldering, isometrical (diameter 40mm), the crystal growth flow for receiving thin (making single crystal diameter slowly attenuate about 5mm by heating) are tight
Lattice control, pulling rate is 1mm/h in growth course, rotating speed 15rpm, is descended in the early stage the seed crystal stage, keeps liquid level dimpling, Ke Yiyou
Effect ensures that crystal enters from impurity；
(4) cooled after the completion of crystal growth using multi-stage procedure, obtain Dy, Tb:YAP monocrystalline；The wherein multistage
Program, which carries out cooling, to be cooled by following procedure：
1) 15 DEG C/h, cool 10h, 1900 DEG C -1780 DEG C；
2) 20 DEG C/h, cool 10h, 1780 DEG C -1580 DEG C；
3) 30 DEG C/h, cool 20h, 1580 DEG C -980 DEG C；
4) 35 DEG C/h, cool 15h, 980 DEG C -455 DEG C；
5) 45 DEG C/h, cool 10h, 455 DEG C-room temperature；
Temperature-fall period amounts to 65 hours, and rate of temperature fall is 15~55 DEG C/h, in the process, if last stage rate of temperature fall
It is too fast, crystallographic cracking can be caused, the post drop stage can accelerate rate of temperature fall, save the energy, reduce cost.
Embodiment 7：
The yttrium aluminate laser crystal preparation method that a kind of dysprosium terbium is co-doped with, using czochralski method, comprises the following steps：
(1) purity is 4N Dy2O3, Tb4O7, Al2O3And Y2O3Raw material is according to formula molecular formula Dyx,Tby:Y(1-x-y)AlO3,
The atomic percent 4at.%, y that wherein x is Dy are Tb atomic percent 2.5%, carry out raw material and weigh, ball mill mixing 24
Hour, 80 DEG C of drying box constant temperature 12 hours removes wherein moisture and alcohol, is then pressed into a shape material embryo using hydraulic press, is put into
1200 DEG C of Muffle furnace high temperature sintering 24 hours, taking-up are put into Iridium Crucible, are fitted into Frequency Induction Heating lifting furnace and are ready for
Growth；
(2) crucible is put into oxidation zircon sand by the thermal field of YAP crystal growths using zircon sand and zirconium oxide insulating brick is aoxidized,
Top uses double-deck zirconium oxide insulating brick, and heat insulation effect, diaphragm are strengthened in insulating brick bottom outer using the covering of zirconium oxide fine sand
Using sapphire sheet, seed crystal is using b to YAP monocrystalline, and loading furnace process will ensure seed crystal center, crucible center, and hub of a spool is in
Unanimously, after the completion of shove charge, retained foreign body in dust catcher cleaning loss of sheet；
(3) start mechanical pump, treat vacuum ＜ 10Pa in stove, be filled with high-purity argon gas as protective gas, prevent Iridium Crucible
Oxidation, is then warming up to 1900 DEG C for 4 hours, constant temperature is completely melt that according to roasting seed crystal, sow, necking down is to about for about 1 hour to raw material
4mm, shouldering, isometrical (diameter 40mm), the crystal growth flow for receiving thin (making single crystal diameter slowly attenuate about 5mm by heating) are tight
Lattice control, pulling rate is 4mm/h in growth course, rotating speed 20rpm, is descended in the early stage the seed crystal stage, keeps liquid level dimpling, Ke Yiyou
Effect ensures that crystal enters from impurity；
(4) cooled after the completion of crystal growth using multi-stage procedure, obtain Dy, Tb:YAP monocrystalline, multi-stage procedure
Carrying out cooling is cooled by following procedure：
1) 15 DEG C/h, cool 10h, 1900 DEG C -1780 DEG C；
2) 20 DEG C/h, cool 10h, 1780 DEG C -1580 DEG C；
3) 30 DEG C/h, cool 20h, 1580 DEG C -980 DEG C；
4) 35 DEG C/h, cool 15h, 980 DEG C -455 DEG C；
5) 45 DEG C/h, cool 10h, 455 DEG C-room temperature；
Temperature-fall period amounts to 65 hours, and rate of temperature fall is 15~55 DEG C/h, in the process, if last stage rate of temperature fall
It is too fast, crystallographic cracking can be caused, the post drop stage can accelerate rate of temperature fall, save the energy, reduce cost.
Gained Dy, Tb:YAP monocrystalline belongs to orthorhombic crystal, cell parameterWith Thermal conductivity is 11Wm-1K-1。
Claims (10)
1. the yttrium aluminate visible waveband laser crystal that a kind of dysprosium terbium is co-doped with, it is characterised in that the molecular formula of the crystal is Dy, Tb:
YAlO3(Dy,Tb:YAP), orthorhombic crystal, cell parameter are belonged toWithThermal conductivity
For 11Wm-1K-1。
2. the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 1 is co-doped with, it is characterised in that the crystal
Molecular formula be Dyx,Tby:Y(1-x-y)AlO3, atomic percent 4at.%, y that wherein x is Dy are Tb atomic percent 1%
~2.5%.
3. a kind of preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium as claimed in claim 1 is co-doped with, its feature
It is, using czochralski method, comprises the following steps：
(1) purity is 4N Dy2O3, Tb4O7, Al2O3And Y2O3Raw material is according to formula molecular formula Dyx,Tby:Y(1-x-y)AlO3, wherein
X is Dy atomic percent, is 4at.%, and y is Tb atomic percent, is 1%~2.5%, carries out raw material and weighs, ball mill
Mixing, dry, be then pressed into a shape material embryo, high temperature sintering using hydraulic press, taking-up is put into Iridium Crucible, loads Medium frequency induction
It is ready for growing in heating lifting furnace；
(2) crucible is put into oxidation zircon sand, top by the thermal field of YAP crystal growths using oxidation zircon sand and zirconium oxide insulating brick
Using individual layer or double-deck zirconium oxide insulating brick, heat insulation effect, window are strengthened in insulating brick bottom outer using the covering of zirconium oxide fine sand
Piece uses sapphire sheet, and for seed crystal using b to YAP monocrystalline, loading furnace process ensures seed crystal center, crucible center, and hub of a spool is in
Unanimously, after the completion of shove charge, retained foreign body in dust catcher cleaning loss of sheet；
(3) start mechanical pump, treat vacuum ＜ 10Pa in stove, be filled with inert gas as protective gas, prevent Iridium Crucible from aoxidizing,
Then 1900 DEG C are warming up within 4 hours, constant temperature is completely melt for about 1 hour to raw material, according to roasting seed crystal, is sowed, necking down, shouldering, etc.
Footpath, receive thin crystal growth flow and grown, descended in the early stage the seed crystal stage, keep liquid level dimpling, crystal can be effectively ensured
Enter from impurity；
(4) cooled after the completion of crystal growth using multi-stage procedure, obtain Dy, Tb:YAP monocrystalline.
4. the preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 3 is co-doped with, its feature exist
In the time of step (1) the ball mill mixing is 24 hours, and the drying is to remove it in 80 DEG C of drying box constant temperature 12 hours
Middle moisture and alcohol, the high temperature sintering are in 1200 DEG C of Muffle furnace high temperature sintering 24 hours.
5. the preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 3 is co-doped with, its feature exist
In, b described in step (2) to the size of YAP seed crystals be 5 × 5 × 60mm；
Described guarantee seed crystal center, crucible center, hub of a spool are in and unanimously refer to rotary pulling bar, and the seed crystal amplitude of oscillation does not surpass
Cross 1mm.
6. the preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 3 is co-doped with, its feature exist
In the inert gas described in step (3) refers to high pure nitrogen or argon gas；
The described inert gas amount of pouring is air pressure in stove is reached an atmospheric pressure.
7. the preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 3 is co-doped with, its feature exist
In pulling rate is 1~4mm/h in the crystal growing process described in step (3), and rotating speed is 15~20rpm.
8. the preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 3 is co-doped with, its feature exist
In the necking down described in step (3) refers to necking down to about 2~4mm；
It is described isometrical to refer to diameter 40mm；
Described receipts carefully refer to that single crystal diameter is slowly attenuated by heating 5mm or directly quickly pulls.
9. the preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 3 is co-doped with, its feature exist
In the multi-stage procedure described in step (4), which carries out cooling, to be cooled by following procedure：
1) 15 DEG C/h, cool 10h, 1900 DEG C -1780 DEG C；
2) 20 DEG C/h, cool 10h, 1780 DEG C -1580 DEG C；
3) 30 DEG C/h, cool 20h, 1580 DEG C -980 DEG C；
4) 35 DEG C/h, cool 15h, 980 DEG C -455 DEG C；
5) 45 DEG C/h, cool 10h, 455 DEG C-room temperature；
Temperature-fall period amounts to 65 hours, and rate of temperature fall is 15~55 DEG C/h.
10. the preparation method for the yttrium aluminate visible waveband laser crystal that dysprosium terbium according to claim 3 is co-doped with, its feature exist
In step (2) zirconium oxide insulating brick is using double-deck；Step (3) necking down is to diameter 2mm；Step (3) receives the thin stage using the side of pulling
Formula so that grown crystal and separated with liquid level.
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| CN112831837A (en) * | 2020-12-30 | 2021-05-25 | 安徽工业大学 | Dysprosium terbium codoped scandium-containing garnet laser crystal, preparation method thereof and application of crystal in realizing yellow laser output by LD pumping |
| CN112952544A (en) * | 2021-01-18 | 2021-06-11 | 枣庄学院 | Dysprosium terbium aluminum tri-doped yellow laser crystal and preparation method and application thereof |
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| CN112952544A (en) * | 2021-01-18 | 2021-06-11 | 枣庄学院 | Dysprosium terbium aluminum tri-doped yellow laser crystal and preparation method and application thereof |
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