CN107628629A - Compound fluoboric acid caesium rubidium and fluoboric acid caesium rubidium nonlinear optical crystal and preparation method and purposes - Google Patents
Compound fluoboric acid caesium rubidium and fluoboric acid caesium rubidium nonlinear optical crystal and preparation method and purposes Download PDFInfo
- Publication number
- CN107628629A CN107628629A CN201710845438.3A CN201710845438A CN107628629A CN 107628629 A CN107628629 A CN 107628629A CN 201710845438 A CN201710845438 A CN 201710845438A CN 107628629 A CN107628629 A CN 107628629A
- Authority
- CN
- China
- Prior art keywords
- crystal
- compound
- csrbb
- compound containing
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Glass Compositions (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention provides a kind of compound fluoboric acid caesium rubidium and fluoboric acid caesium rubidium nonlinear optical crystal and preparation method and purposes, and the chemical formula of the compound is CsRbB8O12F2, molecular weight 534.86, it is made of solid-phase synthesis or Vacuum Package method.The chemical formula of the crystal is CsRbB8O12F2, molecular weight 534.86 belongs to hexagonal crystal system, and space group isP‑62c, cell parameter isa=b=6.5878,c=7.813,α=β=90 °,γ=120 °, unit-cell volume 293.63.The frequency-doubled effect of the crystal is about KH2PO4 (KDP) 2 times, the nm of ultraviolet absorption edge 150 200.CsRbB8O12F2Using high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method growth crystal, the crystal not deliquescence in atmosphere, chemical stability is good, can be applied as ultraviolet, deep ultraviolet nonlinear optical crystal in all solid state laser.
Description
Technical field
The present invention relates to a kind of compound fluoboric acid caesium rubidium CsRbB8O12F2With fluoboric acid caesium rubidium CsRbB8O12F2Nonlinear optical
Learn crystal and preparation method and purposes.
Background technology
Deep ultraviolet (λ<200nm) non-linear optical crystal material is to obtain deep ultraviolet laser based on nonlinear optical effect
Main Means, the working range of all solid state laser can greatly be promoted.By semicentennial research, it has been found that a series of
The nonlinear optical crystal of excellent performance.The representational nonlinear optical crystal of visible light wave range has KTiOPO4(KTP),
KH2PO4(KDP) etc..In ultraviolet band, the nonlinear optical crystal LiB of industrialization3O5(LBO)、CsB3O5(CBO)、
CsLiB6O10And BaB (CLBO)2O4(BBO) etc..But in below 200nm deep ultraviolet band, practical non-linear optical crystal
Body only has KBe2BO3F2(KBBF).Due to the crystal growth cycles are long, containing hypertoxic Be elements, layer growth habit etc., necessarily
Its application is limited in degree.Therefore, it is that extremely have must to explore the new deep ultraviolet nonlinear optical crystal with premium properties
Want.
In research before, existing compound ammonium fluoroborate NH4B4O6F and ammonium fluoroborate NH4B4O6F non-linear optical crystals
Body (number of patent application 201611128283.3), and compound fluoboric acid caesium and fluoboric acid caesium nonlinear optical crystal and preparation
Two Patents of method and purposes (number of patent application 201710215337.8).The present invention and ammonium fluoroborate NH4B4O6F and fluorine
Boric acid caesium CsB4O6The F main distinction is, compound CsRbB of the present invention8O12F2Belong to hexagonal crystal system, space group is
P-62c, molecular formula and crystal structure are entirely different.In addition, habit, growth technique key parameter, crystal is linearly and non-thread
Property optical property etc. is different from the above two.The simple isomorphism that the compound is not belonging to known compound is replaced.
The content of the invention
Present invention aims at, there is provided a kind of compound fluoboric acid caesium rubidium, the chemical formula of the compound is CsRbB8O12F2,
Molecular weight is 534.86, is prepared using solid reaction process or Vacuum Package method.
It is a further object of the invention to provide fluoboric acid caesium rubidium CsRbB8O12F2Nonlinear optical crystal, the crystal
Chemical formula be CsRbB8O12F2, molecular weight 534.86, crystal category hexagonal crystal system, space group P-62c, cell parameter is α=β=90 °, γ=120 °, unit-cell volume are
Further object of the present invention is, there is provided fluoboric acid caesium rubidium CsRbB8O12F2The preparation side of nonlinear optical crystal
Method, using high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method growth crystal.
Another object of the present invention is, there is provided fluoboric acid caesium rubidium CsRbB8O12F2The purposes of nonlinear optical crystal.
A kind of compound fluoboric acid caesium rubidium of the present invention, the chemical formula of the compound is CsRbB8O12F2, molecular weight
For 534.86, the compound is crystal structure.
The preparation method of the compound fluoboric acid caesium rubidium, using solid-phase synthesis or Vacuum Package method prepare compound,
Concrete operations follow these steps to carry out：
The solid-phase synthesis prepare compound fluoboric acid caesium rubidium：
Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2 will be contained:
0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature 3-
96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、
CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Containing B
Compound is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、
RbBF4Or CsBF4；
The Vacuum Package method prepare compound fluoboric acid caesium rubidium：
Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2 will be contained:
0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into Φ 40mm quartz ampoule, quartz ampoule is vacuumized, vacuum reaches 1 × 10- 3Pa, flame is sealed under high temperature, is put into Muffle furnace, and 350-600 DEG C is warming up to 10-50 DEG C of speed, constant temperature 3-96 hours,
Obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、
CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Containing B
Compound is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、
RbBF4Or CsBF4。
A kind of fluoboric acid caesium rubidium nonlinear optical crystal, the chemical formula of the crystal is CsRbB8O12F2, molecular weight is
534.86, crystal category hexagonal crystal system, space group P-62c, cell parameter isα=β
=90 °, γ=120 °, unit-cell volume is
The preparation method of the fluoboric acid caesium rubidium nonlinear optical crystal, using high temperature solution method, Vacuum Package method, hydro-thermal
Method or solution at room temperature method growth crystal；
The high temperature solution method grows fluoboric acid caesium rubidium nonlinear optical crystal, follows these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5- will be contained
2: 0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature
3-96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、
CsOH、CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or
RbBF4；Boride alloy is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、
RbF、HF、HBF4、RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder 1: 0.1-0.5 mixes in molar ratio with fluxing agent
Uniformly, it is reloaded into clean platinum crucible, is warming up to 400-700 DEG C with 35-45 DEG C/h of temperature speed, constant temperature 7-15 is small
When, mixed molten liquid is obtained, wherein fluxing agent is LiF, NaF, KF, RbF, CsF, H3BO3、B2O3, PbO or PbF2；
C, seed crystal is prepared：The obtained mixed molten liquids of step b are placed in single crystal growing furnace, then cooled with 0.1-5 DEG C/h of temperature
Speed is down to 350-610 DEG C, and 300-385 DEG C, then the drop with 3-10 DEG C/h of temperature are cooled to 0.2-0.6 DEG C/h of temperature speed
Warm speed is down to 30 DEG C, obtains CsRbB8O12F2Seed crystal；
D, crystal is grown：The CsRbB that step c is obtained8O12F2Seed crystal is fixed on seed rod, from equipped with mixed molten liquid
At the top of crystal growing furnace under seed rod, to mixed molten liquid ullage 1mm, 10-25 minutes will be preheated, then make seed crystal with mixing
Liquation liquid level contacts, and is cooled to crystal growth with 0.1-2 DEG C/h of temperature speed and terminates, by crystal lift-off mixed molten liquid surface,
30 DEG C are cooled to 3-10 DEG C/h of temperature speed again, that is, obtains CsRbB8O12F2Nonlinear optical crystal；
The concrete operations of the Vacuum Package method growth fluoboric acid caesium rubidium nonlinear optical crystal follow these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5- will be contained
2: 0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature
3-96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、
CsOH、CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or
RbBF4；Boride alloy is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、
RbF、HF、HBF4、RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder and fluxing agent are LiF, NaF, KF, RbF, CsF,
H3BO3、B2O3, PbO or PbF21: 0.1-1 it is well mixed, is reloaded into quartz ampoule in molar ratio, quartz ampoule is vacuumized, vacuum
Degree reaches 1 × 10-3Pa, with flame gun Vacuum Package, it is put into Muffle furnace, 400- is warming up to 10-50 DEG C/h of temperature speed
700 DEG C, constant temperature 3-96 hours, be then cooled to 330-450 DEG C with the speed of 0.5-1.5 DEG C/day of temperature, then with 2-5 DEG C of temperature/
H speed is down to 30 DEG C, cuts quartz ampoule, that is, obtains CsRbB8O12F2Nonlinear optical crystal；
The concrete operations of the Hydrothermal Growth fluoboric acid caesium rubidium nonlinear optical crystal follow these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5- will be contained
2: 0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature
3-96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、
CsOH、CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or
RbBF4；Boride alloy is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、
RbF、HF、HBF4、RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder, insert in 5-30mL deionized waters and dissolve, will not
Ultrasonication 5-30 minute of the mixture being completely dissolved at 20-50 DEG C of temperature makes it be sufficiently mixed dissolving；
C, the obtained mixed solutions of step b are transferred in the autoclave that clean, free of contamination volume is 100mL
In lining, and by reactor screwing hermetic；
D, autoclave is placed in insulating box, is warming up to 150-500 DEG C with 5-50 DEG C/h of temperature speed, constant temperature
3-15 days, then room temperature is down to the rate of temperature fall of 5-30 DEG C/day of temperature, that is, obtain CsRbB8O12F2Nonlinear optical crystal；
The concrete operations of the solution at room temperature method growth fluoboric acid caesium rubidium nonlinear optical crystal follow these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5- will be contained
2: 0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature
3-96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、
CsOH、CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or
RbBF4；Boride alloy is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、
RbF、HF、HBF4、RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder, it is put into the glass container of wash clean, adds
20-100mL deionized water, then ultrasonication 5-60 minutes, it is sufficiently mixed dissolving, then add HF regulation solution
PH value 1-11；
C, the container that solution is housed in step b is sealed with pan paper, is placed on nothing and rocks, be pollution-free, without cross-ventilated
In static environment, it is 0.2-2mL/ days that sealing is pricked into aperture by evaporation rate control, stands 5-20 days at room temperature；
D, treat that the solution in step c grows crystal grain in container bottom, until the no longer significant change of crystal grain size,
Growth terminates, and obtains seed crystal；
E, by surplus solution qualitative filter paper by other contaminant filters in crystal grain and solution, the preferable seed of quality is selected
Crystalline substance, seed crystal is fixed with platinum wire, hung in the solution after filtering, it is 0.2- that sealing is pricked into aperture by evaporation rate control
2mL/ days, growth 10-30 days are stood at room temperature, you can obtain CsRbB8O12F2Nonlinear optical crystal.
The fluoboric acid caesium rubidium nonlinear optical crystal is preparing Nd:The fundamental frequency light for the 1064nm that YAG laser is exported
Carry out the purposes in the harmonic wave light output of 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication or 6 frequencys multiplication.
The fluoboric acid caesium rubidium nonlinear optical crystal is in the deep ultraviolet frequency multiplication light output for producing 150-200nm is prepared
Purposes.
The 7 compound fluoboric acid caesium rubidium nonlinear optical crystals are preparing times frequency generator, up or down frequency converter
Or the purposes in optical parametric oscillator.
The preparation method of fluoboric acid caesium rubidium nonlinear optical crystal of the present invention, is being prepared used in mixed solution
Compound CsRbB8O12F2Polycrystal powder, it can also be replaced with the raw material directly weighed, Cs compounds, chemical combination containing Rb will be contained
Thing, boride alloy and compound containing F Cs: Rb: B: F=0.5-2: 0.5-2: 3-10: 0.5-2 are weighed and mixed in molar ratio
Even, the compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、CH3COOCs, CsF or CsBF4；Compound containing Rb is
Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Boride alloy is H3BO3、B2O3、K2B2O4.3H2O、
KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、RbBF4Or CsBF4。
The preparation method of fluoboric acid caesium rubidium nonlinear optical crystal of the present invention, container used is in preparation process
Platinum crucible, iridium crucible, ceramic crucible, quartz ampoule, conical flask, beaker, liner is for polytetrafluoroethyllining lining or equipped with platinum set
The water heating kettle of the stainless steel inner lining of pipe；When container is quartz ampoule, needs to vacuumize before sealing, avoid raw material in course of reaction
Volatilization bursts quartz ampoule；, must be first clean by cleaning container with acid when container is conical flask or beaker, then moistened with deionized water
Wash, dry.
The preparation method of fluoboric acid caesium rubidium nonlinear optical crystal of the present invention, the resistance furnace used in preparation process
For Muffle furnace or drying box.
Use the method for the invention to obtain size as the fluoboric acid caesium rubidium nonlinear optical crystal of Centimeter Level, use big chi
Very little crucible or container, and extend the growth cycle of crystal, then it can obtain corresponding large-sized CsRbB8O12F2Non-linear optical crystal
Body, in the CsRbB8O12F2The growing crystals of nonlinear optical crystal are easily grown up transparent no parcel, have that the speed of growth is fast, into
This is low, the advantages that being readily available large-size crystals.
Using the preparation method of fluoboric acid caesium rubidium nonlinear optical crystal of the present invention, the large scale of acquisition
CsRbB8O12F2Nonlinear optical crystal, according to the crystallography data of crystal, crystal blank is oriented, by required angle, thickness
With sectional dimension sliced crystal, by the thang-kng mirror polish of crystal, you can used as device for non-linear optical, the CsRbB8O12F2
Nonlinear optical crystal has wider transmission region, and physical and chemical performance is stable, and mechanical hardness is big, not easily broken and deliquescence, is easy to
The advantages that cutting, polishing and preservation.
Brief description of the drawings
Fig. 1 is the compounds of this invention CsRbB8O12F2Powder X-ray RD spectrograms, spectrogram is consistent with theoretical XRD spectrum, it was demonstrated that
Compound CsRbB8O12F2Presence；
Fig. 2 is CsRbB of the present invention8O12F2The structure chart of crystal；
Fig. 3 is CsRbB of the present invention8O12F2The fundamental diagram for the device for non-linear optical that crystal makes, wherein 1 is laser
Device, 2 is send light beam, and 3 be CsRbB8O12F2Crystal, 4 be outgoing beam, and 5 be filter plate.
Embodiment
The present invention is described further, it is necessary to which explanation is with reference to embodiments, the present invention is not limited only to be enumerated
The embodiment gone out, all without prejudice to spirit of the invention, the present invention is raw materials used or sets for any improvement made on the basis of the present invention
It is standby, it is unless otherwise specified, commercial to be commercially available.
Embodiment 1
Prepare compound：
By reaction equation：CsF+RbF+4B2O3→CsRbB8O12F2, compound CsRbB is synthesized using solid-phase synthesis8O12F2：
By CsF, RbF, B2O3In molar ratio 1:1:4 is well mixed, loads the platinum that clean, free of contamination volume is 28mL
In crucible, Muffle furnace is then placed in, 450 DEG C is warming up to, constant temperature 96 hours, that is, obtains compound CsRbB8O12F2Polycrystal powder.
Embodiment 2
Prepare compound：
By reaction equation：CsF+RbF+8H3BO3→CsRbB8O12F2+12H2O ↑, compound is synthesized using solid reaction process
CsRbB8O12F2：
By CsF, RbF, H3BO3In molar ratio 1:1:4 is well mixed, loads the platinum that clean, free of contamination volume is 28mL
In crucible, Muffle furnace is then placed in, 500 DEG C is warming up to, constant temperature 3 hours, that is, obtains compound CsRbB8O12F2Polycrystal powder.
Embodiment 3
Prepare compound：
By reaction equation：CsF+RbBF4+4B2O3→CsRbB8O12F2+BF3↑, compound is synthesized using Vacuum Package method
CsRbB8O12F2：
By CsF, RbBF4, B2O3In molar ratio 1:1:2 is well mixed, is fitted into Φ 40mm quartz ampoule, quartz ampoule is taken out
Vacuum, vacuum reach 1 × 10-3Pa, flame gun Vacuum Package is used under high temperature, is put into Muffle furnace, heated up with 50 DEG C of speed
To 350 DEG C, constant temperature 96 hours, temperature opens quartz ampoule after being down to room temperature, that is, obtains compound CsRbB8O12F2Polycrystal powder.
Embodiment 4
Prepare compound：
By reaction equation：CsBF4+RbF+4B2O3→CsRbB8O12F2+BF3↑, compound is synthesized using Vacuum Package method
CsRbB8O12F2：
By CsBF4, RbF, B2O3In molar ratio 1:2:5 is well mixed, is fitted into Φ 40mm quartz ampoule, quartz ampoule is taken out
Vacuum, vacuum reach 1 × 10-3Pa, flame gun Vacuum Package is used under high temperature, is put into Muffle furnace, heated up with 10 DEG C of speed
To 400 DEG C, constant temperature 96 hours, temperature opens quartz ampoule after being down to room temperature, that is, obtains compound CsRbB8O12F2Polycrystal powder.
Embodiment 5
Prepare compound：
By reaction equation：CsBF4+RbBF4+4B2O3→CsRbB8O12F2+2BF3↑, compound is synthesized using solid reaction process
CsRbB8O12F2：
By CsBF4, RbBF4And B2O3In molar ratio 1:2:3 is well mixed, loads platinum crucible, is placed in Muffle furnace, rises
Temperature constant temperature 56 hours, that is, obtains compound CsRbB to 450 DEG C8O12F2Polycrystal powder.
Embodiment 6
Prepare compound：
By reaction equation：3CsNO3+3RbOH+12B2O3+6NH4F=3CsRbB8O12F2+12H2O↑+4N2↑+NH3↑, using true
Empty package method synthesis compound CsRbB8O12F2：
By CsNO3, RbOH, B2O3And NH4F in molar ratio 1.5:1.5:6:2 is well mixed, loads Φ 40mm quartz ampoule
In, quartz ampoule is vacuumized, vacuum reaches 1 × 10-3Pa, flame seals under high temperature, is put into Muffle furnace, with 30 DEG C of speed
350 DEG C are warming up to, constant temperature 90 hours, that is, obtains compound CsRbB8O12F2Polycrystal powder.
Embodiment 7
Prepare compound：
By reaction equation：Cs2CO3+2RbOH+16H3BO3+4NH4F=2CsRbB8O12F2+27H2O↑+4NH3↑+CO2↑, use
Solid reaction process synthesis compound CsRbB8O12F2：
By Cs2CO3,RbOH,H3BO3And NH4F in molar ratio 0.5:1:8:2 is well mixed, loads platinum crucible, is placed in horse
Not in stove, 460 DEG C are warming up to, constant temperature 96 hours, that is, obtains compound CsRbB8O12F2Polycrystal powder.
Embodiment 8
High temperature solution method synthesizes CsRbB8O12F2Nonlinear optical crystal：
The compound CsRbB that embodiment 1 is obtained8O12F2Polycrystal powder is that CsF is mixed at 1: 0.1 in molar ratio with fluxing agent
Uniformly, it is reloaded into clean platinum crucible, is warming up to 400 DEG C with 35 DEG C/h of temperature speed, constant temperature 7 hours, is mixed
Liquation；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 350 DEG C are cooled to 0.1 DEG C/h of temperature speed,
300 DEG C are cooled to 0.2 DEG C/h of temperature speed, then 30 DEG C are down to 3 DEG C/h of temperature speed, obtains CsRbB8O12F2Seed
It is brilliant；
Grow crystal：The CsRbB that will be obtained8O12F2Seed crystal is fixed on seed rod, from equipped with obtained mixed molten liquid
Seed crystal is dropped into mixed molten liquid ullage 1mm at the top of crystal growing furnace, preheats 10 minutes, then makes seed crystal and mixed molten liquid
Liquid level contacts, and is cooled to crystal growth with 0.1 DEG C/h of temperature speed and terminates, and proposes the crystal on seed rod, then with 3 DEG C/h's
Speed is down to 30 DEG C, that is, obtains the CsRbB that size is 12mm × 13mm × 16mm8O12F2Nonlinear optical crystal.
Embodiment 9
High temperature solution method synthesizes CsRbB8O12F2Nonlinear optical crystal：
The compound CsRbB that embodiment 2 is obtained8O12F 2Polycrystal powder and fluxing agent are PbF21: 0.5 is mixed in molar ratio
Close, be reloaded into clean platinum crucible, be warming up to 700 DEG C with temperature 45 C/h speed, constant temperature 15 hours, it is molten to obtain mixing
Liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 610 DEG C are cooled to 5 DEG C/h of temperature speed, with
0.6 DEG C/h of temperature speed is cooled to 385 DEG C, then is down to 30 DEG C with 10 DEG C/h of temperature speed, obtains CsRbB8O12F2Crystal
Seed crystal；
Grow crystal：The CsRbB that will be obtained8O12F2Seed crystal is fixed on seed rod, from equipped with obtained mixed molten liquid
Seed crystal is dropped into mixed molten liquid ullage 1mm at the top of crystal growing furnace, preheats 25 minutes, then makes seed crystal and mixed molten liquid
Liquid level contacts, and is cooled to crystal growth with 2 DEG C/h of temperature speed and terminates, and proposes the crystal on seed rod, then with 10 DEG C of temperature/
H speed is down to 30 DEG C, that is, obtains the CsRbB that size is 15mm × 17mm × 18mm8O12F2Nonlinear optical crystal.
Embodiment 10
High temperature solution method synthesizes CsRbB8O12F2Nonlinear optical crystal：
The compound CsRbB that embodiment 3 is obtained8O12F2Polycrystal powder and fluxing agent are B2O31: 0.5 mixing in molar ratio
Uniformly, it is fitted into clean platinum crucible, is warming up to 690 DEG C with 40 DEG C/h of temperature speed, constant temperature 10 hours, it is molten to obtain mixing
Liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 580 DEG C are cooled to 3 DEG C/h of temperature speed, with
0.6 DEG C/h of temperature speed is cooled to 330 DEG C, then is down to 30 DEG C with 8 DEG C/h of temperature speed, obtains CsRbB8O12F2Crystal
Seed crystal；
Grow crystal：The CsRbB that will be obtained8O12F2Seed crystal is fixed on seed rod, from the crystal of obtained mixed molten liquid
Seed crystal is dropped into mixed molten liquid ullage 1mm at the top of growth furnace, preheats 20 minutes, then makes seed crystal and mixed molten liquid liquid level
Contact, is cooled to crystal growth with 0.3 DEG C/h of temperature speed and terminates, and the crystal on seed rod is proposed, with 8 DEG C/h of temperature speed
Rate is down to 30 DEG C, that is, obtains the CsRbB that size is 12mm × 15mm × 19mm8O12F2Nonlinear optical crystal.
Embodiment 11
High temperature solution method synthesizes CsRbB8O12F2Nonlinear optical crystal：
The compound CsRbB that embodiment 4 is obtained8O12F2Polycrystal powder is that NaF is mixed at 1: 0.2 in molar ratio with fluxing agent
Uniformly, it is fitted into clean platinum crucible, is warming up to 660 DEG C with 35 DEG C/h of temperature speed, constant temperature 8 hours, it is molten to obtain mixing
Liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 575 DEG C are cooled to 2 DEG C/h of temperature speed, with
0.2 DEG C/h of temperature speed is cooled to 380 DEG C, then is down to 30 DEG C with 7 DEG C/h of temperature speed, obtains CsRbB8O12F2Seed crystal；
Grow crystal：The CsRbB that will be obtained8O12F2Seed crystal is fixed on seed rod, from the crystal of obtained mixed molten liquid
Seed crystal is dropped into mixed molten liquid ullage 1mm at the top of growth furnace, preheats 25 minutes, then makes seed crystal and mixed molten liquid liquid level
Contact, is cooled to crystal growth with 0.1 DEG C/h of temperature speed and terminates, and the crystal on seed rod is proposed, with 7 DEG C/h of temperature speed
Rate is down to 30 DEG C, that is, obtains the CsRbB that size is 11mm × 12mm × 15mm8O12F2Nonlinear optical crystal.
Embodiment 12
High temperature solution method synthesizes CsRbB8O12F2Nonlinear optical crystal：
CsF in molar ratio:RbF:H3BO3=1:1:8 weigh raw material, are that RbF is mixed at 1: 0.4 in molar ratio with fluxing agent
It is even, it is fitted into clean platinum crucible, is warming up to 665 DEG C with 37 DEG C/h of temperature speed, constant temperature 7 hours, obtains mixed molten liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 570 DEG C are cooled to 2.4 DEG C/h of temperature speed,
385 DEG C are cooled to 0.15 DEG C/h of temperature speed, then 30 DEG C are down to 7.5 DEG C/h of temperature speed, obtains CsRbB8O12F2
Seed crystal；
Grow crystal：The CsRbB that will be obtained8O12F2Seed crystal is fixed on seed rod, from the crystal of obtained mixed molten liquid
Seed crystal is dropped into mixed molten liquid ullage 1mm at the top of growth furnace, preheats 20 minutes, then makes seed crystal and mixed molten liquid liquid level
Contact, is cooled to crystal growth with 0.15 DEG C/h of temperature speed and terminates, and proposes the crystal on seed rod, then with 7.5 DEG C of temperature/
H speed is down to 30 DEG C, that is, obtains the CsRbB that size is 13mm × 14mm × 16mm8O12F2Nonlinear optical crystal.
Embodiment 13
Vacuum Package method grows CsRbB8O12F2Crystal：
The compound CsRbB that embodiment 1 is obtained8O12F2Polycrystal powder and fluxing agent are B2O31: 0.1 mixing in molar ratio
Uniformly, it is fitted into Φ 40mm quartz ampoule, quartz ampoule is vacuumized, vacuum reaches 1 × 10-3Pa, with flame gun Vacuum Package,
It is put into Muffle furnace, is warming up to 400 DEG C with 10 DEG C/h of temperature speed, constant temperature 3 hours, then with the speed of DEG C/day of temperature 0.5
Be cooled to 330 DEG C, then 30 DEG C be down to 2 DEG C/h of temperature speed, cut quartz ampoule, that is, obtain size be 13mm × 16mm ×
21mm CsRbB8O12F2Nonlinear optical crystal.
Embodiment 14
Vacuum Package method grows CsRbB8O12F2Crystal：
The compound CsRbB that will be obtained according to embodiment 28O12F2It is that CsF is well mixed at 1: 1 in molar ratio with fluxing agent,
It is fitted into Φ 40mm quartz ampoule, quartz ampoule is vacuumized, vacuum reaches 1 × 10-3Pa, with flame gun Vacuum Package, it is put into
In Muffle furnace, 700 DEG C are warming up to temperature 50 C/h speed, constant temperature 96 hours, is then dropped with the speed of DEG C/day of temperature 1.5
Temperature is down to 30 DEG C to 450 DEG C, then with 5 DEG C/h of temperature speed, cuts quartz ampoule, that is, it is 15mm × 18mm × 23mm to obtain size
CsRbB8O12F2Nonlinear optical crystal.
Embodiment 15
Vacuum Package method grows CsRbB8O12F2Crystal：
The compound CsRbB that embodiment 3 is obtained8O12F2It is H with fluxing agent3BO31: 0.3 is well mixed in molar ratio, dress
In the quartz ampoule for entering Φ 40mm, quartz ampoule is vacuumized, vacuum reaches 1 × 10-3Pa, with flame gun Vacuum Package, it is put into horse
Not in stove, 500 DEG C are warming up to 35 DEG C/h of temperature speed, constant temperature 50 hours, is then cooled with the speed of DEG C/day of temperature 0.5
30 DEG C are down to 430 DEG C, then with 4 DEG C/h of temperature speed, cuts quartz ampoule, that is, it is 14mm × 16mm × 17mm's to obtain size
CsRbB8O12F2Nonlinear optical crystal.
Embodiment 16
Vacuum Package method grows CsRbB8O12F2Crystal：
The compound CsRbB that embodiment 4 is obtained8O12F2It is that PbO is well mixed at 1: 0.4 in molar ratio with fluxing agent, fills
In the quartz ampoule for entering Φ 40mm, quartz ampoule is vacuumized, vacuum reaches 1 × 10-3Pa, with flame gun Vacuum Package, it is put into horse
Not in stove, 520 DEG C are warming up to 32 DEG C/h of temperature speed, constant temperature 52 hours, is then cooled with the speed of DEG C/day of temperature 0.8
30 DEG C are down to 435 DEG C, then with 4.5 DEG C/h of temperature speed, cuts quartz ampoule, that is, it is 14mm × 16mm × 17mm to obtain size
CsRbB8O12F2Nonlinear optical crystal.
Embodiment 17
Vacuum Package method grows CsRbB8O12F2Crystal：
By CsF:RbF:H3BO3=1:1:8 directly weigh raw material, are PbF with fluxing agent21: 0.5 mixing is equal in molar ratio
It is even, it is fitted into Φ 40mm quartz ampoule, quartz ampoule is vacuumized, vacuum reaches 1 × 10-3Pa, with flame gun Vacuum Package, put
Enter in Muffle furnace, be warming up to 510 DEG C with 37 DEG C/h of temperature speed, constant temperature 96 hours, then with the speed of DEG C/day of temperature 1.2
Be cooled to 445 DEG C, then 30 DEG C be down to 3.5 DEG C/h of temperature speed, cut quartz ampoule, that is, obtain size be 10mm × 10mm ×
17mm CsRbB8O12F2Nonlinear optical crystal.
Embodiment 18
Solution at room temperature method synthesizes CsRbB8O12F2Nonlinear optical crystal：
The compound CsRbB that embodiment 1 is obtained8O12F2Polycrystal powder is put into the glass container of wash clean, is added
100mL deionized water, then ultrasonication 5 minutes, make it be sufficiently mixed dissolving, then add HF regulations solution ph and arrive
1；
Container equipped with solution is sealed with pan paper, nothing is placed on and rocks, be pollution-free, without cross-ventilated static environment
In, it is 2mL/ days that sealing is pricked into aperture by evaporation rate control, stands 5 days；
Treat that solution grows crystal grain in container bottom, until the no longer significant change of crystal grain size, growth terminate, obtained
To seed crystal；
By surplus solution qualitative filter paper by other contaminant filters in crystal grain and solution, the preferable seed crystal of quality is selected,
Seed crystal to be fixed with platinum wire, is hung in the solution after filtering, it is 2mL/ days that sealing is pricked into aperture by evaporation rate control,
30 days are stood at room temperature, that is, obtains the CsRbB that size is 8mm × 14mm × 17mm8O12F2Nonlinear optical crystal.
Embodiment 19
Solution at room temperature method synthesizes CsRbB8O12F2Nonlinear optical crystal：
By CsF:RbOH:B2O3:NH4F=1:1:4:0.5 directly weighs raw material, is put into the glass container of wash clean, adds
Enter 20mL deionized water, then ultrasonication 30 minutes, it is sufficiently mixed dissolving, then add HF regulation solution ph
To 11；
Container equipped with solution is sealed with pan paper, nothing is placed on and rocks, be pollution-free, without cross-ventilated static environment
In, it is 0.2mL/ days that sealing is pricked into aperture by evaporation rate control, stands 20 days；
Treat that solution grows crystal grain in container bottom, until the no longer significant change of crystal grain size, growth terminate, obtained
To seed crystal；
By surplus solution qualitative filter paper by other contaminant filters in crystal grain and solution, seed crystal is fixed with platinum wire, will
It is hung in the solution after filtering, and it is 0.2mL/ days that sealing is pricked into aperture by evaporation rate control, stands 30 days at room temperature,
Obtain the CsRbB that size is 4mm × 8mm × 9mm8O12F2Nonlinear optical crystal.
Embodiment 20
Hydro-thermal method synthesizes CsRbB8O12F2Nonlinear optical crystal：
The compound CsRbB that embodiment 1 is obtained8O12F2Polycrystal powder, insert in 5mL deionized waters and dissolve, will be endless
The mixture of fully dissolved is handled 5 minutes in the ultrasonic wave at 20 DEG C of temperature, is sufficiently mixed it；
Obtained mixed solution is transferred in the liner for the autoclave that clean, free of contamination volume is 100mL, and
By reactor screwing hermetic；
Autoclave is placed in insulating box, 500 DEG C are warming up to temperature 50 C/h speed, constant temperature 3 days, then with
The rate of temperature fall of DEG C/day of temperature 5 is down to room temperature, opens autoclave, that is, it is 8mm × 9mm × 15mm's to obtain size
CsRbB8O12F2Nonlinear optical crystal.
Embodiment 21
Hydro-thermal method synthesizes CsRbB8O12F2Nonlinear optical crystal：
By CsF:RbF:H3BO3=1:1:8 directly weigh raw material, insert in 30mL deionized waters and dissolve, by endless fully dissolved
Mixture temperature be 50 DEG C at ultrasonic wave in handle 30 minutes, be sufficiently mixed it；
Obtained mixed solution is transferred in the liner for the autoclave that clean, free of contamination volume is 100mL, and
By reactor screwing hermetic；
Autoclave is placed in insulating box, 150 DEG C are warming up to 5 DEG C/h of temperature speed, constant temperature 15 days, then with
The rate of temperature fall of DEG C/day of temperature 30 is down to room temperature, opens autoclave, that is, it is 22mm × 24mm × 27mm's to obtain size
CsRbB8O12F2Nonlinear optical crystal.
Embodiment 22
Hydro-thermal method synthesizes CsRbB8O12F2Nonlinear optical crystal：
The compound CsRbB that embodiment 2 is obtained8O12F2Polycrystal powder, insert in 8mL deionized waters and dissolve, will be endless
The mixture of fully dissolved is handled 30 minutes in the ultrasonic wave at temperature is 45 DEG C, is sufficiently mixed it；
Obtained mixture is transferred in the liner for the autoclave that clean, free of contamination volume is 100mL, and will
Reactor screwing hermetic；
Autoclave is placed in insulating box, 330 DEG C are warming up to by 40 DEG C/h of temperature speed, constant temperature 10 days, then
Room temperature is down to the rate of temperature fall of DEG C/day of temperature 8, opens autoclave, that is, it is 12mm × 18mm × 20mm's to obtain size
CsRbB8O12F2Nonlinear optical crystal.
Embodiment 23
By any CsRbB obtained by embodiment 1-228O12F2Crystal is disposed by the direction processing that matches as accompanying drawing 3 Suo Shi
On 3 position, at room temperature, with tune Q-Nd:YAG laser makees light source, incident wavelength 1064nm, by adjusting Q-Nd:YAG swashs
Light device 1 sends the infrared beam 2 that wavelength is 1064nm and injects CsRbB8O12F2Monocrystalline 3, produce the green frequency multiplication that wavelength is 532nm
Light, output intensity are about 2 times of equal conditions KDP.
Embodiment 24
By any CsRbB obtained by embodiment 1-228O12F2Crystal is disposed by the direction processing that matches as accompanying drawing 3 Suo Shi
On 3 position, at room temperature, with tune Q Nd:YAG laser makees light source, incident wavelength 532nm, by the Nd for adjusting Q:YAG swashs
Light device 1 sends the infrared beam 2 that wavelength is 532nm and injects CsRbB8O12F2Monocrystalline 3, the frequency doubled light that wavelength is 266nm is produced, it is defeated
Go out 0.5 times that intensity is about equal conditions BBO.
Embodiment 25
By any CsRbB obtained by embodiment 1-228O12F2Crystal is disposed by the direction processing that matches as accompanying drawing 3 Suo Shi
On 3 position, at room temperature, with tune Q-Nd:YAG laser makees light source, incident wavelength 355nm, by adjusting Q-Nd:YAG swashs
Light device 1 sends the infrared beam 2 that wavelength is 355nm and injects CsRbB8O12F2Monocrystalline 3, the depth that wavelength is 177.3nm can be observed
Ultraviolet frequency double light output.
Claims (7)
1. a kind of compound fluoboric acid caesium rubidium, it is characterised in that the chemical formula of the compound is CsRbB8O12F2, molecular weight is
534.86, the compound is crystal structure.
2. a kind of preparation method of compound fluoboric acid caesium rubidium as claimed in claim 1, it is characterised in that using synthesis in solid state
Method or Vacuum Package method prepare compound, concrete operations follow these steps to carry out：
The solid-phase synthesis prepare compound fluoboric acid caesium rubidium：
Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2: 0.5- will be contained
2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature 3-96 is small
When, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、
CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Containing B
Compound is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、
RbBF4Or CsBF4；
The Vacuum Package method prepare compound fluoboric acid caesium rubidium：
Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2: 0.5- will be contained
2: 3-10: 0.5-2 is well mixed, and is fitted into Φ 40mm quartz ampoule, quartz ampoule is vacuumized, vacuum reaches 1 × 10−3Pa,
Flame seals under high temperature, is put into Muffle furnace, is warming up to 350-600 DEG C with 10-50 DEG C of speed, constant temperature 3-96 hours, produces
To compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、CH3COOCs、
CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Boride alloy is
H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、RbBF4Or
CsBF4。
3. a kind of fluoboric acid caesium rubidium nonlinear optical crystal, it is characterised in that the chemical formula of the crystal is CsRbB8O12F2, molecular weight
For 534.86, crystal category hexagonal crystal system, space group isP-62c, cell parameter isa = b =6.5878,c =7.813,α= β =90 °,γ =120 °, unit-cell volume 293.63。
4. a kind of preparation method of fluoboric acid caesium rubidium nonlinear optical crystal as claimed in claim 3, it is characterised in that use
High temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method growth crystal；
The high temperature solution method grows fluoboric acid caesium rubidium nonlinear optical crystal, follows these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2 will be contained:
0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature 3-
96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、
CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Containing B
Compound is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、
RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder 1: 0.1-0.5 is well mixed in molar ratio with fluxing agent,
It is reloaded into clean platinum crucible, is warming up to 400-700 DEG C with 35-45 DEG C/h of temperature speed, constant temperature 7-15 hours, obtains
Mixed molten liquid, wherein fluxing agent are LiF, NaF, KF, RbF, CsF, H3BO3、B2O3, PbO or PbF2；
C, seed crystal is prepared：The obtained mixed molten liquids of step b are placed in single crystal growing furnace, then with temperature 0.1-5 DEG C/h rate of temperature fall
350-610 DEG C is down to, 300-385 DEG C, then the cooling speed with 3-10 DEG C/h of temperature are cooled to 0.2-0.6 DEG C/h of temperature speed
Rate is down to 30 DEG C, obtains CsRbB8O12F2Seed crystal；
D, crystal is grown：The CsRbB that step c is obtained8O12F2Seed crystal is fixed on seed rod, from the crystal equipped with mixed molten liquid
At the top of growth furnace under seed rod, to mixed molten liquid ullage 1mm, 10-25 minutes will be preheated, then make seed crystal and mixed molten liquid
Liquid level contacts, and is cooled to crystal growth with 0.1-2 DEG C/h of temperature speed and terminates, by crystal lift-off mixed molten liquid surface, then with
3-10 DEG C of temperature/h speed is cooled to 30 DEG C, that is, obtains CsRbB8O12F2Nonlinear optical crystal；
The concrete operations of the Vacuum Package method growth fluoboric acid caesium rubidium nonlinear optical crystal follow these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2 will be contained:
0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature 3-
96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、
CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Containing B
Compound is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、
RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder and fluxing agent are LiF, NaF, KF, RbF, CsF, H3BO3、
B2O3, PbO or PbF21: 0.1-1 it is well mixed, is reloaded into quartz ampoule in molar ratio, quartz ampoule is vacuumized, vacuum reaches
1×10−3Pa, with flame gun Vacuum Package, it is put into Muffle furnace, 400-700 DEG C is warming up to 10-50 DEG C/h of temperature speed,
Constant temperature 3-96 hours, 330-450 DEG C, then the speed with 2-5 DEG C/h of temperature are then cooled to the speed of 0.5-1.5 DEG C/day of temperature
Rate is down to 30 DEG C, cuts quartz ampoule, that is, obtains CsRbB8O12F2Nonlinear optical crystal；
The concrete operations of the Hydrothermal Growth fluoboric acid caesium rubidium nonlinear optical crystal follow these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2 will be contained:
0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature 3-
96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、
CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Containing B
Compound is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、
RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder, insert in 5-30mL deionized waters and dissolve, will be incomplete
Ultrasonication 5-30 minute of the mixture of dissolving at 20-50 DEG C of temperature makes it be sufficiently mixed dissolving；
Step b obtained mixed solutions are transferred to the liner for the autoclave that clean, free of contamination volume is 100mL c,
In, and by reactor screwing hermetic；
D, autoclave is placed in insulating box, is warming up to 150-500 DEG C with 5-50 DEG C/h of temperature speed, constant temperature 3-15
My god, then room temperature is down to the rate of temperature fall of 5-30 DEG C/day of temperature, that is, obtain CsRbB8O12F2Nonlinear optical crystal；
The concrete operations of the solution at room temperature method growth fluoboric acid caesium rubidium nonlinear optical crystal follow these steps to carry out：
A, Cs compounds, compound containing Rb, boride alloy and compound containing F in molar ratio Cs: Rb: B: F=0.5-2 will be contained:
0.5-2: 3-10: 0.5-2 is well mixed, and is fitted into platinum crucible, is then placed in Muffle furnace, is warming up to 350-600 DEG C, constant temperature 3-
96 hours, that is, obtain compound CsRbB8O12F2Polycrystal powder, wherein compound containing Cs is Cs2CO3、CsNO3、CsHCO3、CsOH、
CH3COOCs, CsF or CsBF4；Compound containing Rb is Rb2CO3、RbNO3、RbHCO3、RbOH、CH3COORb, RbF or RbBF4；Containing B
Compound is H3BO3、B2O3、K2B2O4.3H2O、KBF4Or CsBF4, compound containing F is NH4F、NH4HF2、CsF、RbF、HF、HBF4、
RbBF4Or CsBF4；
B, the compound CsRbB for obtaining step a8O12F2Polycrystal powder, it is put into the glass container of wash clean, adds 20-
100mL deionized water, then ultrasonication 5-60 minutes, it is sufficiently mixed dissolving, then add HF regulation pH value of solution
Value 1-11；
C, the container that solution is housed in step b is sealed with pan paper, is placed on nothing and rocks, be pollution-free, without cross-ventilated static state
In environment, it is 0.2-2mL/ days that sealing is pricked into aperture by evaporation rate control, stands 5-20 days at room temperature；
D, treat that the solution in step c grows crystal grain in container bottom, until the no longer significant change of crystal grain size, growth
Terminate, obtain seed crystal；
E, by surplus solution qualitative filter paper by other contaminant filters in crystal grain and solution, the preferable seed crystal of quality is selected, is used
Platinum wire fix seed crystal, hung on filtering after solution in, will sealing prick aperture by evaporation rate control for 0.2-2mL/
My god, growth 10-30 days are stood at room temperature, you can obtain CsRbB8O12F2Nonlinear optical crystal.
5. a kind of fluoboric acid caesium rubidium nonlinear optical crystal as claimed in claim 3 is preparing Nd:What YAG laser was exported
1064nm fundamental frequency light carries out the purposes in the harmonic wave light output of 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication or 6 frequencys multiplication.
6. a kind of fluoboric acid caesium rubidium nonlinear optical crystal as claimed in claim 3 is preparing the dark purple of generation 150-200nm
Purposes in outer frequency multiplication light output.
7. a kind of compound fluoboric acid caesium rubidium nonlinear optical crystal as claimed in claim 3 prepare times frequency generator, on
Or the purposes in lower frequency converter or optical parametric oscillator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710845438.3A CN107628629B (en) | 2017-09-19 | 2017-09-19 | Compound cesium rubidium fluoroborate, nonlinear optical crystal of cesium rubidium fluoroborate, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710845438.3A CN107628629B (en) | 2017-09-19 | 2017-09-19 | Compound cesium rubidium fluoroborate, nonlinear optical crystal of cesium rubidium fluoroborate, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107628629A true CN107628629A (en) | 2018-01-26 |
| CN107628629B CN107628629B (en) | 2020-04-10 |
Family
ID=61103233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710845438.3A Active CN107628629B (en) | 2017-09-19 | 2017-09-19 | Compound cesium rubidium fluoroborate, nonlinear optical crystal of cesium rubidium fluoroborate, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107628629B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108560044A (en) * | 2018-06-01 | 2018-09-21 | 中国科学院理化技术研究所 | For CsB4O6The double crucible and CsB of F crystal growths4O6F growing methods |
| CN109748256A (en) * | 2019-01-03 | 2019-05-14 | 新疆大学 | The preparation method and purposes of phosphoric acid rubidium lead bismuth and its nonlinear optical crystal |
| CN110725004A (en) * | 2019-12-05 | 2020-01-24 | 河北大学 | Cesium rubidium fluoroboroaluminate nonlinear optical crystal and preparation method and application thereof |
| CN111020702A (en) * | 2019-11-21 | 2020-04-17 | 新疆大学 | Rubidium barium bismuth phosphate and cesium barium bismuth phosphate compound, and preparation method and application of nonlinear optical crystal thereof |
| CN112575375A (en) * | 2019-09-30 | 2021-03-30 | 天津理工大学 | Compound cesium fluorozincate and cesium fluorozincate nonlinear optical crystal as well as preparation method and application thereof |
| CN114074944A (en) * | 2021-12-17 | 2022-02-22 | 中国科学院新疆理化技术研究所 | Compound rubidium, boron, phosphorus and oxygen nonlinear optical crystal and preparation method and application thereof |
| CN114197043A (en) * | 2021-12-15 | 2022-03-18 | 中国科学院新疆理化技术研究所 | Compound potassium cesium fluoroborate iodine, potassium cesium fluoroborate iodine nonlinear optical crystal, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS276083B6 (en) * | 1990-11-21 | 1992-03-18 | Fyzikalni Ustav Csav | Process for making visible defects on aluminium oxide-based single crystal polished surfaces |
| CN1712576A (en) * | 2004-06-25 | 2005-12-28 | 中国科学院理化技术研究所 | Non-linear optical crystal of cesium rubidium borate, its growth and use |
| CN106894085A (en) * | 2017-04-03 | 2017-06-27 | 中国科学院新疆理化技术研究所 | Compound fluoboric acid caesium and fluoboric acid caesium nonlinear optical crystal and preparation method and purposes |
-
2017
- 2017-09-19 CN CN201710845438.3A patent/CN107628629B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS276083B6 (en) * | 1990-11-21 | 1992-03-18 | Fyzikalni Ustav Csav | Process for making visible defects on aluminium oxide-based single crystal polished surfaces |
| CN1712576A (en) * | 2004-06-25 | 2005-12-28 | 中国科学院理化技术研究所 | Non-linear optical crystal of cesium rubidium borate, its growth and use |
| CN106894085A (en) * | 2017-04-03 | 2017-06-27 | 中国科学院新疆理化技术研究所 | Compound fluoboric acid caesium and fluoboric acid caesium nonlinear optical crystal and preparation method and purposes |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108560044A (en) * | 2018-06-01 | 2018-09-21 | 中国科学院理化技术研究所 | For CsB4O6The double crucible and CsB of F crystal growths4O6F growing methods |
| CN109748256A (en) * | 2019-01-03 | 2019-05-14 | 新疆大学 | The preparation method and purposes of phosphoric acid rubidium lead bismuth and its nonlinear optical crystal |
| CN109748256B (en) * | 2019-01-03 | 2023-01-10 | 新疆大学 | Rubidium-lead-bismuth phosphate and preparation method and application of nonlinear optical crystal thereof |
| CN112575375A (en) * | 2019-09-30 | 2021-03-30 | 天津理工大学 | Compound cesium fluorozincate and cesium fluorozincate nonlinear optical crystal as well as preparation method and application thereof |
| CN111020702A (en) * | 2019-11-21 | 2020-04-17 | 新疆大学 | Rubidium barium bismuth phosphate and cesium barium bismuth phosphate compound, and preparation method and application of nonlinear optical crystal thereof |
| CN110725004A (en) * | 2019-12-05 | 2020-01-24 | 河北大学 | Cesium rubidium fluoroboroaluminate nonlinear optical crystal and preparation method and application thereof |
| CN110725004B (en) * | 2019-12-05 | 2021-04-20 | 河北大学 | Cesium rubidium fluoroboroaluminate nonlinear optical crystal and preparation method and application thereof |
| CN114197043A (en) * | 2021-12-15 | 2022-03-18 | 中国科学院新疆理化技术研究所 | Compound potassium cesium fluoroborate iodine, potassium cesium fluoroborate iodine nonlinear optical crystal, preparation method and application |
| CN114197043B (en) * | 2021-12-15 | 2023-07-25 | 中国科学院新疆理化技术研究所 | Compound potassium cesium iodine fluoroborate and potassium cesium iodine fluoroborate nonlinear optical crystal, preparation method and application |
| CN114074944A (en) * | 2021-12-17 | 2022-02-22 | 中国科学院新疆理化技术研究所 | Compound rubidium, boron, phosphorus and oxygen nonlinear optical crystal and preparation method and application thereof |
| CN114074944B (en) * | 2021-12-17 | 2024-05-03 | 中国科学院新疆理化技术研究所 | Compound rubidium boron phosphorus oxygen and rubidium boron phosphorus oxygen nonlinear optical crystal, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107628629B (en) | 2020-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106894085B (en) | Compound fluoboric acid caesium and fluoboric acid caesium nonlinear optical crystal and preparation method and purposes | |
| CN107628629A (en) | Compound fluoboric acid caesium rubidium and fluoboric acid caesium rubidium nonlinear optical crystal and preparation method and purposes | |
| CN107265473B (en) | Compound fluoboric acid rubidium and fluoboric acid rubidium nonlinear optical crystal and preparation method and purposes | |
| CN107585777A (en) | Compound fluoboric acid caesium potassium and fluoboric acid caesium nonlinear optical crystal of potassium and preparation method and purposes | |
| CN108588833B (en) | Compound fluoboric acid calcium and fluoroboric acid calcium non-linear optical crystal and preparation method and purposes | |
| CN107937981B (en) | Compound fluoboric acid strontium and fluoboric acid strontium nonlinear optical crystal and preparation method and purposes | |
| CN106948003B (en) | Compound potassium fluoborate and potassium fluoborate nonlinear optical crystal and preparation method and purposes | |
| CN111334858B (en) | Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application | |
| CN101435108B (en) | Large size nonlinear optical crystal lead bromoborate preparation method | |
| CN106745022B (en) | Compound ammonium fluoroborate and ammonium fluoroborate nonlinear optical crystal and preparation method and purposes | |
| CN109680332A (en) | Compound tin boron oxygen chlorine and tin boron oxygen chlorine nonlinear optical crystal and preparation method and purposes | |
| US10564514B1 (en) | Nonlinear optical crystal of cesium fluorooxoborate, and method of preparation and use thereof | |
| CN110921676B (en) | Compound lead fluoroborate and lead fluoroborate nonlinear optical crystal, preparation method and application | |
| CN114057207B (en) | Compound sodium octadecafluoride and sodium octafluoride nonlinear optical crystal, and preparation method and application thereof | |
| CN108286072B (en) | Compound one is fluorinated sodium tetraborate and a fluorination sodium tetraborate nonlinear optical crystal and preparation method and purposes | |
| CN109748256B (en) | Rubidium-lead-bismuth phosphate and preparation method and application of nonlinear optical crystal thereof | |
| CN111139524B (en) | Potassium fluoborate, potassium fluoborate nonlinear optical crystal, preparation method and application | |
| CN104651933B (en) | Chlorine barium borate, chlorine barium borate nonlinear optical crystal, and preparation method and uses of chlorine barium borate nonlinear optical crystal | |
| CN110143610A (en) | Compound lithium potassium titanium germanate and lithium potassium titanium germanate nonlinear optical crystal and preparation method and purposes | |
| CN106192005A (en) | Compound lithium phosphate caesium nonlinear optical crystal and preparation method and purposes | |
| CN114672880A (en) | Compound rubidium fluoroborophosphate and rubidium fluoroborophosphate nonlinear optical crystal, and preparation method and application thereof | |
| CN109056065A (en) | MZnPO4The preparation method and purposes of (M=Li, K) nonlinear optical crystal | |
| CN109656079B (en) | Application of BaHgSnS4 nonlinear optical crystal | |
| CN116427031A (en) | Compound sodium fluoroborate and sodium fluoroborate nonlinear optical crystal, preparation method and application | |
| CN113913936A (en) | Compound lanthanum boron oxygen fluorine and lanthanum boron oxygen fluorine nonlinear optical crystal, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |