CN106048721A - Spectral property adjustable rare-earth ion doped alkali earth fluoride laser crystal and preparation method thereof - Google Patents
Spectral property adjustable rare-earth ion doped alkali earth fluoride laser crystal and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
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- H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
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- H01S3/1645—Solid materials characterised by a crystal matrix halide
- H01S3/165—Solid materials characterised by a crystal matrix halide with the formula MF2, wherein M is Ca, Sr or Ba
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Abstract
The invention relates to spectral property adjustable rare-earth ion doped alkali earth fluoride laser crystal and a preparation method thereof. The chemical formula of the rare-earth ion doped alkali earth fluoride laser crystal is (Pr<3+>, R<3+>):MF2, in the formula, R<3+> is at least one of Y<3+>, La<3+>, Gd<3+>, Sc<3+> and Lu<3+>; the doping concentration of praseodymium ions Pr<3+> is 0.1-2.0at%; the doping concentration of R<3+> is 0.5-20.0at%. As the rare-earth praseodymium ions Pr<3+> and trivalent cation R<3+> (Y<3+>, La<3+>, Gd<3+>, Sc<3+>, Lu<3+> and the like) are added simultaneously in an MF2 medium, and the concentrations of the rare-earth praseodymium ions Pr<3+> and the trivalent cation R<3+> are adjusted, the emission intensity of fluorescence peaks of crystal visible wave bands can be improved, and the intensity ratio can be increased.
Description
Technical field
The invention belongs to artificial intraocular lenses and laser material field, be specifically related to the alkaline-earth metal fluorine of a kind of praseodymium ion doping
Compound laser crystal.This crystal can be used as the working-laser material of visible light wave range.
Background technology
The fast development of laser instrument industry, greatly promotes exploration and the research and development of laser crystal material.Visible light wave range swashs
Light is owing to having extensive use in the numerous areas such as medical science, biology, mapping measurement, optical storage Display Technique, and becomes
One of the focus of research and advanced subject.
Currently acquired visible light lasers mainly has three kinds of methods, i.e. obtains visible light lasers by frequency multiplication, by upper conversion
Phenomenon obtains visible ray and directly obtains visible ray by LD pumping.The current indigo plant using infrared band laser frequency multiplication to obtain,
Green (light) laser has obtained commercial applications, but this laser instrument exists the shortcoming that structure is complicated and lasing efficiency is low.
Additionally, obtain visible light lasers by upper conversion phenomena be the most only limited to the laboratory research stage, still do not have at wave band red, orange
Obtain the output of effective laser.Obtaining visible ray by LD pumping to have obtained studying widely, it has simple in construction, and efficiency is high
Advantage.GaN blue laser excitation wavelength is 440nm, correspond to Pr3+Absworption peak, in this context, praseodymium ion
(Pr3+) paid close attention to by people because of the level structure of its uniqueness.Pr3+Energy level transition can produce the visible of several colors
Light, including peony (695nm and 720nm), red (640nm), orange (605nm), green (522nm), blue (490nm).
It is currently based on Pr3+The research of laser crystal makes some progress, at LiYF4, YAP, Pr, BaY2F8, LaF3And KY3F10Deng
Substrate all achieves laser output.But, Pr3+Ion doping, in above same host crystal, often can only realize certain
The high efficiency laser output of individual specific band, can not play Pr3+Ion all can realize the special of laser output at multiple wavelength
Advantage.Bivalent cation crystal of fluoride (the MF of praseodymium ion doping2, M=Ca or Sr etc.) and there is wider emission spectrum, but send out
Light intensity is relatively low.
Summary of the invention
For the problems referred to above, present invention is primarily targeted at raising Pr3+:MF2(M=Ca, Sr) visible light wave range is each glimmering
Photopeak fluorescence intensity, regulates and controls each fluorescence peak fluorescence intensity ratio, to obtain the reddest, orange, the green or crystalline substance of blue laser output
Body.
To this end, the invention provides a kind of regulatable rare earth ion doped alkaline earth fluoride laser crystal of spectrum property,
The chemical formula of described rare earth ion doped alkaline earth fluoride laser crystal is (Pr3+, R3+):MF2, wherein R3+For Y3+、La3+、Gd3 +、Sc3+And Lu3+In at least one, described praseodymium ion Pr3+Doping content be 0.1at%～2.0at%, described R3+Mix
Miscellaneous concentration is 0.5at%～20.0at%.
The present invention has wider emission spectrum by the bivalent cation crystal of fluoride that praseodymium ion adulterates, then by making
Non-luminous three valence state sun R itself3+Ion (such as, Y3+、La3+、Gd3+、Sc3+And Lu3+Deng) and Pr3+Ion is co-doped with alkaline earth fluorination
Thing crystal, greatly improves the luminous intensity of crystal.Additionally, by regulation R3+The concentration of ion, and then regulation and control Pr3+Fluorescence
In spectrum, the width of spectral peak and each fluorescence peak spectral strength ratio, reach to realize different-waveband visible ray in same substrate and send out
The purpose of light, makes the working-laser material of visible light wave range.
The regulatable rare earth ion doped alkaline earth fluoride laser crystal (Pr of spectrum property that the present invention provides3+, R3+):
MF2, wherein M is Ca or Sr.
On the other hand, the invention provides the preparation method of a kind of rare-earth ion-doped doping alkaline earth Fluoride Laser Crystals,
Raw material PrF is weighed according to stoichiometric3、RF3And MF2, use melt method to grow crystalline substance under fine vacuum or protective atmosphere
Body.
It is preferred that add PbF in material powder2Powder as oxygen scavenger, described PbF2The addition of powder is MF2Powder
The 0.1～2.0wt% of end.PbF2As low melting point (800 DEG C) oxygen scavenger, the most fully volatilized before fluoride raw material melts,
So Pb will not remain in crystal.Preferably, described MF2(Me=Ca, Sr), RF3、PrF2It is dried dehydration before combination
Process.
About the growth of crystal, can use Bridgman-Stockbarger method or Growth by Temperature Gradient Technique crystal, crucible material uses height
Pure graphite or platinum, crystal growth is carried out in protective atmosphere or fine vacuum atmosphere.
About the growth of crystal, crucible bottom is added without seed crystal or puts into employing through X-ray diffractometer orientation normal line of butt end
Direction is the MF of [111]2Monocrystal rod is as seed crystal.
It is preferred that described protective atmosphere is high-purity Ar atmosphere and/or fluorine-containing atmosphere.Preferably, described fluorine-containing atmosphere is CF4
And/or HF gas or CF4And/or the gaseous mixture of HF gas and argon.
The present invention is at MF2Substrate mixes rare earth ion praseodymium ion Pr simultaneously3+With three valence state cationes R3+(Y3+、La3+、
Gd3+、Sc3+And Lu3+Deng), by regulation and control rare earth ion praseodymium ion Pr3+With three valence state cationes R3+Concentration, improve crystal can
See optical band each fluorescence peak emissive porwer and intensity.Rare-earth ion-doped doping alkaline earth fluoride laser prepared by the present invention is brilliant
Body, under visible light wave range, has 460nm～500nm, 510nm～a 560nm, 580nm～630nm, 640～660nm and 720～
730nm fluorescence peak, each fluorescence peak intensity, peak position and halfwidth are with three valence state cationes R3+Kind and concentration change and become
Change.
Accompanying drawing explanation
Fig. 1 is the 0.6at%Pr:CaF of embodiment 1 preparation2, 0.6at%Pr 0.6at%Y:CaF2And 0.6at%Pr
1.2at%Y:CaF2Crystal emission spectrum at room temperature；
Fig. 2 is the 0.6at%Pr:CaF of embodiment 1 preparation2, embodiment 2 preparation 0.6at%Pr 3.0at%Gd:CaF2With
0.6at%Pr3.0at%Y:CaF2Crystal emission spectrum at room temperature；
Fig. 3 is the 0.6at%Pr:SrF of embodiment 5 preparation2, embodiment 6 preparation 0.6at%Pr 0.6at%Y:SrF2With
0.6at%Pr3.0at%Y:SrF2Crystal emission spectrum at room temperature；
Fig. 4 is the 0.6at%Pr:SrF of embodiment 5 preparation2, embodiment 6 preparation 0.6at%Pr 0.6at%Gd:SrF2And
The 0.6at%Pr3.0at%Gd:SrF of embodiment 7 preparation2Crystal emission spectrum at room temperature.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that following embodiment is merely to illustrate this below by way of following embodiment
Invention, and the unrestricted present invention.
The present invention is by regulation MF2Pr in crystal3+Ion and R3+The concentration proportioning of ion (three valence state cationes), it is achieved
To (Pr3+, R3+):MF2The each fluorescence peak of crystal visible light wave range (intensity, peak position and halfwidth etc.) regulates and controls, and then acquisition has
The reddest, orange, the crystal of green and blue ray laser output.
Rare earth ion doped its chemical formula of alkaline earth fluoride laser crystal of the present invention is (Pr3+, R3+):MF2, wherein R3+
Can be Y3+、La3+、Gd3+、Sc3+And Lu3+In at least one.Described praseodymium ion Pr3+Doping content be 0.1at%～
2.0at%, the bivalent cation crystal of fluoride (MF of praseodymium ion doping2, M=Ca or Sr etc.) and there is wider emission spectrum,
But luminous intensity is relatively low.Described R3+Doping content be 0.5at%～20.0at%, by the present invention in that itself non-luminous three
Valence state sun R3+Ion and Pr3+Ion is co-doped with, and greatly improves the luminous intensity of crystal.Pr3+, R3+With PrF3And RF3Form
Mix.M is Ca or Sr.Prepare composition of raw materials as follows: initial feed uses PrF3、RF3And MF2And PbF2, first two raw material is massaged
You are equal to (0.001～0.02) by ratio: (0.005～0.2): 1 carries out dispensing.PbF2Addition be CaF20.1～2.0wt%,
Preferably scope is 0.5～1wt%.
Melt method can be used to grow the rare earth ion doped alkaline earth fluorination of the present invention under fine vacuum or protective atmosphere
Thing laser crystal ((Pr3+, R3+):MF2, or Pr, R:MF2).Described melt method includes Bridgman-Stockbarger method or temperature gradient method.First
Weigh all raw materials by above-mentioned formula proportion, load in crucible after being sufficiently mixed uniformly, use the above-mentioned monocrystal of melt method for growing.
For Bridgman-Stockbarger method or temperature gradient method, crucible material uses high purity graphite, and crucible bottom can not put seed crystal,
Or put into the MF of specific direction2(M=Ca, Sr) seed crystal (such as, is put into employing and is oriented end face normal direction through X-ray diffractometer
MF for [111]2Monocrystal rod), crystal growth is at protective atmosphere (such as high-purity Ar atmosphere and/or fluorine-containing atmosphere) or fine vacuum gas
Atmosphere is carried out.Described fluorine-containing atmosphere can be CF4And/or HF gas or CF4And/or HF gas is with other noble gas (such as
Ar) gaseous mixture.Such as, CF4Or HF.
As an example, for temperature gradient method, crucible material is high purity graphite, and crucible bottom is not put seed crystal or puts into
Through the MF that X-ray diffractometer orientation end face normal direction is [111]2Monocrystal rod, crystal growth is under condition of high vacuum degree or high-purity
In Ar atmosphere.
As an example, for Bridgman-Stockbarger method, crucible material uses platinum, crucible bottom do not put seed crystal or put into through
X-ray diffractometer orientation end face normal direction is the MF of [111]2Monocrystal rod, crystal growth is under condition of high vacuum degree or in high-purity Ar
In atmosphere.
The present invention is by being co-doped with adjustment ion (the praseodymium ion Pr of three valence states3+, and three valence state cationes R3+(Y3+、La3+、
Gd3+、Sc3+And Lu3+Deng)), at same alkaline earth fluoride MF2In (M=Ca, Sr), formed by crystal and regulate and control acquisition respectively
The crystal that the reddest, orange, green or blue laser exports.
(Pr by above-mentioned growth3+, R3+):MF2Crystal-cut is in blocks, at FLsP960 fluorescence light after optical grade polishes
Room temperature emission spectra is tested, the flicker xenon lamp that pumping source uses wavelength to be 443nm on spectrometer.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Invention is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential improvement and adjustment that bright foregoing is made belong to protection scope of the present invention.Following example is concrete
Technological parameters etc. are the most only that an example in OK range, i.e. those skilled in the art can be done properly by explanation herein
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Bridgman-Stockbarge method for growing 0.6at%Pr:CaF2, 0.6at%Pr0.6at%Y:CaF2, 0.6at%Pr1.2at%Y:CaF2
Crystal；
(1) 0.6at%Pr:CaF2Crystal: weigh PrF in proportion3(5N) 2.21g, CaF2(5N)144.79g；
(2) 0.6at%Pr0.6at%Y:CaF2Crystal: weigh PrF in proportion3(5N) 2.70g, YF3(5N) 1.99g and CaF2
(5N)175.31g；
(3) 0.6at%Pr1.2at%Y:CaF2Crystal: weigh PrF in proportion3(5N) 2.68g, YF3(5N) 3.96g and CaF2
(5N)173.36g。
By above-mentioned respective proportion scale weighing, it is sufficiently mixed in vacuum glove box, is placed in platinum crucible.Use crucible
Descent method for growing crystal, atmosphere is fine vacuum, and vacuum is 2.5 × 10-3Pa, 1400 DEG C of fused raw materials also start growth, crucible
Fall off rate is 1.5mm/h, and after 120h, crystal growth is complete, is then cooled to room temperature by 20 DEG C/h.
Fig. 1 is the 0.6at%Pr:CaF of embodiment 1 growth2, 0.6at%Pr 0.6at%Y:CaF2And 0.6at%Pr
1.2at%Y:CaF2The Room temperature emission spectra of crystal.It is co-doped with into Y3+After, crystallofluorescence intensity is compared and is singly mixed Pr3+Sample, each fluorescence
Peak fluorescence intensity is greatly improved, and each fluorescence peak intensity changes.Wherein blue light region 482nm fluorescence peak fluorescence intensity is
Height, other are once 598nm orange light peak, 642nm HONGGUANG peak and 535nm green light peak.Along with Y3+The raising of ion concentration, 482nm
535nm green light peak is compared at blue light peak and 598nm orange light peak and 642nm HONGGUANG peak amplification is bigger.
Embodiment 2 Growth by Temperature Gradient Technique 0.6at%Pr 3.0at%Gd:CaF2And 0.6at%Pr3.0at%Y:CaF2
Crystal
Weigh PrF in proportion3(5N) 2.00g, GdF3(5N) 10.9g and CaF2(5N) 127.1g and PrF3(5N) 2.06g, YF3
(5N) 7.58g and CaF2(5N), after 130.36g is sufficiently mixed in vacuum glove box, it is placed in graphite crucible, seed crystal employing <
111 > the pure CaF in direction2Crystal, seed size is Φ 6*30mm.Using temperature gradient method, atmosphere is fine vacuum, and 1400 DEG C melt
Raw material also starts growth, and cooling growth rate is 1.5 DEG C/h, and after 120h, crystal growth completes, and is then cooled to room by 20 DEG C/h
Temperature.
Fig. 2 is the 0.6at%Pr:CaF in embodiment 120.6at%Pr 3.0at%Gd in crystal and embodiment 2:
CaF2And 0.6at%Pr3.0at%Y:CaF2The Room temperature emission spectra of crystal, test excitation wavelength is 443nm, and excitation source is
Flicker xenon lamp.It can be seen that be co-doped with non-luminous Y itself3+Ion or Gd3+After ion, crystal each fluorescence peak fluorescence is strong
Degree is greatly improved.Additionally, Y3+Ion and Gd3+Ion pair Pr:CaF2The regulating effect of crystallofluorescence peak fluorescence intensity also differs.
Y3+Ion for the reinforced effects at orange light peak near 600nm more than the HONGGUANG peak near 640nm, and Gd3+Ion is for 640nm
The reinforced effects at neighbouring HONGGUANG peak is better than the orange light peak near 600nm.From overall regulating effect, Gd3+Ion is for Pr:
CaF2The regulating and controlling effect of crystallofluorescence intensity is better than Y3+Ion.
Embodiment 3 Bridgman-Stockbarge method for growing 0.6at%Pr1.2at%La:CaF2Crystal
Weigh PrF in proportion3(5N) 1.48g, LaF3(5N) 2.93g and CaF2(5N)95.59g.It is placed in platinum crucible.Adopt
Using Bridgman-Stockbarge method for growing crystal, atmosphere is fine vacuum, and vacuum is 2.5 × 10-3Pa, 1400 DEG C of fused raw materials also start raw
Long, crucible fall off rate is 1.5mm/h, and after 120h, crystal growth is complete, is then cooled to room temperature by 20 DEG C/h.
Embodiment 4 Bridgman-Stockbarge method for growing 0.6at%Pr1.2at%Sc:CaF2Crystal
Weigh PrF in proportion3(5N) 1.50g, ScF3(5N) 1.55g and CaF2(5N)96.95g.It is placed in platinum crucible.Adopt
Using Bridgman-Stockbarge method for growing crystal, atmosphere is fine vacuum, and vacuum is 2.5 × 10-3Pa, 1400 DEG C of fused raw materials also start raw
Long, crucible fall off rate is 1.5mm/h, and after 120h, crystal growth is complete, is then cooled to room temperature by 20 DEG C/h.
Embodiment 5 Bridgman-Stockbarge method for growing 0.3at%Pr:SrF2, 0.6at%Pr:SrF2And 1.5at%Pr:SrF2Crystal
(1) 0.3at%Pr:SrF2Crystal: weigh PrF in proportion3(5N) 0.57g, SrF2(5N)119.43g；
(2) 0.6at%Pr:SrF2Crystal: weigh PrF in proportion3(5N) 1.88g, SrF2(5N)118.12g；
(3) 1.5at%Pr:SrF2Crystal: weigh PrF in proportion3(5N) 2.81g, SrF2(5N)117.19g；
By above-mentioned respective proportion scale weighing, it is sufficiently mixed in vacuum glove box, is placed in platinum crucible.Employing crucible declines
Method growth crystal, atmosphere is fine vacuum, and vacuum is 2.5 × 10-3Pa, 1500 DEG C of fused raw materials also start growth, and crucible declines
Speed is 1.5mm/h, and after 140h, crystal growth is complete, is then cooled to room temperature by 20 DEG C/h.
Embodiment 6 Bridgman-Stockbarge method for growing 0.6at%Pr0.6at%Y:SrF2And 0.6at%Pr:3.0at%Y:SrF2Brilliant
Body
(1) 0.6at%Pr0.6at%Y:SrF2Crystal: weigh PrF in proportion3(5N) 0.84g, YF3(5N)0.69g,SrF2
(5N)98.37g；
(2) 0.6at%Pr:3.0at%Y:SrF2Crystal: weigh PrF in proportion3(5N) 0.83g, YF3(5N)3.46g,SrF2
(5N)95.61g；
By above-mentioned respective proportion scale weighing, it is sufficiently mixed in vacuum glove box, is placed in platinum crucible.Employing crucible declines
Method growth crystal, atmosphere is fine vacuum, and vacuum is 2.5 × 10-3Pa, 1500 DEG C of fused raw materials also start growth, and crucible declines
Speed is 1.5mm/h, and after 140h, crystal growth is complete, is then cooled to room temperature by 20 DEG C/h.
Fig. 3 is the 0.6at%Pr:SrF in embodiment 52The 0.6at%Pr0.6at%Y of growth in crystal and embodiment 6:
SrF2And 0.6at%Pr:3.0at%Y:SrF2The Room temperature emission spectra of crystal.It can be seen that Y3+Ion is greatly improved
Glow peak luminous intensity near crystal 480nm and 699nm, and make the 600nm fluorescence peak-to-peak by force more than fluorescence near 480nm
Peak, is i.e. co-doped with Y3+This crystal is made to be suitable as the operation material of 600nm orange laser.
Embodiment 7 Bridgman-Stockbarge method for growing 0.6at%Pr0.6at%Gd:SrF2And 0.6at%Pr:3.0at%Gd:SrF2
Crystal
(1) 0.6at%Pr0.6at%Gd:SrF2Crystal: weigh PrF in proportion3(5N) 0.94g, GdF3(5N) 1.02g, SrF2
(5N)98.04g；
(2) 0.6at%Pr:3.0at%Gd:SrF2Crystal: weigh PrF in proportion3(5N) 0.92g, GdF3(5N)4.99g,SrF2
(5N)94.09g；
By above-mentioned respective proportion scale weighing, it is sufficiently mixed in vacuum glove box, is placed in platinum crucible.Employing crucible declines
Method growth crystal, atmosphere is fine vacuum, and vacuum is 2.5 × 10-3Pa, 1500 DEG C of fused raw materials also start growth, and crucible declines
Speed is 1.5mm/h, and after 140h, crystal growth is complete, is then cooled to room temperature by 20 DEG C/h.
Fig. 4 is the 0.6at%Pr:SrF in embodiment 52Crystal, the 0.6at%Pr0.6at%Y of growth in embodiment 6:
SrF2And the 0.6at%Pr:0.6at%Gd:SrF of growth in embodiment 72The Room temperature emission spectra of crystal.As can be seen from the figure
It is co-doped with Y3+Be co-doped with Gd3+The most all improve the fluorescence intensity of each emission peak of crystal.Wherein Y3+To with 600nm orange light
Region promotes the most obvious, and Gd3+Promote the most obvious for red light region near 640nm.
Industrial applicability: the praseodymium ion (Pr that the present invention provides3+) and Tricationic (R3+) the bivalent cation fluorine that is co-doped with
Compound (MF2) laser crystal, compare Pr3+M mixed by ion list2Crystal, has each regulatable characteristic of fluorescence peak fluorescence intensity, passes through
Adjustment is co-doped with R3+The kind of ion and concentration, regulate and control the intensity at crystallofluorescence peak, so that obtain can the photism of phase
Energy.
Claims (8)
1. the regulatable rare earth ion doped alkaline earth fluoride laser crystal of spectrum property, it is characterised in that described rare earth
The chemical formula of ion doping alkaline earth fluoride laser crystal is (Pr3+, R3+): MF2, wherein R3+For Y3+、La3+、Gd3+、Sc3+With
Lu3+In at least one, described praseodymium ion Pr3+Doping content be 0.1at%～2.0at%, described R3+Doping content be
0.5at%～20.0at%.
Rare earth ion doped alkaline earth fluoride laser crystal the most according to claim 1, it is characterised in that wherein M is Ca
Or Sr.
3. a preparation method for rare-earth ion-doped doping alkaline earth Fluoride Laser Crystals as described in claim 1 or 2, it is special
Levy and be, weigh raw material PrF according to stoichiometric3、RF3And MF2, use melt method under fine vacuum or protective atmosphere
Growth crystal.
Preparation method the most according to claim 3, it is characterised in that add PbF in material powder2Powder is as deoxygenation
Agent, described PbF2The addition of powder is MF2The 0.1～2.0wt% of powder.
5. according to the preparation method described in claim 3 or 4, it is characterised in that use Bridgman-Stockbarger method or temperature gradient method
Growth crystal, crucible material uses high purity graphite or platinum, and crystal growth is carried out in protective atmosphere or fine vacuum atmosphere.
6. according to the preparation method according to any one of claim 3-5, it is characterised in that crucible bottom be added without seed crystal or
Put into the MF used through X-ray diffractometer orientation end face normal direction is [111]2Monocrystal rod is as seed crystal.
7. according to the preparation method according to any one of claim 3-6, it is characterised in that described protective atmosphere is high-purity Ar gas
Atmosphere and/or fluorine-containing atmosphere.
Preparation method the most according to claim 7, it is characterised in that described fluorine-containing atmosphere is CF4And/or HF gas or
CF4And/or the gaseous mixture of HF gas and argon.
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Cited By (11)
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| CN106673658A (en) * | 2016-12-27 | 2017-05-17 | 武汉理工大学 | Praseodymium-doped strontium fluoride laser ceramics capable of facilitating red and orange light laser output, and preparation method of laser ceramics |
| CN107740186A (en) * | 2017-10-30 | 2018-02-27 | 中国科学院上海硅酸盐研究所 | A kind of large scale Yb, R:CaF2/SrF2Laser crystal and preparation method thereof |
| CN109181684A (en) * | 2018-08-17 | 2019-01-11 | 中国科学院上海硅酸盐研究所 | A kind of crystalline material and preparation method thereof for realizing white light emission by upper conversion |
| CN109778314A (en) * | 2019-02-01 | 2019-05-21 | 淮安红相光电科技有限公司 | A kind of La doped barium fluoride crystal and preparation method thereof |
| CN110541198A (en) * | 2018-05-29 | 2019-12-06 | 中国科学院上海硅酸盐研究所 | Europium ion doped fluoride crystal with display color gamut capable of being regulated and controlled in large range and preparation method thereof |
| CN110607557A (en) * | 2019-09-04 | 2019-12-24 | 同济大学 | Spectrum-doped lead fluoride visible-band laser crystal and preparation method thereof |
| CN110760930A (en) * | 2019-11-07 | 2020-02-07 | 中国科学院上海硅酸盐研究所 | Alkaline earth metal fluoride laser crystal doped with multiple trivalent modulator ions and preparation method thereof |
| CN112144119A (en) * | 2020-08-19 | 2020-12-29 | 中国科学院福建物质结构研究所 | Rare earth doped barium calcium fluoborate laser crystal, preparation method thereof and method for realizing laser |
| CN113502538A (en) * | 2021-06-28 | 2021-10-15 | 同济大学 | Praseodymium-doped lutetium fluoride calcium composite visible band laser crystal and preparation method and application thereof |
| CN113502539A (en) * | 2021-06-28 | 2021-10-15 | 同济大学 | Praseodymium-gadolinium co-doped mixed calcium fluoride laser crystal and preparation method and application thereof |
| CN114276803A (en) * | 2021-12-21 | 2022-04-05 | 河南工程学院 | Carbon dot and rare earth ion doped SrF2Composite material and synthesis method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673658A (en) * | 2016-12-27 | 2017-05-17 | 武汉理工大学 | Praseodymium-doped strontium fluoride laser ceramics capable of facilitating red and orange light laser output, and preparation method of laser ceramics |
| CN107740186A (en) * | 2017-10-30 | 2018-02-27 | 中国科学院上海硅酸盐研究所 | A kind of large scale Yb, R:CaF2/SrF2Laser crystal and preparation method thereof |
| CN110541198A (en) * | 2018-05-29 | 2019-12-06 | 中国科学院上海硅酸盐研究所 | Europium ion doped fluoride crystal with display color gamut capable of being regulated and controlled in large range and preparation method thereof |
| CN109181684B (en) * | 2018-08-17 | 2021-07-13 | 中国科学院上海硅酸盐研究所 | Crystal material for realizing white light emission through up-conversion and preparation method thereof |
| CN109181684A (en) * | 2018-08-17 | 2019-01-11 | 中国科学院上海硅酸盐研究所 | A kind of crystalline material and preparation method thereof for realizing white light emission by upper conversion |
| CN109778314A (en) * | 2019-02-01 | 2019-05-21 | 淮安红相光电科技有限公司 | A kind of La doped barium fluoride crystal and preparation method thereof |
| CN110607557A (en) * | 2019-09-04 | 2019-12-24 | 同济大学 | Spectrum-doped lead fluoride visible-band laser crystal and preparation method thereof |
| CN110760930A (en) * | 2019-11-07 | 2020-02-07 | 中国科学院上海硅酸盐研究所 | Alkaline earth metal fluoride laser crystal doped with multiple trivalent modulator ions and preparation method thereof |
| CN110760930B (en) * | 2019-11-07 | 2021-10-01 | 中国科学院上海硅酸盐研究所 | Alkaline earth metal fluoride laser crystal doped with multiple trivalent modulator ions and preparation method thereof |
| CN112144119A (en) * | 2020-08-19 | 2020-12-29 | 中国科学院福建物质结构研究所 | Rare earth doped barium calcium fluoborate laser crystal, preparation method thereof and method for realizing laser |
| CN112144119B (en) * | 2020-08-19 | 2022-04-01 | 中国科学院福建物质结构研究所 | Rare earth doped barium calcium fluoborate laser crystal, preparation method thereof and method for realizing laser |
| CN113502538A (en) * | 2021-06-28 | 2021-10-15 | 同济大学 | Praseodymium-doped lutetium fluoride calcium composite visible band laser crystal and preparation method and application thereof |
| CN113502539A (en) * | 2021-06-28 | 2021-10-15 | 同济大学 | Praseodymium-gadolinium co-doped mixed calcium fluoride laser crystal and preparation method and application thereof |
| CN114276803A (en) * | 2021-12-21 | 2022-04-05 | 河南工程学院 | Carbon dot and rare earth ion doped SrF2Composite material and synthesis method thereof |
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