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 PDF

Info

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
Application number
CN201710845438.3A
Other languages
Chinese (zh)
Other versions
CN107628629B (en
Inventor
潘世烈
王颖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Technical Institute of Physics and Chemistry of CAS
Original Assignee
Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Xinjiang Technical Institute of Physics and Chemistry of CAS filed Critical Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority to CN201710845438.3A priority Critical patent/CN107628629B/en
Publication of CN107628629A publication Critical patent/CN107628629A/en
Application granted granted Critical
Publication of CN107628629B publication Critical patent/CN107628629B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

Compound fluoboric acid caesium rubidium and fluoboric acid caesium rubidium nonlinear optical crystal and preparation method And purposes
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.
CN201710845438.3A 2017-09-19 2017-09-19 Compound cesium rubidium fluoroborate, nonlinear optical crystal of cesium rubidium fluoroborate, preparation method and application Active CN107628629B (en)

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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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