CN110396721A - Fluorine boron aluminic acid cesium compound, fluorine boron aluminic acid caesium nonlinear optical crystal and its preparation method and application - Google Patents
Fluorine boron aluminic acid cesium compound, fluorine boron aluminic acid caesium nonlinear optical crystal and its preparation method and application Download PDFInfo
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- CN110396721A CN110396721A CN201910688722.3A CN201910688722A CN110396721A CN 110396721 A CN110396721 A CN 110396721A CN 201910688722 A CN201910688722 A CN 201910688722A CN 110396721 A CN110396721 A CN 110396721A
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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
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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
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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
- C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
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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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
Abstract
The present invention provides a kind of fluorine boron aluminic acid cesium compound, fluorine boron aluminic acid caesium nonlinear optical crystal and its preparation method and application, the chemical formula of the crystal is CsAlB3O6F, molecular weight 307.32, the structure of the crystal belong to rhombic system, and space group isPna21, cell parameter isa=8.064,b=11.970,c=7.036,α=β=γ=90 °, unit-cell volume 679.23.Czochralski method can be used in the crystal or the growth of high temperature solution method is prepared.Crystal of the invention has stronger nonlinear optical effect, its ultraviolet cut-on side is shorter than 180 nm, can be used in the nm of Nd:YAG(λ=1064) 2 frequencys multiplication of laser, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication even 6 multiplied frequency harmonic generators, or even for generating the harmonic wave light output for being shorter than 200 nm.
Description
Technical field
The present invention relates to technical field of optoelectronic functional materials, a kind of fluorine boron aluminic acid cesium compound, fluorine are related in particular to
Boron aluminic acid caesium nonlinear optical crystal and its preparation method and application.
Background technique
The nonlinear optical effect of crystal refers to Zhe Yang ー kind effect: when a branch of laser with certain polarization direction is by one
When determining incident direction and leading to ー block nonlinear optical crystal, the frequency of the light beam will change.Fig. 1 is to be swashed based on the effect
The canonical schema applied in light device.
Crystal with non-linear optical effect is known as nonlinear optical crystal.The nonlinear effect herein referred to is in particular to
Second order nonlinear optical effect (similarly hereinafter), the only crystal without symmetrical centre have been likely to this effect.Using the effect,
Quartz crystal device can be assembled and second-harmonic conversion device, the nonlinear opticses such as upper and lower frequency converter, optical parametric oscillator are made
Device, so that the limited laser light source of wave-length coverage is expanded to visible, ultraviolet or even dark purple outskirt (wavelength is shorter than 200 nm),
The range for widening optical maser wavelength makes being more widely applied for laser.
In this field, it is suitable for visible, ultraviolet band non-linear optical crystal material such as KDP (KH at present2PO4)、
KTP (KTiOPO4)、BBO (β-BaB2O4)、LBO (LiB3O5) etc. have excellent optical property, have been carried out industrialization, and
It is widely used in photo-optics, photoengraving, precision instrument processing and other fields.But it for deep ultraviolet band, is applicable in
In the non-linear optical crystal material of the wave band, apart from practical application, there are also gaps.Reason is that current material is unsatisfactory for deep ultraviolet
Wave band penetrates or the requirement of phase matched.Currently, only KBe2BO3F2 (KBBF) and its isomorphism crystal RbBe2BO3F2It can be real
Border is applied to the stable output of direct six frequency multiplication (177.3 nm) laser of Nd:YAG laser and 200 nm laser of 170- can
Tuning operation (referring to Opt. Mater., 1996,5,105-109.).However, there is also very significant disadvantages for KBBF crystal:
With layer growth habit, it is difficult to obtain large-size crystals, significantly limit its large-scale production and application.In addition,
Beryllium oxide containing severe toxicity in KBBF raw material, also affects its preparation of industrialization to a certain extent.Since wavelength is less than 200nm
Deep ultraviolet laser, the fields such as medical treatment, communication, scientific research have significant application value, preparation synthesis excellent combination property
Novel deep ultraviolet nonlinear optical crystal material be of great significance and practical value.
How research for deep ultraviolet nonlinear optical crystal realizes big nonlinear optical coefficients (> 1 times of KDP), width
Transparency range (ultraviolet cut-on side be lower than 200 nm), the balance of moderate birefringent (n ~ 0.08 meets phase matched),
It is key scientific problems.It is also required that new crystalline material is easy growth, physical and chemical performance stabilization, advantages of nontoxic raw materials, is suitable for adding
The requirement such as work.It is stranded very much however, design filters out whole novel deep ultraviolet nonlinear optical crystal materials for meeting above-mentioned requirements
It is difficult.
Summary of the invention
It is an object of the invention to provide a kind of fluorine boron aluminic acid cesium compound, fluorine boron aluminic acid caesium nonlinear optical crystal and its
Preparation method and purposes, to solve the problems, such as that existing nonlinear optical crystal comprehensive performance is undesirable.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of fluorine boron aluminic acid cesium compound, chemical formula are
CsAlB3O6F。
A kind of preparation method of above-mentioned fluorine boron aluminic acid cesium compound, comprising the following steps:
A, weighing the compound containing Cs, Al, B, O and F respectively according to the molar ratio of chemical formula is raw material；
B, raw material mixed grinding is placed in Muffle furnace, is warming up to 350 ~ 450 DEG C, pre-burning 1 ~ 5 hour；
C, it is cooled to room temperature after the completion of pre-burning, takes out grinding, then heat to 500 ~ 650 DEG C, be sintered 24 ~ 96 hours, Zhi Houleng
But it takes out up to fluorine boron aluminic acid cesium compound polycrystal powder.
Further, in step a, the raw materials of compound containing Cs is oxide, hydroxide, carbonate, fluorination containing caesium
Object, nitrate or borate；Raw materials of compound containing Al is oxide, hydroxide or fluoride containing aluminium；Compound containing B
Raw material is H3BO3Or B2O3；Raw materials of compound containing F is CsF, CsBF4Or NH4F。
A kind of fluorine boron aluminic acid caesium nonlinear optical crystal, the chemical formula of the crystal are CsAlB3O6F, molecular weight are
307.32, the structure of the crystal belongs to rhombic system, and space group isPna21, cell parameter isa=8.064,b =
11.970,c=7.036,α = β = γ=90 °, unit-cell volume 679.23。
A kind of preparation method of the fluorine boron aluminic acid caesium nonlinear optical crystal of preceding claim, comprising the following steps:
A, fluorine boron aluminic acid cesium compound polycrystal powder prepared by Claims 2 or 3 is packed into platinum crucible, is subsequently placed in crystal
In furnace, 750 ~ 800 DEG C are warming up to, is completely melt uniformly, to be cooled to freezing point or more rapidly later to raw material within constant temperature 10 ~ 48 hours
0.5 ~ 2 DEG C, obtain melt, wherein the freezing point is 560 DEG C；
B, seed crystal is fixed on the lower end of seed rod and is contacted with melt liquid level, be cooled to freezing point or low after preheating 1 ~ 10min
In 0.1 ~ 1 DEG C of freezing point, start to carry out crystal growth；
C, by crystal growth controller apply 2 ~ 20rpm crystalline substance turn, with 0 ~ 10 mm/ days speed lift seed crystal (do not lift
Seed crystal or to lift seed crystal no more than 10 mm/ days speed), then by the rate slow cooling of 0.1 ~ 5 DEG C/day, cooling terminates
Afterwards by crystal lift-off liquid level, room temperature is down to get the fluorine boron aluminic acid caesium nonlinear optics with 10 ~ 30 DEG C/h of rate
Crystal.
Another preparation method of above-mentioned fluorine boron aluminic acid caesium nonlinear optical crystal, comprising the following steps:
A, fluorine boron aluminic acid cesium compound polycrystal powder prepared by Claims 2 or 3 and fluxing agent are packed into platinum crucible, then
It is placed in crystal oven, is warming up to 600 ~ 700 DEG C, constant temperature 10 ~ 48 hours are completely melt uniformly to raw material, are cooled to rapidly later full
It is 5 ~ 10 DEG C above with point, obtain blend melt, wherein the saturation point temperature is 500 ~ 550 DEG C；
B, seed crystal is fixed on the lower end of seed rod and is contacted with blend melt liquid level, be cooled to saturation point after preheating 1 ~ 10min,
Start to carry out crystal growth；
C, turned by the crystalline substance that crystal growth controller applies 2 ~ 20rpm, then press the rate slow cooling of 0.1 ~ 5 DEG C/day, cooling
After by crystal lift-off liquid level, it is non-linear to get the fluorine boron aluminic acid caesium that room temperature is down to 10 ~ 30 DEG C/h of rate
Optical crystal.
Further, the fluxing agent is B2O3、H3BO3、CsF、(NH4)2AlF6One or both of mixture；Institute
The molar ratio for stating fluorine boron aluminic acid cesium compound polycrystal powder and fluxing agent is 1: 0.3 ~ 3；The crystal ruler that the preparation method obtains
It is very little to be greater than 3.0 mm.
A kind of purposes of above-mentioned fluorine boron aluminic acid caesium nonlinear optical crystal, the crystal are used to be 1064 nm's to wavelength
Laser beam generates the harmonic wave light output of 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication or 6 frequencys multiplication.
A kind of purposes of above-mentioned fluorine boron aluminic acid caesium nonlinear optical crystal, harmonic wave of the crystal for dark purple outskirt occur
Device, optical parameter and amplifying device or fiber waveguide device.
A kind of purposes of above-mentioned fluorine boron aluminic acid caesium nonlinear optical crystal, the crystal are used for the outskirt from infrared to dark purple
Optical parameter and amplifying device.
Nonlinear optical crystal of the invention has stronger nonlinear optical effect, and (powder frequency doubling test shows its powder
The commercialization crystal KH that frequency-doubled effect is about 2.4 times2PO4)；Its ultraviolet cut-on side is shorter than 180 nm.In addition, crystal of the invention
Non-linear optical property can be used in the nm of Nd:YAG(λ=1064 close to KBBF) 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 times of laser
Frequency even 6 multiplied frequency harmonic generators, or even the harmonic wave light output for generating shorter than 200 nm.Further more, crystal of the invention is
Mono-crystalline structures, colorless and transparent, stable in the air, thermal stability is good, does not use hypertoxic Material synthesis, crystal stratiform habit
It is not significant.
Fluorine boron aluminic acid caesium nonlinear optical crystal (abbreviation CABF) of the invention has excellent optical property, crystal knot
With B in structure3O6And AlO3F group composed structure primitive.On the one hand conjugation group B3O6Be capable of providing big nonlinear effect and compared with
Big birefringence, another aspect AlO3F group plays the role of eliminating terminal oxygen atom dangling bonds, increases crystal UV transmission model
It encloses.Therefore, CABF crystal of the invention has both wide UV transmission range, big nonlinear effect and biggish birefringence
Advantage.With the crystal phase ratio of existing KBBF, non-linear optical property is close, but the interlamellar spacing of CABF crystal is obviously shortened, and improves
Layer growth habit, and without using BeO severe toxicity raw material, it is easy to carry out large-size crystals growth and realizes industrialization.This hair
Bright CABF crystal is able to satisfy from the infrared demand used to deep ultraviolet light area nonlinear optical crystal.
Detailed description of the invention
Fig. 1 is that fluorine boron aluminic acid caesium nonlinear optical crystal shows as the typical case of frequency-doubling crystal application non-linear hour optical effect
It is intended to, wherein 1 is laser, and 2 is issue light beam, and 3 be the fluorine boron aluminic acid caesium crystal after processing, and 4 be outgoing beam, and 5 be filtering
Piece.
Fig. 2 is the XRD x ray diffraction map that fluorine boron aluminic acid caesium crystal is pulverized last.
Fig. 3 is the structural schematic diagram of fluorine boron aluminic acid caesium crystal.
Specific embodiment
Below with specific embodiment the present invention is described in detail.Following embodiments cannot function as the limit to the scope of the present invention
System, any improvement made on the basis of the present invention is all without prejudice to spirit of that invention.The raw materials used in the present invention or equipment, such as without spy
Different explanation, can commercially be commercially available.The process conditions that the present invention does not mention are by the routine operation of the prior art
It carries out.
Embodiment 1
Prepare fluorine boron aluminic acid cesium compound:
By reaction equation: 2CsF+Al2O3 + 3B2O3 = 2CsAlB3O6F synthesizes compound CsAlB3O6The throwing of F agents useful for same
Doses are as follows:
3.038 g of CsF (0.02mol)
Al2O31.020 g (0.01mol)
B2O32.089 g (0.03mol)
Specific steps are as follows:
By above-mentioned quality precise raw material, be put into agate mortar, be uniformly mixed and carefully grind, be then charged into φ 60mm ×
In the corundum crucible of 60mm, compacting is put into Muffle furnace and is warming up to 400 DEG C with 50 DEG C/h of heating rate, constant temperature 3 is small
When.It is taken out after then cooling to room temperature, compacting is put into Muffle furnace after being fully ground again, with 200 DEG C/h of heating speed
Rate is warming up to 600 DEG C and calcination 24 hours.It is repeated twice previous step, is aggregated in after 600 DEG C of calcining 72h to get compound is arrived
CsAlB3O6F.Reaction product purity is determined with powder x-ray diffraction.
Embodiment 2:
Prepare fluorine boron aluminic acid cesium compound:
By reaction equation: 2CsF+ 2Al (OH)3+3B2O3 = 2CsAlB3O6F+3H2O synthesizes compound CsAlB3O6F agents useful for same
Inventory are as follows:
3.038 g of CsF (0.02mol)
Al(OH)31.560 g (0.02mol)
B2O32.089 g (0.03mol)
Specific steps are as follows:
It by above-mentioned quality precise raw material, is put into agate mortar, is uniformly mixed and carefully grinds, be then charged into 40 mm of φ
In the platinum crucible of × 40 mm, compacting is put into Muffle furnace and is warming up to 500 DEG C with 50 DEG C/h of heating rate, constant temperature 3
Hour.It is taken out after then cooling to room temperature, compacting is put into Muffle furnace after being fully ground again, with 100 DEG C/h of heating
Rate is warming up to 650 DEG C and calcination 96 hours to get to compound CsAlB3O6F.Reaction product is determined with powder x-ray diffraction
Purity.
Embodiment 3:
Czochralski grown CsAlB3O6F nonlinear optical crystal:
By the fluorine boron aluminic acid cesium compound polycrystal powder of the preparation platinum (as described in example 1 above) for being packed into φ 40 mm × 60 mm
In golden crucible, it is placed in crystal oven, is warming up to 800 DEG C with 300 DEG C/h of heating rate, constant temperature 10 hours, until raw material is complete
Fusing uniformly, is cooled to rapidly 1 DEG C of freezing point or more (about 561 DEG C).Then seed crystal is fixed on to lower end and the melt of seed rod
Liquid level contact is cooled to freezing point after overheating 10min or lower than 1 DEG C of freezing point (559 DEG C), starts crystal growth.Pass through crystal
The crystalline substance turn that controller applies 10 rpm is grown, seed crystal was lifted with 5mm/ days rates, then presses the rate slow cooling of 1 DEG C/day.
By crystal lift-off liquid level after crystal growth, with 30 DEG C/h of rate be down to room temperature to get to having a size of 3 mm ×
The CsAlB of the mm of 3 mm × 43O6F nonlinear optical crystal.Gained crystal has structure as shown in Figure 3, and crystal is pulverized
Last XRD x ray diffraction map is as shown in Figure 2.
Embodiment 4:
Kyropoulos grow CsAlB3O6F nonlinear optical crystal:
By the fluorine boron aluminic acid cesium compound polycrystal powder of the preparation platinum (as described in example 2 above) for being packed into φ 50 mm × 50 mm
In golden crucible, it is placed in crystal oven, is warming up to 750 DEG C with 200 DEG C/h of heating rate, constant temperature 48 hours, until raw material is complete
Fusing uniformly, is cooled to rapidly 0.5 DEG C of freezing point or more (560.5 DEG C).Then by seed crystal be fixed on the lower end of seed rod with
Melt liquid level contact is cooled to freezing point after overheating 1min or lower than 0.1 DEG C of freezing point (559.9 DEG C), starts crystal growth.
Turned by the crystalline substance that crystal growth controller applies 2 rpm, do not lift seed crystal, then presses the rate slow cooling of 0.1 DEG C/day.
By crystal lift-off liquid level after crystal growth, room temperature is down to get to having a size of 3 mm × 3 with 10 DEG C/h of rate
The CsAlB of the mm of mm × 23O6F nonlinear optical crystal.Gained crystal structure and XRD x ray diffraction map and 3 class of embodiment
Seemingly.
Embodiment 5:
High temperature solution method grows CsAlB3O6F nonlinear optical crystal:
The conjunction object CsAlB prepared according to embodiment 23O6F polycrystal powder is uniformly mixed at 1: 1 in molar ratio with fluxing agent CsF, is packed into
In platinum crucible, 650 DEG C are warming up to 200 DEG C/h of heating rate, constant temperature 24 hours, obtains mixed molten liquid；Drop rapidly
More than temperature to saturation point 10 DEG C (530 DEG C).Then seed crystal is fixed on to lower end and the liquid fused salt face contact of seed rod, overheat 10
It is cooled to after min saturation temperature (520 DEG C), starts crystal growth.Turned by the crystalline substance that crystal growth controller applies 3 rpm, so
The rate slow cooling of 0.1 DEG C/day is pressed afterwards.By crystal lift-off liquid level after cooling, dropped with 10 ~ 30 DEG C/h of rate
To room temperature, the CsAlB having a size of the mm × 2 of 5 mm × 4 mm is arrived after crystal growth stopping3O6F nonlinear optics
Crystal.Gained crystal structure and XRD x ray diffraction map are similar to Example 3.
Embodiment 6:
High temperature solution method grows CsAlB3O6F nonlinear optical crystal:
The conjunction object CsAlB prepared according to embodiment 23O6F polycrystal powder and fluxing agent B2O3It is uniformly mixed at 1: 0.3 in molar ratio, dress
Enter in platinum crucible, is warming up to 750 DEG C with 150 DEG C/h of heating rate, constant temperature 12 hours, obtains mixed molten liquid；Rapidly
It is cooled to 5 DEG C of saturation point or more (555 DEG C).Then seed crystal is fixed on to lower end and the liquid fused salt face contact of seed rod, overheat 5
It is cooled to after min saturation temperature (550 DEG C), starts crystal growth.Turned by the crystalline substance that crystal growth controller applies 5 rpm,
Then the rate slow cooling of 0.5 DEG C/day is pressed.By crystal lift-off liquid level after cooling, it is down to 20 DEG C/h of rate
Room temperature arrives the CsAlB having a size of the mm × 1 of 5 mm × 4 mm after crystal growth stopping3O6F non-linear optical crystal
Body.Gained crystal structure and XRD x ray diffraction map are similar to Example 3.
Embodiment 7:
High temperature solution method grows CsAlB3O6F nonlinear optical crystal:
The compound CsAlB prepared according to embodiment 13O6F polycrystal powder and composite fluxing agent (CsF: B2O3=1: 1) by mole
It is uniformly mixed than 1: 3, is fitted into platinum crucible, is warming up to 650 DEG C with 100 DEG C/h of heating rate, constant temperature 36 hours, obtains
To mixed molten liquid；It is cooled to 3 DEG C of saturation point or more (503 DEG C) rapidly.Then seed crystal is fixed on to lower end and the fused salt of seed rod
Liquid level contact, is cooled to saturation temperature (500 DEG C) after overheating 8 min, starts crystal growth.It is applied by crystal growth controller
Add the crystalline substance of 10 rpm to turn, then presses the rate slow cooling of 2 DEG C/day.By crystal lift-off liquid level after cooling, with 30 DEG C
The rate of/hour is down to room temperature, to get to having a size of the mm × 1 of 4 mm × 4 mm's after crystal growth stopping
CsAlB3O6F nonlinear optical crystal.Gained crystal structure and XRD x ray diffraction map are similar to Example 3.
Embodiment 8
By CsAlB3O6F crystal is placed on 3 position, at room temperature, with tune by the direction processing that matches as shown in attached drawing 1
Q-Nd:YAG laser light source, incident wavelength are 1064 nm, are 1064nm's by adjusting Q-Nd:YAG laser 1 to issue wavelength
Light beam 2 injects CsAlB3O6F monocrystalline 3 eliminates fundamental frequency light by optical filter 5, can get the green frequency doubled light that wavelength is 532nm.
Embodiment 9
By CsAlB3O6F crystal is placed on 3 position, at room temperature, with tune by the direction processing that matches as shown in attached drawing 1
Q-Nd:YAG laser light source, incident wavelength are 532 nm, are 532 nm's by adjusting the Nd:YAG laser 1 of Q to issue wavelength
Light beam 2 injects CsAlB3O6F monocrystalline 3 eliminates fundamental frequency light by optical filter 5, can get the ultraviolet frequency double light that wavelength is 266 nm.
Embodiment 10
By CsAlB3O6F crystal is placed on 3 position, at room temperature, with tune by the direction processing that matches as shown in attached drawing 1
Q-Nd:YAG laser light source, incident wavelength are 355 nm, by adjusting Q-Nd:YAG laser 1 to issue the light that wavelength is 355 nm
Beam 2 injects CsAlB3O6F monocrystalline 3 eliminates fundamental frequency light by optical filter 5, and the deep ultraviolet frequency multiplication that wavelength is 177.3 nm can be observed
Light output.
Claims (10)
1. a kind of fluorine boron aluminic acid cesium compound, chemical formula CsAlB3O6F。
2. a kind of preparation method of fluorine boron aluminic acid cesium compound described in claim 1, characterized in that the following steps are included:
A, weighing the compound containing Cs, Al, B, O and F respectively according to the molar ratio of chemical formula is raw material；
B, raw material mixed grinding is placed in Muffle furnace, is warming up to 350 ~ 450 DEG C, pre-burning 1 ~ 5 hour；
C, it is cooled to room temperature after the completion of pre-burning, takes out grinding, then heat to 500 ~ 650 DEG C, be sintered 24 ~ 96 hours, Zhi Houleng
But it takes out up to fluorine boron aluminic acid cesium compound polycrystal powder.
3. the preparation method of fluorine boron aluminic acid cesium compound according to claim 2, characterized in that in step a, the change containing Cs
Closing raw material is oxide, hydroxide, carbonate, fluoride, nitrate or borate containing caesium；Raw materials of compound containing Al
For oxide, hydroxide or fluoride containing aluminium；Raw materials of compound containing B is H3BO3Or B2O3；Raw materials of compound containing F is
CsF、CsBF4Or NH4F。
4. a kind of fluorine boron aluminic acid caesium nonlinear optical crystal, characterized in that the chemical formula of the crystal is CsAlB3O6F, molecular weight
It is 307.32, the structure of the crystal belongs to rhombic system, and space group isPna21, cell parameter isa=8.064,b =
11.970,c=7.036,α = β = γ=90 °, unit-cell volume 679.23。
5. a kind of preparation method of fluorine boron aluminic acid caesium nonlinear optical crystal as claimed in claim 4, characterized in that including following
Step:
A, fluorine boron aluminic acid cesium compound polycrystal powder prepared by Claims 2 or 3 is packed into platinum crucible, is subsequently placed in crystal
In furnace, 750 ~ 800 DEG C are warming up to, is completely melt uniformly, to be cooled to freezing point or more rapidly later to raw material within constant temperature 10 ~ 48 hours
0.5 ~ 2 DEG C, obtain melt, wherein the freezing point is 560 DEG C；
B, seed crystal is fixed on the lower end of seed rod and is contacted with melt liquid level, be cooled to freezing point or low after preheating 1 ~ 10min
In 0.1 ~ 1 DEG C of freezing point, start to carry out crystal growth；
C, by crystal growth controller apply 2 ~ 20rpm crystalline substance turn, with 0 ~ 10 mm/ days speed lifting seed crystal, then press
The rate slow cooling of 0.1 ~ 5 DEG C/day is down to room by crystal lift-off liquid level after cooling with 10 ~ 30 DEG C/h of rate
Temperature is to get the fluorine boron aluminic acid caesium nonlinear optical crystal.
6. a kind of preparation method of fluorine boron aluminic acid caesium nonlinear optical crystal as claimed in claim 4, characterized in that including following
Step:
A, fluorine boron aluminic acid cesium compound polycrystal powder prepared by Claims 2 or 3 and fluxing agent are packed into platinum crucible, then
It is placed in crystal oven, is warming up to 600 ~ 700 DEG C, constant temperature 10 ~ 48 hours are completely melt uniformly to raw material, are cooled to rapidly later full
It is 5 ~ 10 DEG C above with point, obtain blend melt, wherein the saturation point temperature is 500 ~ 550 DEG C；
B, seed crystal is fixed on the lower end of seed rod and is contacted with blend melt liquid level, be cooled to saturation point after preheating 1 ~ 10min,
Start to carry out crystal growth；
C, turned by the crystalline substance that crystal growth controller applies 2 ~ 20rpm, then press the rate slow cooling of 0.1 ~ 5 DEG C/day, cooling
After by crystal lift-off liquid level, it is non-linear to get the fluorine boron aluminic acid caesium that room temperature is down to 10 ~ 30 DEG C/h of rate
Optical crystal.
7. a kind of preparation method of fluorine boron aluminic acid caesium nonlinear optical crystal as claimed in claim 6, characterized in that described fluxing
Agent is B2O3、H3BO3、CsF、(NH4)2AlF6One or both of mixture；The fluorine boron aluminic acid cesium compound polycrystal powder
The molar ratio of end and fluxing agent is 1: 0.3 ~ 3；The crystalline size that the preparation method obtains is greater than 3.0 mm.
8. the purposes of fluorine boron aluminic acid caesium nonlinear optical crystal described in a kind of claim 4, characterized in that the crystal for pair
Wavelength is that the laser beam of 1064 nm generates the harmonic wave light output of 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication or 6 frequencys multiplication.
9. the purposes of fluorine boron aluminic acid caesium nonlinear optical crystal described in a kind of claim 4, characterized in that the crystal is for deep
Harmonic oscillator, optical parameter and the amplifying device or fiber waveguide device of ultra-violet (UV) band.
10. the purposes of fluorine boron aluminic acid caesium nonlinear optical crystal described in a kind of claim 4, characterized in that the crystal is used for
The optical parameter and amplifying device of outskirt from infrared to dark purple.
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| CN110725004A (en) * | 2019-12-05 | 2020-01-24 | 河北大学 | Cesium rubidium fluoroboroaluminate nonlinear optical crystal and preparation method and application thereof |
| CN113046822A (en) * | 2021-04-01 | 2021-06-29 | 河北大学 | Rubidium aluminum fluoborate nonlinear optical crystal and preparation method and application thereof |
| CN114108085A (en) * | 2021-11-10 | 2022-03-01 | 河北大学 | Barium fluoborate aluminate second-order nonlinear optical crystal and preparation method and application thereof |
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| CN113046822A (en) * | 2021-04-01 | 2021-06-29 | 河北大学 | Rubidium aluminum fluoborate nonlinear optical crystal and preparation method and application thereof |
| CN114108085A (en) * | 2021-11-10 | 2022-03-01 | 河北大学 | Barium fluoborate aluminate second-order nonlinear optical crystal and preparation method and application thereof |
| CN114108085B (en) * | 2021-11-10 | 2022-08-19 | 河北大学 | Barium borofluoride aluminate second-order nonlinear optical crystal and preparation method and application thereof |
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