CN108588833A - Compound fluoboric acid calcium and fluoroboric acid calcium non-linear optical crystal and preparation method and purposes - Google Patents
Compound fluoboric acid calcium and fluoroboric acid calcium non-linear optical crystal and preparation method and purposes Download PDFInfo
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- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C30B11/06—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt at least one but not all components of the crystal composition being added
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Abstract
The chemical formula of a kind of compound fluoboric acid calcium of present invention offer and fluoroboric acid calcium non-linear optical crystal and preparation method and purposes, the compound is CaB5O7F3, molecular weight 263.13 is made of solid-phase synthesis or Vacuum Package method；The chemical formula of the crystal is CaB5O7F3, molecular weight 263.13 belongs to rhombic system, and space group isCmc21, cell parameter isa=9.926 (10),b=8.400 (8),c=7.966 (8),α=β=γ=90 °, unit-cell volume is 664.2 (11)3, the frequency-doubled effect of crystal is about KH2PO4 (KDP) 2 times, ultraviolet absorption edge is shorter than 190nm, using melt method, high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method grow crystal, the chemical stability of the crystal is good, can be used as ultraviolet, deep ultraviolet nonlinear optical crystal and is applied in all solid state laser.
Description
Technical field
The present invention relates to a kind of compound fluoboric acid calcium CaB5O7F3With fluoboric acid calcium CaB5O7F3Nonlinear optical crystal and
Preparation method and purposes.
Background technology
Deep ultraviolet nonlinear optical crystal can utilize its frequency conversion property to turn the laser of the wave bands such as near-infrared, visible
It changes the deep ultraviolet laser that wavelength is less than 200nm into, there is significant application value in fields such as medical treatment, communication, scientific researches.Many institutes
Known, the deep ultraviolet nonlinear optical crystal of currently the only functionization is the KBe of China scientist invention2BO3F2(KBBF) brilliant
Body, the crystal have layer growth habit, and growing large-size crystal is difficult, limits its application to a certain extent.Therefore it prepares
The novel deep ultraviolet nonlinear optical crystal material of synthesis excellent combination property is of great significance and practical value.
The present invention has invented compound ammonium fluoroborate NH in research before this4B4O6F and ammonium fluoroborate NH4B4O6F is non-thread
Property optical crystal (number of patent application 201611128283.3), compound fluoboric acid rubidium and fluoboric acid rubidium nonlinear optical crystal and
Preparation method and purposes (number of patent application 201710215347.1), compound fluoboric acid caesium and fluoboric acid caesium non-linear optical crystal
Body and preparation method and purposes (number of patent application 201710215337.8) compound sodium fluoborate and sodium fluoborate birefringence are brilliant
Body and preparation method and purposes (number of patent application 201610932882.4), compound fluoboric acid caesium rubidium and fluoboric acid caesium rubidium are non-thread
Property optical crystal and preparation method and purposes (number of patent application 201710845438.3) and compound fluoboric acid caesium potassium and fluorine
Six related patents of boric acid caesium nonlinear optical crystal of potassium and preparation method and purposes (number of patent application 201710845730.5).
Present invention main distinction of six patents with more than is, fluoboric acid calcium CaB5O7F3Middle Ca ions and boron-oxygen anionic framework with
Ca-O ions are keyed, and the bonding active force of structure is different, causes structure and habit entirely different, fluoboric acid calcium
CaB5O7F3It can grow at enclosed system or stablize in open system and grow, growth technique key parameter and crystallographic
It can be different from the first six crystal.
Invention content
Present invention aims at provide a kind of compound fluoboric acid calcium, the chemical formula of the compound is CaB5O7F3, molecule
Amount is 263.13, is prepared using solid reaction process or Vacuum Package method.
It is a further object of the invention to provide fluoboric acid calcium CaB5O7F3Nonlinear optical crystal, the chemistry of the crystal
Formula is CaB5O7F3, molecular weight 263.13.Its crystal structure belongs to rhombic system, space group Cmc21, cell parameter is α=β=γ=90 °, unit-cell volume are
Further object of the present invention is, provides fluoboric acid calcium CaB5O7F3The preparation method of nonlinear optical crystal uses
Melt method, high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method grow crystal.
Another object of the present invention is, provides fluoboric acid calcium CaB5O7F3The purposes of nonlinear optical crystal.
The chemical formula of a kind of compound fluoboric acid calcium of the present invention, the compound is CaB5O7F3, molecular weight is
263.13, it is made of solid-phase synthesis or Vacuum Package method.
The preparation method of the compound fluoboric acid calcium, is made, concrete operations of solid-phase synthesis or Vacuum Package method
It follows these steps to carry out：
The solid-phase synthesis prepare compound fluoboric acid calcium：
Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into platinum
Golden crucible is placed in Muffle furnace and is warming up to 350-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3, wherein institute
It is CaF to state compound containing Ca2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is H3BO3、
B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
The Vacuum Package method prepare compound fluoboric acid calcium：
Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into stone
Ying Guanzhong vacuumizes quartz ampoule, and vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, with 5-10 DEG C of temperature/
The rate of h is warming up to 350-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3, wherein the compound containing Ca
For CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is H3BO3、B2O3、Ca(BF4)2；
It is compound CaF containing F2Or Ca (BF4)2。
The chemical formula of a kind of fluoroboric acid calcium non-linear optical crystal, the crystal is CaB5O7F3, molecular weight 263.13 belongs to
Rhombic system, space group Cmc21, cell parameter is
α=β=γ=90 °, unit-cell volume are
The preparation method of the fluoroboric acid calcium non-linear optical crystal, using melt method, high temperature solution method, Vacuum Package
Method, hydro-thermal method or solution at room temperature method grow crystal；
The concrete operations of the melt method for growing fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into
Platinum crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder
End, wherein the compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy
For H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for preparing step a5O7F3Polycrystal powder is packed into platinum crucible, is placed in Muffle furnace, is warming up to
550-750 DEG C, constant temperature 10-120 hours obtains blend melt；
C, the blend melt that step b is obtained is slowly dropped to 350 DEG C with the rate of 0.1-2 DEG C/h, then with 5-10 DEG C/h's
Rate fast cooling obtains CaB to room temperature5O7F3Seed crystal；
D, crystal is grown in compound melt using czochralski method：The obtained seed crystals of step c are fixed on seed rod, from
Seed crystal under the top of blend melt made from step b, the crystalline substance for applying 2-20rpm by crystal growth controller turns, with 1-10mm/
It speed lifts seed crystal, while being cooled down with the rate of 0.1-10 DEG C/h, to get to CaB after crystal growth stopping5O7F3It is non-
Linear optical crystal；
Or crystal is grown in compound melt with kyropoulos：The obtained seed crystals of step c are fixed on seed rod, from step
Seed crystal under the top of melt made from rapid b, is cooled down with the rate of 0.1-10 DEG C/h, makes crystal growth 5-15 hours, is slowly promoted
Crystal, continued growth so repeat, to get to CaB after crystal growth stopping5O7F3Nonlinear optical crystal；
Or crystal is grown in compound melt with Bridgman-Stockbarger method：The step c seed crystals prepared are placed on crucible bottom, then
Compound CaB prepared by step a5O7F3Polycrystalline is put into crucible, then seals platinum crucible, and growth furnace temperature is risen to
550-750 DEG C, constant temperature 10-120 hours, adjustment bushing position keeps seed crystal micro- molten, then reduces earthenware with 1-10mm/ days speed
Crucible, meanwhile, keep growth temperature constant, or 350 DEG C are down to the rate of temperature fall of 3 DEG C/h of prestissimo temperature, end to be grown
Afterwards, then with the rate of 5-10 DEG C/h room temperature is quickly down to get to CaB5O7F3Nonlinear optical crystal；
The concrete operations of the high temperature solution method growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into
Platinum crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder
End, wherein the compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy
For H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3Polycrystal powder 1: 0.1-6 is uniformly mixed in molar ratio with fluxing agent,
It is reloaded into platinum crucible, is warming up to 550-750 DEG C, constant temperature 5-120 hours obtains mixed molten liquid, wherein the cosolvent is
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, are slowly dropped with the rate of 0.1-2 DEG C/h
To 350 DEG C, then with the rate fast cooling of 5-10 DEG C/h CaB is obtained to room temperature5O7F3Seed crystal；
D, crystal is grown：The obtained seed crystals of step c are fixed on seed rod, the mixed molten liquid made from the step b it is upper
The lower seed crystal in side, the crystalline substance for applying 2-20rpm by crystal growth controller are turned, are cooled down with the rate of 0.1-3 DEG C/h of temperature, wait for crystal
Growth stop after to get to CaB5O7F3Nonlinear optical crystal；
The concrete operations of the Vacuum Package method growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into
Platinum crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder
End, wherein the compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy
For H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3Polycrystal powder 0-1: 0.1-6 mixes in molar ratio with fluxing agent
It is even, it is fitted into quartz ampoule, elevated-temperature seal is placed in Muffle furnace, is warming up to 550-700 DEG C, constant temperature 5-120 hours, then with temperature
The rate of 0.1-3 DEG C/h of degree is cooled to 350 DEG C, then with the rate fast cooling of 5-10 DEG C/h of temperature to room temperature to get to
CaB5O7F3Nonlinear optical crystal, wherein the cosolvent is H3BO3, B2O3, PbO or PbF2；
The concrete operations of the Hydrothermal Growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into
Platinum crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder
End, wherein the compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy
For H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3It is dissolved in polycrystal powder merging deionized water, by endless fully dissolved
Mixture makes it be sufficiently mixed dissolving in temperature 60 C ultrasonication, with HF and Ca (OH)2Adjusting pH value is 8-11；
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 reaction kettle screwing hermetic；
D, autoclave is placed in insulating box, is warming up to 150-350 DEG C, constant temperature 5-8 days, then with temperature 5-20
The rate of temperature fall of DEG C/day is down to room temperature to get to CaB5O7F3Nonlinear optical crystal；
The concrete operations of the solution at room temperature method growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into
Platinum crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder
End, wherein the compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy
For H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3Polycrystal powder is put into the glass container of wash clean, and 20- is added
100mL deionized waters, then ultrasonication make to be sufficiently mixed dissolving, with HF and Ca (OH)2Adjusting pH value is 8-11, uses filter paper
Mixed solution is obtained by filtration；
C, the obtained mixed solutions of step b are placed in clean glass container, are sealed with pan paper, be placed on without shake,
It is pollution-free, without in cross-ventilated static environment, sealing is pricked into several apertures to adjust the evaporation rate of water in aqueous solution,
Stand 5-20 days at room temperature；
D, wait for that the solution in step c grows crystal grain in container bottom, until the no longer significant change of crystal grain size,
Obtain seed crystal；
E, the preferable seed crystal of quality in selection step d, is hung in mixed solution made from step b, at room temperature
Growth is stood 10-30 days to get to CaB5O7F3Nonlinear optical crystal.
The fluoroboric acid calcium non-linear optical crystal is preparing Nd:The fundamental frequency light for the 1064nm that YAG laser is exported into
The purposes of 2 frequency multiplication of row, 3 frequencys multiplication, 4 frequencys multiplication, the harmonic wave light output of 5 frequencys multiplication or 6 frequencys multiplication.
The fluoroboric acid calcium non-linear optical crystal is preparing the use in generating the deep ultraviolet frequency multiplication light output less than 200nm
On the way.
The compound fluoroboric acid calcium non-linear optical crystal is preparing times frequency generator, up or down frequency converter or light
Purposes in parametric oscillator.
Compound fluoboric acid calcium and fluoroboric acid calcium non-linear optical crystal of the present invention and preparation method and purposes, are making
Container used in the process of standby is platinum crucible, and iridium crucible, ceramic crucible, quartz ampoule, conical flask, beaker, liner is polytetrafluoro
The water heating kettle of ethylene liner or stainless steel inner lining equipped with platinum casing.When container is quartz ampoule, need to take out before sealing true
Sky avoids volatility of raw material in reaction process that quartz ampoule is made to burst.When container is conical flask or beaker, first acid must be used cleaning container
Totally, then with deionized water rinse, it dries.
Compound fluoboric acid calcium and fluoroboric acid calcium non-linear optical crystal of the present invention and preparation method and purposes,
Resistance furnace used in preparation process is Muffle furnace or drying box.
Using compound fluoboric acid calcium of the present invention and fluoroboric acid calcium non-linear optical crystal and preparation method and use
On the way, the CaB that size is Centimeter Level is obtained by this method5O7F3Nonlinear optical crystal, using large scale crucible or container, and
Extend the growth cycle of crystal, then can get corresponding large-sized nonlinear optical crystal CaB5O7F3, in the CaB5O7F3It is non-thread
Property optical crystal growing crystals easily grow up transparent no package, have the speed of growth fast, it is at low cost, be easy to get large scale crystalline substance
The advantages that body.
Using compound fluoboric acid calcium of the present invention and fluoroboric acid calcium non-linear optical crystal and preparation method and use
On the way, the large scale CaB of acquisition5O7F3Nonlinear optical crystal orients crystal blank according to the crystallography data of crystal, by institute
Angle, thickness and sectional dimension sliced crystal are needed, by the thang-kng mirror polish of crystal, you can it is used as device for non-linear optical,
The CaB5O7F3There is nonlinear optical crystal transmission region to reach dark purple outskirt, and physical and chemical performance is stablized, is not easy to deliquesce, easy to process
The advantages that with preserving.
Description of the drawings
Fig. 1 is the compounds of this invention CaB5O7F3Powder X-ray RD spectrograms；
Fig. 2 is CaB of the present invention5O7F3The structure chart of crystal；
Fig. 3 is CaB of the present invention5O7F3The fundamental diagram for the device for non-linear optical that crystal makes, wherein 1 is laser,
2 be convex lens, and 3 be CaB5O7F3Crystal, 4 be prism, and 5 be filter plate.
Specific implementation mode
The present invention is described further with reference to embodiments, it should be noted that：The present invention is not limited only to given
Embodiment, any improvement made on the basis of the present invention is all without prejudice to spirit of that invention.The raw materials used in the present invention or equipment,
Unless otherwise specified, commercial to be commercially available.
Embodiment 1
Prepare compound：
By reaction equation：2CaF2+5B2O3→2CaB5O7F3, using solid reaction process synthesis compound CaB5O7F3：
By CaF2, B2O3In molar ratio 2:5 are uniformly mixed, and are packed into platinum crucible, are placed in Muffle furnace and are warming up to 600 DEG C, perseverance
Temperature 48 hours is to get to compound CaB5O7F3。
Embodiment 2
Prepare compound：
By reaction equation：2CaF2+10H3BO3→2CaB5O7F3+15H2O synthesizes compound using solid reaction process
CaB5O7F3：
By CaF2, H3BO3In molar ratio 1:5 are uniformly mixed, and are packed into platinum crucible, are placed in Muffle furnace and are warming up to 650 DEG C,
Constant temperature 24 hours is to get to compound CaB5O7F3。
Embodiment 3
Prepare compound：
By reaction equation：14Ca(OH)2+5Ca(BF4)2→2CaB5O7F3+17CaF2+14H2O is synthesized using solid reaction process
Compound CaB5O7F3：
By Ca (OH)2, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are packed into platinum crucible, are placed in Muffle furnace and are warming up to
350 DEG C, constant temperature 120 hours is to get to compound CaB5O7F3。
Embodiment 4
Prepare compound：
By reaction equation：14Ca(HCO3)2+5Ca(BF4)2→2CaB5O7F3+17CaF2+14H2O+28CO2, anti-using solid phase
Answer method synthesis compound CaB5O7F3：
By Ca (HCO3)2, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are packed into platinum crucible, are placed in Muffle furnace and heat up
To 550 DEG C, constant temperature 72 hours is to get to compound CaB5O7F3。
Embodiment 5
Prepare compound：
By reaction equation：14CaCO3+5Ca(BF4)2→2CaB5O7F3+17CaF2+14CO2, using solid reaction process synthesisization
Close object CaB5O7F3：
By CaCO3, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are packed into platinum crucible, are placed in Muffle furnace and are warming up to
600 DEG C, constant temperature 72 hours is to get to compound CaB5O7F3。
Embodiment 6
Prepare compound：
By reaction equation：14Ca(NO3)2+5Ca(BF4)2→2CaB5O7F3+17CaF2+14N2O5, closed using solid reaction process
At compound CaB5O7F3：
By Ca (NO3)2, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are packed into platinum crucible, are placed in Muffle furnace and heat up
To 650 DEG C, constant temperature 72 hours is to get to compound CaB5O7F3。
Embodiment 7
Prepare compound：
By reaction equation：2CaF2+5B2O3→2CaB5O7F3, using Vacuum Package method synthesis compound CaB5O7F3：
By CaF2, B2O3In molar ratio 2:5 are uniformly mixed, and are fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, very
Reciprocal of duty cycle reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, and 650 DEG C are warming up to the rate of 10 DEG C/h, constant temperature 24 hours,
Obtain compound CaB5O7F3。
Embodiment 8
Prepare compound：
By reaction equation：2CaF2+10H3BO3→2CaB5O7F3+15H2O synthesizes compound using Vacuum Package method
CaB5O7F3：
By CaF2, B2O3In molar ratio 1:5 are uniformly mixed, and are fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, very
Reciprocal of duty cycle reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, and 500 DEG C are warming up to the rate of 5 DEG C/h, constant temperature 72 hours,
Obtain compound CaB5O7F3。
Embodiment 9
Prepare compound：
By reaction equation：14Ca(OH)2+5Ca(BF4)2→2CaB5O7F3+17CaF2+14H2O is synthesized using Vacuum Package method
Compound CaB5O7F3：
By Ca (OH)2, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are fitted into the quartz ampoule of Φ 40mm, quartz ampoule is taken out
Vacuum, vacuum degree reach 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 350 DEG C with the rate of 8 DEG C/h, constant temperature
72 hours to get to compound CaB5O7F3。
Embodiment 10
Prepare compound：
By reaction equation：14Ca(HCO3)2+5Ca(BF4)2→2CaB5O7F3+17CaF2+14H2O+28CO2, using vacuum seal
Dress method synthesizes compound CaB5O7F3：
By Ca (HCO3)2, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are fitted into the quartz ampoule of Φ 40mm, by quartz ampoule
It vacuumizes, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 600 DEG C with the rate of 5 DEG C/h, perseverance
Temperature 96 hours is to get to compound CaB5O7F3。
Embodiment 11
Prepare compound：
By reaction equation：14CaCO3+5Ca(BF4)2→2CaB5O7F3+17CaF2+14CO2, using Vacuum Package method synthesisization
Close object CaB5O7F3：
By CaCO3, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are fitted into the quartz ampoule of Φ 40mm, quartz ampoule are taken out true
Sky, vacuum degree reach 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 650 DEG C with the rate of 10 DEG C/h, constant temperature
120 hours to get to compound CaB5O7F3。
Embodiment 12
Prepare compound：
By reaction equation：14Ca(NO3)2+5Ca(BF4)2→2CaB5O7F3+17CaF2+14N2O5, closed using Vacuum Package method
At compound CaB5O7F3：
By Ca (NO3)2, Ca (BF4)2In molar ratio 14:5 are uniformly mixed, and are fitted into the quartz ampoule of Φ 40mm, by quartz ampoule
It vacuumizes, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 580 DEG C with the rate of 5 DEG C/h, perseverance
Temperature 96 hours is to get to compound CaB5O7F3。
Embodiment 13
Solution method grows CaB5O7F3Nonlinear optical crystal：
The conjunction object CaB prepared according to embodiment 15O7F3Polycrystal powder is packed into platinum crucible, is placed in Muffle furnace, is warming up to
750 DEG C, constant temperature 10 hours obtains blend melt；
Obtained blend melt is slowly dropped to 350 DEG C with the rate temperature of 0.1 DEG C/h, then quick with the rate of 5 DEG C/h
It is cooled to room temperature, obtains CaB5O7F3Seed crystal；
Using Czochralski grown crystal：Obtained seed crystal is fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top, the crystalline substance for applying 2rpm by crystal growth controller turn, and seed crystal are lifted with 1mm/ days speed, with 0.1 DEG C/h
Rate cooling, after crystal growth stopping after to get to size be 18mm × 15mm × 11mm CaB5O7F3Non-linear optical crystal
Body.
Embodiment 13
Solution method grows CaB5O7F3Nonlinear optical crystal：
The conjunction object CaB prepared according to embodiment 35O7F3Polycrystal powder is packed into platinum crucible, is placed in Muffle furnace, is warming up to
550 DEG C, constant temperature 120 hours obtains blend melt；
Obtained blend melt is slowly dropped to 350 DEG C with the rate temperature of 2 DEG C/h, then with the fast prompt drop of the rate of 10 DEG C/h
It warms to room temperature, obtains CaB5O7F3Seed crystal；
Using Czochralski grown crystal：Obtained seed crystal is fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top, the crystalline substance for applying 20rpm by crystal growth controller turn, and seed crystal are lifted with 10mm/ days speed, with temperature 10
DEG C/cooling of the rate of h, to get to the CaB that size is 18mm × 15mm × 13mm after crystal growth stopping5O7F3Nonlinear optical
Learn crystal.
Embodiment 14
Melt method for growing CaB5O7F3Nonlinear optical crystal：
The conjunction object CaB prepared according to embodiment 25O7F3Polycrystal powder is packed into platinum crucible, is placed in Muffle furnace, is warming up to
700 DEG C, constant temperature 100 hours obtains blend melt；
Obtained blend melt is slowly dropped to 350 DEG C with the rate temperature of 1.5 DEG C/h, then quick with the rate of 8 DEG C/h
It is cooled to room temperature, obtains CaB5O7F3Seed crystal；
Crystal is grown using kyropoulos：Obtained seed crystal is fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top is cooled down with the rate of 0.1 DEG C/h, makes crystal growth 5 hours, is slowly promoted crystal but is not departed from liquid level, continues
Growth is so repeated 3 times to get the CaB to size for 15mm × 15mm × 10mm5O7F3Nonlinear optical crystal.
Embodiment 15
Melt method for growing CaB5O7F3Nonlinear optical crystal：
The conjunction object CaB prepared according to embodiment 45O7F3Polycrystal powder is packed into platinum crucible, is placed in Muffle furnace, is warming up to
700 DEG C, constant temperature 24 hours obtains blend melt；
Obtained blend melt is slowly dropped to 350 DEG C with the rate temperature of 1 DEG C/h, then with the fast prompt drop of the rate of 6 DEG C/h
It warms to room temperature, obtains CaB5O7F3Seed crystal；
Crystal is grown using kyropoulos：Obtained seed crystal is fixed on seed rod, from equipped with blend melt obtained
Seed crystal under top is cooled down with the rate of 10 DEG C/h, makes crystal growth 15 hours, is slowly promoted crystal but is not departed from liquid level, continues
Growth is so repeated 3 times to get the CaB to size for 20mm × 19mm × 16mm5O7F3Nonlinear optical crystal.
Embodiment 16
Melt method for growing CaB5O7F3Nonlinear optical crystal：
The conjunction object CaB prepared according to embodiment 55O7F3Polycrystal powder is packed into platinum crucible, is warming up to 700 DEG C, constant temperature 10 is small
When, obtain blend melt；
Obtained blend melt is slowly dropped to 350 DEG C with the rate temperature of 2 DEG C/h, then with the fast prompt drop of the rate of 5 DEG C/h
It warms to room temperature, obtains CaB5O7F3Seed crystal；
Crystal is grown in compound melt using Bridgman-Stockbarger method：Obtained seed crystal is placed on crucible bottom, then will be real
Apply the compound CaB of the preparation of example 55O7F3Polycrystal powder is put into crucible, then seals platinum crucible, will grow furnace temperature liter
To 750 DEG C, constant temperature 10 hours, adjustment bushing position keeps seed crystal micro- molten, then crucible is reduced with 1mm/ days speed, with 3 DEG C/h
Rate of temperature fall be down to 350 DEG C, after to be grown, then room temperature is quickly down to the rate of 10 DEG C/h and is to get to size
The CaB of 16mm × 15mm × 13mm5O7F3Nonlinear optical crystal.
Embodiment 17
Melt method for growing CaB5O7F3Nonlinear optical crystal：
The conjunction object CaB prepared according to embodiment 65O7F3Polycrystal powder is packed into platinum crucible, is warming up to 730 DEG C, constant temperature 60 is small
When, obtain blend melt；
Obtained blend melt is slowly dropped to 350 DEG C with the rate temperature of 1.5 DEG C/h, then quick with the rate of 5 DEG C/h
It is cooled to room temperature, obtains CaB5O7F3Seed crystal；
Crystal is grown in compound melt using Bridgman-Stockbarger method：Obtained seed crystal is placed on crucible bottom, then will be real
Apply the compound CaB of the preparation of example 65O7F3Polycrystal powder is put into crucible, then seals platinum crucible, will grow furnace temperature liter
To 550 DEG C, constant temperature 120 hours, adjustment bushing position keeps seed crystal micro- molten, then reduces crucible with 10mm/ days speed, meanwhile,
Keep growth temperature it is constant, after to be grown, then with the rate of 10 DEG C/h be quickly down to room temperature to get to size be 13mm ×
The CaB of 10mm × 9mm5O7F3Nonlinear optical crystal.
Embodiment 18
High temperature solution method grows CaB5O7F3Nonlinear optical crystal：
The conjunction object CaB prepared according to embodiment 85O7F3Polycrystal powder and fluxing agent B2O3It is uniformly mixed at 1: 0.1 in molar ratio,
It is fitted into platinum crucible, is warming up to 750 DEG C, constant temperature 5 hours obtains mixed molten liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 350 DEG C are slowly dropped to the rate of 0.1 DEG C/h, then
With the rate fast cooling of 5 DEG C/h to room temperature, CaB is obtained5O7F3Seed crystal；
Grow crystal：Obtained seed crystal is fixed on seed rod, from seed crystal under the top equipped with mixed molten liquid obtained,
The crystalline substance for applying 2rpm by crystal growth controller turns, and is cooled down with the rate of 0.1 DEG C/h, after crystal growth stopping to get to
Size is the CaB of 18mm × 15mm × 14mm5O7F3Nonlinear optical crystal.
Embodiment 19
High temperature solution method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 95O7F3Polycrystal powder and fluxing agent H3BO31: 6 mixing in molar ratio
Uniformly, it is fitted into platinum crucible, is warming up to 730 DEG C, constant temperature 52 hours obtains mixed molten liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 350 DEG C are slowly dropped to the rate of 1 DEG C/h, then with
The rate fast cooling of 8 DEG C/h obtains CaB to room temperature5O7F3Seed crystal；
Grow crystal：Obtained seed crystal is fixed on seed rod, from seed crystal under the top equipped with mixed molten liquid obtained,
The crystalline substance for applying 10rpm by crystal growth controller turns, and is cooled down with the rate of 1 DEG C/h, to get to ruler after crystal growth stopping
The very little CaB for 14mm × 12mm × 10mm5O7F3Nonlinear optical crystal.
Embodiment 20
High temperature solution method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 105O7F3Polycrystal powder mixes at 1: 4 in molar ratio with fluxing agent PbO
Uniformly, it is fitted into platinum crucible, is warming up to 600 DEG C, constant temperature 5 hours obtains mixed molten liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 350 DEG C are slowly dropped to the rate of 1.5 DEG C/h, then
With the rate fast cooling of 10 DEG C/h to room temperature, CaB is obtained5O7F3Seed crystal；
Grow crystal：Obtained seed crystal is fixed on seed rod, from seed crystal under the top equipped with mixed molten liquid obtained,
The crystalline substance for applying 10rpm by crystal growth controller turns, and is cooled down with the rate of 1 DEG C/h, to get to ruler after crystal growth stopping
The very little CaB for 15mm × 15mm × 10mm5O7F3Nonlinear optical crystal.
Embodiment 21
High temperature solution method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 115O7F3Polycrystal powder and fluxing agent PbF21: 3 is mixed in molar ratio
It closes uniformly, is reloaded into platinum crucible, is warming up to 600 DEG C, constant temperature 120 hours obtains mixed molten liquid；
Prepare seed crystal：Obtained mixed molten liquid is placed in single crystal growing furnace, 350 DEG C are slowly dropped to the rate of 2 DEG C/h, then with
The rate fast cooling of 10 DEG C/h obtains CaB to room temperature5O7F3Seed crystal；
Grow crystal：Obtained seed crystal is fixed on seed rod, from seed crystal under the top equipped with mixed molten liquid obtained,
The crystalline substance for applying 15rpm by crystal growth controller turns, and is cooled down with the rate of 0.2 DEG C/h, after crystal growth stopping to get to
Size is the CaB of 20mm × 19mm × 16mm5O7F3Nonlinear optical crystal.
Embodiment 22
Vacuum Package method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 115O7F3Polycrystal powder is fitted into the quartz ampoule of Φ 40mm, by stone
English pipe vacuumizes, and vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed in Muffle furnace, are warming up to 650 DEG C, constant temperature 5 hours, so
Be cooled to 350 DEG C afterwards with the rate of 0.1 DEG C/h, then with the rate fast cooling of 8 DEG C/h to room temperature to get to size be 4mm ×
The CaB of 4mm × 2mm5O7F3Nonlinear optical crystal.
Embodiment 23
Vacuum Package method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 15O7F3Polycrystal powder and cosolvent H3BO3In molar ratio 1:6 mixing
Uniformly, it is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed on horse
Not in stove, 550 DEG C are warming up to, then constant temperature 50 hours is cooled to 350 DEG C with the rate of 2 DEG C/h, then fast with the rate of 10 DEG C/h
Prompt drop warms to room temperature to get the CaB to size for 3mm × 3mm × 2mm5O7F3Nonlinear optical crystal.
Embodiment 24
Vacuum Package method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 15O7F3Polycrystal powder and cosolvent B2O3In molar ratio 1:1 mixing
Uniformly, it is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed on horse
Not in stove, 705 DEG C are warming up to, then constant temperature 120 hours is cooled to 350 DEG C with the rate of 1 DEG C/h, then fast with the rate of 8 DEG C/h
Prompt drop warms to room temperature to get the CaB to size for 4mm × 3mm × 2mm5O7F3Nonlinear optical crystal.
Embodiment 25
Vacuum Package method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 15O7F3Polycrystal powder and cosolvent PbO in molar ratio 1:2 mixing
Uniformly, it is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed on horse
Not in stove, 600 DEG C are warming up to, then constant temperature 48 hours is cooled to 350 DEG C with the rate of 1.5 DEG C/h, then with the rate of 5 DEG C/h
Fast cooling is to room temperature to get the CaB to size for 5mm × 3mm × 2mm5O7F3Nonlinear optical crystal.
Embodiment 26
Vacuum Package method grows CaB5O7F3Nonlinear optical crystal：
The compound CaB being prepared according to embodiment 15O7F3Polycrystal powder and cosolvent PbF2In molar ratio 1:4 mixing
Uniformly, it is fitted into the quartz ampoule of Φ 40mm, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, elevated-temperature seal are placed on horse
Not in stove, 580 DEG C are warming up to, then constant temperature 96 hours is cooled to 350 DEG C with the rate of 0.2 DEG C/h, then with the rate of 5 DEG C/h
Fast cooling is to room temperature to get the CaB to size for 6mm × 5mm × 4mm5O7F3Nonlinear optical crystal.
Embodiment 27
Hydrothermal Growth fluoroboric acid calcium non-linear optical crystal：
The compound CaB being prepared according to embodiment 45O7F3It is dissolved in polycrystal powder merging deionized water, it will be incomplete
The mixture of dissolving makes it be sufficiently mixed dissolving in temperature 60 C ultrasonication；With HF and Ca (OH)2It is 8 to adjust pH value；
Obtained mixed solution is transferred in the liner for the autoclave that clean, free of contamination volume is 100mL, and
By reaction kettle screwing hermetic；
Autoclave is placed in insulating box, is warming up to 150 DEG C, constant temperature 8 days, then dropped with the rate of temperature fall of 5 DEG C/day
To room temperature；Obtain the CaB that size is 3mm × 2mm × 1mm5O7F3Nonlinear optical crystal.
Embodiment 28
Hydrothermal Growth fluoroboric acid calcium non-linear optical crystal：
The compound CaB being prepared according to embodiment 85O7F3It is dissolved in polycrystal powder merging deionized water, it will be incomplete
The mixture of dissolving makes it be sufficiently mixed dissolving in temperature 60 C ultrasonication；With HF and Ca (OH)2It is 11 to adjust pH value；
Obtained mixed solution is transferred in the liner for the autoclave that clean, free of contamination volume is 100mL, and
By reaction kettle screwing hermetic；
Autoclave is placed in insulating box, is warming up to 350 DEG C, constant temperature 5 days, then with the rate of temperature fall of 20 DEG C/day
It is down to room temperature；Obtain the CaB that size is 5mm × 5mm × 3mm5O7F3Nonlinear optical crystal.
Embodiment 29
Solution at room temperature method grows fluoroboric acid calcium non-linear optical crystal
The compound CaB being prepared according to step 95O7F3Polycrystal powder is put into the glass container of wash clean, is added
20mL deionized waters, then ultrasonication make to be sufficiently mixed dissolving, with HF and Ca (OH)2It is 8 to adjust solution ph, uses filter paper
Mixed solution is obtained by filtration；
Obtained mixed solution is placed in clean triangular flask, is sealed with pan paper, is placed on without shaking, pollution-free, nothing
In cross-ventilated static environment, sealing is pricked into several apertures to adjust the evaporation rate of water in aqueous solution, at room temperature
Stand 5 days；
Wait for that solution grows crystal grain in container bottom, until the no longer significant change of crystal grain size, obtains seed crystal；
The preferable seed crystal of quality is selected, is hung in mixed solution obtained, stands growth at room temperature 30 days i.e.
The CaB that size is 10mm × 8mm × 6mm can be obtained5O7F3Nonlinear optical crystal.
Embodiment 30
Solution at room temperature method grows fluoroboric acid calcium non-linear optical crystal
The compound CaB being prepared according to step 105O7F3Polycrystal powder is put into the glass container of wash clean, is added
100mL deionized waters, then ultrasonication make to be sufficiently mixed dissolving, with HF and Ca (OH)2It is 11 to adjust solution ph, with filter
Solution is obtained by filtration in paper；
Obtained solution is placed in clean triangular flask, is sealed with pan paper, be placed on without shake, it is pollution-free, without air
In the static environment of convection current, sealing is pricked into several apertures to adjust the evaporation rate of water in aqueous solution, stands 5 at room temperature
It；
Wait for that solution grows crystal grain in container bottom, until the no longer significant change of crystal grain size, obtains seed crystal；
The preferable seed crystal of quality is selected, is hung in mixed solution obtained, stands growth at room temperature 10 days i.e.
The CaB that size is 5mm × 4mm × 3mm can be obtained5O7F3Nonlinear optical crystal.
Embodiment 31
By the arbitrary CaB obtained by embodiment 1-305O7F3Crystal is placed in 3 by the direction processing that matches by shown in attached drawing 3
Position on, at room temperature, with adjust Q-Nd:YAG laser makees light source, incident wavelength 1064nm, by adjusting Q-Nd:YAG laser
Device 1 sends out the infrared beam 2 that wavelength is 1064nm and injects CaB5O7F3Monocrystalline 3, generation wavelength is the green frequency doubled light of 532nm, defeated
Go out 2 times that intensity is about equal conditions KDP.
Embodiment 32
By the arbitrary CaB obtained by embodiment 1-305O7F3Crystal is placed in 3 by the direction processing that matches by shown in attached drawing 3
Position on, adjust Q Nd:YAG laser makees light source, and it is 532nm to send out wavelength by frequency-doubling crystal, injects CaB5O7F3Monocrystalline,
Generation wavelength is the frequency doubled light of 266nm, and output intensity is about 0.4 times of equal conditions BBO.
Embodiment 33
By the arbitrary CaB obtained by embodiment 1-305O7F3Crystal is placed in 3 by the direction processing that matches by shown in attached drawing 3
Position on, with incident wavelength be 1064nm and light beam that the laser of 532nm and the wavelength that takes place frequently out are 355nm at room temperature,
Inject CaB5O7F3The deep ultraviolet frequency multiplication light output that wavelength is 177.3nm can be observed in monocrystalline.
Claims (7)
1. a kind of compound fluoboric acid calcium, it is characterised in that the chemical formula of the compound is CaB5O7F3, molecular weight 263.13,
It is made of solid-phase synthesis or Vacuum Package method.
2. a kind of preparation method of compound fluoboric acid calcium as described in claim 1, it is characterised in that use solid-phase synthesis
Or Vacuum Package method is made, concrete operations follow these steps to carry out：
The solid-phase synthesis prepare compound fluoboric acid calcium：
Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into platinum earthenware
Crucible is placed in Muffle furnace and is warming up to 350-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3, wherein described contain
Ca compounds are CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is H3BO3、B2O3、
Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
The Vacuum Package method prepare compound fluoboric acid calcium：
Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into quartz ampoule
In, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10−3Pa, elevated-temperature seal are placed in Muffle furnace, with 5-10 DEG C/h's of temperature
Rate is warming up to 350-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3, wherein the compound containing Ca is
CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is H3BO3、B2O3、Ca(BF4)2；Containing F
For compound CaF2Or Ca (BF4)2。
3. a kind of fluoroboric acid calcium non-linear optical crystal, it is characterised in that the chemical formula of the crystal is CaB5O7F3, molecular weight is
263.13, belong to rhombic system, space group isCmc21, cell parameter isa =9.926 (10),b =8.400 (8),c =
7.966 (8),α= β = γ =90 °, unit-cell volume is 664.2 (11)3。
4. a kind of preparation method of fluoroboric acid calcium non-linear optical crystal as claimed in claim 3, it is characterised in that using molten
Body method, high temperature solution method, Vacuum Package method, hydro-thermal method or solution at room temperature method grow crystal；
The concrete operations of the melt method for growing fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into platinum
Crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder,
The wherein described compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is
H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for preparing step a5O7F3Polycrystal powder is packed into platinum crucible, is placed in Muffle furnace, is warming up to 550-
750 DEG C, constant temperature 10-120 hours obtains blend melt；
C, the blend melt that step b is obtained is slowly dropped to 350 DEG C with the rate of 0.1-2 DEG C/h, then with the rate of 5-10 DEG C/h
Fast cooling obtains CaB to room temperature5O7F3Seed crystal；
D, crystal is grown in compound melt using czochralski method：The obtained seed crystals of step c are fixed on seed rod, from step
Seed crystal under the top of blend melt made from b, the crystalline substance for applying 2-20rpm by crystal growth controller turns, with 1-10 mm/ days
Speed lift seed crystal, while being cooled down with the rate of 0.1-10 DEG C/h, to get to CaB after crystal growth stopping5O7F3It is non-thread
Property optical crystal；
Or crystal is grown in compound melt with kyropoulos：The obtained seed crystals of step c are fixed on seed rod, from step b
Seed crystal under the top of melt obtained is cooled down with the rate of 0.1-10 DEG C/h, makes crystal growth 5-15 hours, is slowly promoted brilliant
Body, continued growth so repeat, to get to CaB after crystal growth stopping5O7F3Nonlinear optical crystal；
Or crystal is grown in compound melt with Bridgman-Stockbarger method：The step c seed crystals prepared are placed on crucible bottom, then will step
Compound CaB prepared by rapid a5O7F3Polycrystalline is put into crucible, then seals platinum crucible, and growth furnace temperature is risen to 550-
750 DEG C, constant temperature 10-120 hours, adjustment bushing position keeps seed crystal micro- molten, then reduces crucible with the speed of 1-10 mm/ days, together
When, keep growth temperature constant, or 350 DEG C, after to be grown are down to the rate of temperature fall of 3 DEG C/h of prestissimo temperature, then
Room temperature is quickly down to get to CaB with the rate of 5-10 DEG C/h5O7F3Nonlinear optical crystal；
The concrete operations of the high temperature solution method growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into platinum
Crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder,
The wherein described compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is
H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3Polycrystal powder 1: 0.1-6 is uniformly mixed in molar ratio with fluxing agent, is refilled
Enter in platinum crucible, be warming up to 550-750 DEG C, constant temperature 5-120 hours obtains mixed molten liquid, wherein the cosolvent is 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, 350 are slowly dropped to the rate of 0.1-2 DEG C/h
DEG C, then CaB is obtained to room temperature with the rate fast cooling of 5-10 DEG C/h5O7F3Seed crystal；
D, crystal is grown：The obtained seed crystals of step c are fixed on seed rod, under the top of mixed molten liquid made from step b
Seed crystal, the crystalline substance for applying 2-20rpm by crystal growth controller are turned, are cooled down with the rate of 0.1-3 DEG C/h of temperature, wait for crystal growth
To get to CaB after stopping5O7F3Nonlinear optical crystal；
The concrete operations of the Vacuum Package method growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into platinum
Crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder,
The wherein described compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is
H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3Polycrystal powder 0-1: 0.1-6 is uniformly mixed in molar ratio with fluxing agent, dress
Enter in quartz ampoule, elevated-temperature seal is placed in Muffle furnace, is warming up to 550-700 DEG C, constant temperature 5-120 hours, then with temperature
The rate of 0.1-3 DEG C/h is cooled to 350 DEG C, then with the rate fast cooling of 5-10 DEG C/h of temperature to room temperature to get to CaB5O7F3
Nonlinear optical crystal, wherein the cosolvent is H3BO3, B2O3, PbO or PbF2；
The concrete operations of the Hydrothermal Growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into platinum
Crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder,
The wherein described compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is
H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3It is dissolved in polycrystal powder merging deionized water, by the mixing of endless fully dissolved
Object makes it be sufficiently mixed dissolving in temperature 60 C ultrasonication, with HF and Ca (OH)2Adjusting pH value is 8-11；
C, step b obtained mixed solutions are transferred to the liner for the autoclave that clean, free of contamination volume is 100 mL
In, and by reaction kettle screwing hermetic；
D, autoclave is placed in insulating box, is warming up to 150-350 DEG C, constant temperature 5-8 days, then with 5-20 DEG C/day of temperature
Rate of temperature fall be down to room temperature to get to CaB5O7F3Nonlinear optical crystal；
The concrete operations of the solution at room temperature method growth fluoroboric acid calcium non-linear optical crystal follow these steps to carry out：
A, Ca compounds, boride alloy and compound containing F will be contained to be uniformly mixed at Ca: B: F=1: 5: 3 in molar ratio, be packed into platinum
Crucible is placed in Muffle furnace and is warming up to 500-650 DEG C, and constant temperature 24-120 hours is to get to compound CaB5O7F3Polycrystal powder,
The wherein described compound containing Ca is CaF2、Ca(OH)2、CaCO3、Ca(NO3)2、Ca(HCO3)2Or Ca (BF4)2；Boride alloy is
H3BO3、B2O3、Ca(BF4)2；It is compound CaF containing F2Or Ca (BF4)2；
B, the compound CaB for obtaining step a5O7F3Polycrystal powder is put into the glass container of wash clean, and 20-100mL is added and goes
Ionized water, then ultrasonication make to be sufficiently mixed dissolving, with HF and Ca (OH)2Adjusting pH value is 8-11, is filtered with filter paper
To mixed solution；
C, the obtained mixed solutions of step b are placed in clean glass container, are sealed with pan paper, is placed on without shaking, without dirt
It contaminates, without in cross-ventilated static environment, sealing is pricked into several apertures to adjust the evaporation rate of water in aqueous solution, in room
Temperature is lower to stand 5-20 days；
D, wait for that the solution in step c grows crystal grain in container bottom, until the no longer significant change of crystal grain size, obtains
Seed crystal；
E, the preferable seed crystal of quality in selection step d, is hung in mixed solution made from step b, is stood at room temperature
Growth 10-30 days is to get to CaB5O7F3Nonlinear optical crystal.
5. a kind of fluoroboric acid calcium non-linear optical crystal as claimed in claim 3 is preparing Nd:What YAG laser was exported
The fundamental frequency light of 1064nm carries out the purposes of 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 fluoroboric acid calcium non-linear optical crystal as claimed in claim 3 is preparing the deep ultraviolet generated less than 200nm
Purposes in frequency multiplication light output.
7. a kind of compound fluoroboric acid calcium non-linear optical crystal as claimed in claim 3 prepare times frequency generator, it is upper or
Purposes in lower frequency converter or optical parametric oscillator.
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